TWI904243B - Resin composition, cured material, laminate, method for manufacturing cured material and semiconductor device - Google Patents

Abstract

The present invention provides a resin composition, a cured product formed by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device comprising the cured product or the laminate, wherein the resin composition comprises: compound A, having a plurality of polymerizable groups bonded by linkers having a structure having two or more directly bonded ester bonds and having a molecular weight of less than 1000; and at least one resin selected from the group consisting of cyclized resins and their precursors.

Description

Resin composition, cured material, laminate, method for manufacturing cured material and semiconductor device

This invention relates to a resin composition, a cured material, a laminate, a method for manufacturing the cured material, and a semiconductor device.

Cyclic resins such as polyimide possess excellent heat resistance and insulation properties, making them suitable for a wide range of applications. While there are no particular limitations on these applications, examples include their use as insulating films or sealing materials, or as protective films, in the practical installation of semiconductor components. Furthermore, they can also be used as base films or cover films for flexible substrates.

For example, in the above-described applications, cyclic resins such as polyimide are used in the form of resin compositions containing cyclic resins or resin compositions containing precursors of cyclic resins such as polyimide precursors. These resin compositions are applied to a substrate, for example, by coating, to form a photosensitive film. Then, exposure, development, heating, etc., are performed as needed, thereby forming a cured material on the substrate. The aforementioned cyclic resin precursors, such as polyimide precursors, are cyclized, for example, by heating, and become cyclic resins such as polyimide in the cured material. Curing resin compositions are adaptable to various applications using well-known coating methods, thus offering excellent manufacturing flexibility. For example, they allow for a high degree of design freedom in terms of shape, size, and application location. Considering this excellent manufacturing flexibility, in addition to the high performance of cyclic resins such as polyimide, there is growing anticipation for the industrial application development of these resin compositions.

For example, Patent Document 1 describes a photosensitive resin composition characterized in that, in a photosensitive resin composition in which polyamide and a triisocyanate derivative having photopolymerizable unsaturated bonds are essential components, (A) the polyamide is a polyamide having a specific structural unit, and (B) the triisocyanate derivative having a photopolymerizable unsaturated bond is a specific triisocyanate derivative, and the content of (B) relative to 100 parts by weight of (A) is 15 to 70 parts by weight. Patent document 2 describes a photosensitive resin composition capable of alkaline development, characterized by comprising, as essential components, a specific polysiloxane compound (A), at least one ester compound (B) selected from the group consisting of phthalates, trimellites, and pyromellitic esters having ethylene-containing unsaturated groups (x), a polyfunctional (meth)acrylate monomer (C), and a photoradical polymerization initiator (D).

[Patent Document 1] Japanese Patent Application Publication No. 2007-241195 [Patent Document 2] Japanese Patent Application Publication No. 2013-76791

In hardened materials composed of resins, it is desirable to improve the resolution of the obtained patterns.

The purpose of this invention is to provide a resin composition with excellent resolution of the obtained pattern, a cured product formed by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate.

Examples of representative embodiments of the present invention are shown below. <1> A resin composition comprising: compound A having a plurality of polymerizable groups bonded by linkers and having a molecular weight less than 1000, wherein the linkers have a structure in which two or more ester bonds are directly bonded to an aromatic ring; and at least one resin selected from the group consisting of cyclized resins and their precursors. <2> The resin composition as described in <1>, wherein the polymerizable groups in compound A are groups having ethylene unsaturated bonds. <3> The resin composition as described in <1> or <2>, wherein compound A is a compound represented by the following general formula (1-1). [Formula 1] In formula (1-1), ^R1 , ^R2 , and ^R3 each independently represent a monovalent organic group having a polymerizable group. <4> The resin composition described in any of <1> to <3> further contains a free radical polymerization initiator. <5> The resin composition described in any of <1> to <4>, wherein the resin contains a polyimide precursor. <6> The resin composition described in <5>, wherein the polyimide precursor has a repeating unit represented by the following formula (2), [Formula 2] In formula (2), ^A1 and ^A2 independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 independently represent a hydrogen atom or a monovalent organic group. <7> A resin composition as described in <6>, wherein at least one of ^R113 and ^R114 in formula (2) contains a free radical polymerizable group. <8> A curable resin composition as described in any one of <1> to <7>, used to form an interlayer insulating film for a redistribution layer. <9> A curable material formed by curing any one of the resin compositions described in <1> to <8>. <10> A laminate comprising two or more layers composed of the curing agent described in <9>, wherein a metal layer is included between any of the curing agent layers. <11> A method of manufacturing a curing agent, comprising a film forming step of adapting a resin composition described in any one of <1> to <8> onto a substrate to form a film. <12> A method of manufacturing a curing agent as described in <11>, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developing solution to form a pattern. <13> A method of manufacturing a curing agent as described in <11> or <12>, comprising a heating step of heating the film at a temperature of 50 to 450°C. <14> A semiconductor device comprising the curing agent described in <9> or the laminate described in <10>. [Invention Effect]

According to the present invention, a resin composition with excellent resolution of the obtained pattern can be provided, a cured product formed by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate.

The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments shown. In this specification, the numerical range indicated by the symbol “~” represents the range including the lower and upper limits of the numerical values recorded before and after the “~”, respectively. In this specification, the term “step” not only refers to an independent step, but also includes steps that cannot be clearly distinguished from other steps, as long as the expected effect of the step can be achieved. Regarding the description of group (atomic group) in this specification, the descriptions without indication of substitution and non-substitution include both unsubstituent group (atomic group) and substituent group (atomic group). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise stated, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include brightline spectra from mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation. In this specification, "(meth)acrylate" means either or both "acrylate" and "methacrylate," "(meth)acrylic acid" means either or both "acrylic acid" and "methacrylic acid," and "(meth)acrylyl" means either or both "acrylyl" and "methacrylyl." In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl in the structural formula. In this specification, total solids content refers to the total mass of all components of the composition, excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise stated, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values determined using gel osmosis chromatography (GPC) and are defined as polystyrene equivalents. In this instruction manual, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise stated, these molecular weights are determined using THF (tetrahydrofuran) as the washing solution. In cases where THF is unsuitable as a washing solution due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise stated, the detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm. In this specification, when describing the positional relationship of the layers constituting the laminate as "upper" or "lower," it is sufficient that there are other layers above or below the standard layer among the layers of interest. That is, a third layer or third element may be sandwiched between the standard layer and the other layers mentioned above, and the standard layer does not need to be in contact with the other layers. Furthermore, unless otherwise stated, the direction of gradual layering of the substrate is referred to as "up," or, in the case of a resin composition layer, the direction from the substrate towards the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Moreover, this up-down direction designation is for ease of explanation of this specification; in actual samples, the "up" direction in this specification may differ from "vertically upward." In this specification, unless otherwise stated, as components included in the composition, the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise stated, the content of each component in the composition represents the total content of all compounds corresponding to that component. Unless otherwise specified, the temperature in this specification is 23°C, the pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, the combination of preferred samples is considered a better sample.

(Resin Composition) The resin composition of the present invention comprises: compound A (hereinafter also referred to as "Compound A"), having a plurality of polymerizable groups bonded by linkers and having a molecular weight of less than 1000, wherein the linkers have a structure in which two or more ester bonds are directly bonded to an aromatic ring; and at least one resin selected from the group consisting of cyclized resins and their precursors (hereinafter also referred to as "specific resin").

The resin composition of this invention is preferably used to form a photosensitive film for exposure and development, and preferably to form a developing film for exposure and development using a developing solution containing an organic solvent. Furthermore, the resin composition of this invention is preferably used to form a photosensitive film for negative development. In this invention, negative development refers to development in which the non-exposed areas are removed by development during exposure and development, and positive development refers to development in which the exposed areas are removed by development. As the above-described exposure method, the above-described developing solution, and the above-described developing method, for example, the exposure method described in the exposure step of the description of the method for manufacturing a cured material described later, and the developing solution and developing method described in the developing step are used.

The resin composition of this invention produces patterns with excellent resolution. While the mechanism by which this effect is achieved is not yet clear, it is hypothesized as follows:

Previous methods have involved forming patterns in resin compositions containing cyclized resin precursors and polymeric compounds through exposure and development. Compound A possesses a linker group, thus exhibiting excellent compatibility with certain resins. This linker group has a structure in which two or more ester bonds are directly bonded to an aromatic ring. Therefore, it is believed that compound A and the resin are easily dispersed in a nearly uniform state in the photosensitive film, and non-image areas are easily removed by the developing solution. Furthermore, in the obtained cured product, compound A, dispersed in a nearly uniform state, forms crosslinks, thus inhibiting the penetration of solvents, etc., and exhibiting excellent chemical resistance.

Here, patent documents 1 and 2 do not describe resin compositions containing compound A and cyclized resin precursors.

The following is a detailed description of the components contained in the resin composition of the present invention.

<Compound A> The resin composition of this invention contains compound A, which has a plurality of polymerizable groups linked by linkers and has a molecular weight of less than 1000. The linkers have a structure in which two or more ester bonds are directly bonded to an aromatic ring. The molecular weight of compound A is preferably less than 1000, less than 900, and more preferably less than 800. There is no particular limitation on the lower limit of the above molecular weight; for example, it is preferred to be 200 or more.

[Polymerizable Group] The polymerizable group contained in compound A is a group capable of cross-linking reactions through the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having ethylene unsaturated bonds, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxacyclobutyl, benzoxazolyl, block isocyanate, and amino groups, with groups having ethylene unsaturated bonds being preferred. As groups possessing vinyl unsaturated bonds, examples include (meth)acryloxy, (meth)acrylamine, vinylphenyl, etc., which are groups formed by direct bonding of vinyl groups to an aromatic ring, allyl, vinyl, etc. From a reactivity perspective, (meth)acryloxy is preferred.

Compound A contains a plurality of polymerizable groups. Compound A may contain, for example, one epoxy group and one (meth)acrylic acid group, so that the total number of polymerizable groups is plurality. However, it is preferable to contain a plurality of epoxy groups or groups having ethylene unsaturated bonds, and even more preferable to contain a plurality of groups having ethylene unsaturated bonds.

The number of polymerizable groups in compound A should be 2 or more, preferably 2–15, more preferably 2–10, further preferably 2–4, and very preferably 2. The molar amount of polymerizable groups contained in 1g of compound A is preferably 2.0 mmol/g or more, more preferably 2.5 mmol/g or more, and further preferably 3.0 mmol/g or more. There is no particular upper limit to the above molar amounts, but 8.0 mmol/g or less is preferred.

[Linking Group] Compound A has a plurality of polymerizable groups linked by linking groups, wherein each linking group has a structure in which two or more ester bonds are directly bonded to an aromatic ring. That is, in compound A, a plurality of polymerizable groups are linked by linking groups, wherein each linking group has a structure in which two or more ester bonds are directly bonded to an aromatic ring.

The aforementioned linker may contain only one aromatic ring or multiple aromatic rings, with one to four being preferred, and one or two being even more preferred. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred and a benzene ring being particularly preferred. The aforementioned ester bond is preferably a carboxylic acid ester structure. Furthermore, when the aforementioned ester bond is a carboxylic acid ester structure, it is preferable that the carbon atom side of the carboxylic acid ester structure (the carbonyl side contained in the carboxylic acid ester structure) is directly bonded to the aromatic ring. It is preferable that the aforementioned ester structure is located in an adjacent position within the aromatic ring. An adjacent position refers to the position of an adjacent ring member within the aromatic ring; if the aromatic ring is a benzene ring, then it is an adjacent position. The polymerizable group can be bonded to any position in the linker, and the structure containing the polymerizable group is preferably formed by the above-mentioned ester bond and the above-mentioned aromatic ring bond. That is, it is preferable that the linker group contains a structure represented by the following formula (L-1). [Chemical Formula 3] In formula (L-1), Ar represents an aromatic ring, n represents an integer greater than 2, m represents an integer greater than 0, n+m is a number below the maximum substituent number of Ar, and * and # represent the bonding sites with other structures, respectively.

In Formula (L-1), the preferred state of Ar is the same as the preferred state of the aromatic ring described above. In Formula (L-1), n represents an integer greater than or equal to 2, with 2 to 4 being preferred and 2 being particularly preferred. In Formula (L-1), m represents an integer greater than or equal to 0, with 0 to 4 being preferred and 0 to 2 being even more preferred. In Formula (L-1), the maximum number of substituents for Ar is the number of hydrogen atoms when Ar is set as an aromatic ring without substituents, for example, 6 when Ar is a benzene ring. In Formula (L-1), * and # represent bonding sites with other structures, respectively, with * representing a preferred bonding site with a polymerizable group.

The aforementioned linker is preferably a group formed by a combination of a structure having two or more ester bonds directly bonded to the aromatic ring and a group selected from at least one group selected from the group consisting of substituted hydrocarbons, (poly)alkoxy groups, -O-, -S-, _-SO₂- , -CO-, and -NHCO-. It is even more preferred that the linker is a group formed by a combination of a structure having two or more ester bonds directly bonded to the aromatic ring and a substituted hydrocarbon. Examples of the aforementioned hydrocarbons include saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, or groups represented by combinations thereof. Saturated aliphatic hydrocarbons, aromatic hydrocarbons, or groups represented by combinations thereof are more preferred, and saturated aliphatic hydrocarbons are particularly preferred. Furthermore, halogen atoms, such as fluorine atoms, can be cited as substituents in the aforementioned hydrocarbon groups. Alkyl groups, such as ethyl, propyl, trimethylene, and butyl, can be cited as alkyl groups, with ethyl or propyl being preferred. The linking group can be divalent or higher; divalent to hexavalent links are preferred, and divalent to tetravalent links are even more preferred.

Of these, compound A is preferably represented by the following formula (1-1). [Chemical Formula 4] In equation (1-1), ^R1 , ^R2 and ^R3 each independently represent an organic group with a monovalent polymericity.

In formula (1-1), it is preferable that ^R1 , ^R2 , and ^R3 are each independently represented by the following formula (P-1). [Chemical Formula 5] In formula (P-1), ^L1 represents a linker with an n+1 valence, ^P1 represents a polymerizable group, n represents an integer greater than or equal to 1, and * represents a bonding site with the oxygen atom in formula (1-1). In formula (P-1), ^L1 can be any group described in the linker above, and the preferred state is the same. In formula (P-1), ^P1 can be any group described in the polymerizable group above, and the preferred state is the same. In formula (P-1), n is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, 1 or 2 is further preferred, and 1 is especially preferred.

Furthermore, it is preferable that the compound represented by formula (1-1) is also represented by formula (1-2). [Chemical Formula 6] In equation (1-2), ^L2 represents a single bond or a divalent linker, and ^R11 to ^R14 represent groups with polymerizable properties, respectively.

In equation (1-2), ^L2 can be a single bond or a group described in the above-mentioned connecting base, with single bond, _-CH2- , -O-, -S-, -SO2-, -CO-, -NHCO-, -C( _CF3 ) _{2- or} -C( _CH3 ) _2- being preferred. In equation (1-2), the meanings of ^R11 to ^R14 are independently the same as the meaning of ^R1 in equation (1-1), and the preferred states are also the same.

Specific examples of compound A include, but are not limited to, the following compounds. [Chemical Formula 7] 【Chemical Formula 8】

The content of compound A relative to the total solid content of the resin composition of the present invention is preferably more than 0% by mass and less than 60% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and less than 30% by mass or less is even more preferred.

<Specific Resin> The resin composition of this invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors. Preferably, the cyclized resin is a resin containing an imine ring structure or an oxazole ring structure in its backbone structure. In this invention, the backbone refers to the relatively longest bond chain in the resin molecule. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamide-imide. Cyclomeric resin precursors refer to resins that undergo chemical structural changes through external stimuli to become cyclized resins. Resins that undergo chemical structural changes through heat to become cyclized resins are preferred, and those that form a ring structure through a heat-induced ring-closing reaction are even better. Examples of cyclized resin precursors include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors. That is, the resin composition of the present invention, as a specific resin, preferably contains at least one resin (the specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. The resin composition of the present invention, as a specific resin, preferably contains polyimide or a polyimide precursor, and more preferably contains a polyimide precursor. Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups. When a particular resin possesses free radical polymerizable groups, it is preferable that the resin composition of the present invention contains the free radical polymerization initiator described later, and it is even more preferable that it contains both the free radical polymerization initiator and the free radical crosslinking agent described later. Furthermore, depending on need, it can contain the sensitizer described later. Such a resin composition of the present invention can, for example, form a negative photosensitive film. Furthermore, a particular resin may possess polar reversible groups such as acid-decomposing groups. When a particular resin possesses acid-decomposing groups, it is preferable that the resin composition of the present invention contains the photoacid generator described later. Such a resin composition of the present invention can, for example, form a chemically amplified positive or negative photosensitive film. Furthermore, it is preferable that the specific resin contains groups that can covalently bond with the polymerizable groups contained in compound A. For example, if compound A contains groups with ethylene unsaturated bonds, it is preferable that the specific resin also contains groups with ethylene unsaturated bonds. Furthermore, if compound A contains epoxy groups, it is preferable that the specific resin also contains epoxy groups. Based on the above, it is believed that cross-linking also occurs between compound A and the specific resin, further improving the chemical resistance of the obtained cured product.

[Polyimide Precursor] The type of polyimide precursor used in this invention is not specifically specified, but it is preferable to include repeating units represented by the following formula (2). [Chemical Formula 9] In formula (2), ^A1 and ^A2 represent oxygen atoms or -NH- respectively, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 represent hydrogen atoms or monovalent organic groups respectively.

In formula (2), ^A1 and ^A2 respectively represent oxygen atoms or -NH-, with oxygen atoms being preferred. In formula (2), ^R111 represents a divalent organic group. Examples of divalent organic groups include aliphatic groups, cyclic aliphatic groups, and aromatic groups that are linear or branched, preferably linear or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof, and more preferably groups that include aromatic groups with 6 to 20 carbon atoms. The aforementioned linear or branched aliphatic groups can be substituted via groups containing heteroatoms in the hydrocarbon chain, and the aforementioned cyclic aliphatic and aromatic groups can be substituted via groups containing heteroatoms in the hydrocarbon chain. As a preferred embodiment of the invention, groups represented by -Ar- and -Ar-L-Ar- are exemplified, with a particular preference for groups represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is a group comprising a single bond, an aliphatic hydrocarbon of 1 to 10 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, _-SO₂- , or -NHCO-, or a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, diamines containing aliphatic groups (2-20 carbon atoms), cyclic aliphatic groups (3-20 carbon atoms), aromatic groups (3-20 carbon atoms), or combinations thereof are preferred, and diamines containing aromatic groups (6-20 carbon atoms) are even more preferred. The linear or branched aliphatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the chain, and the cyclic aliphatic and aromatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the ring member. Examples of groups containing aromatic groups include the following.

【Chemical Formula 10】 In the formula, A represents a single bond or a divalent linker. A single bond or a group selected from aliphatic hydrocarbons of 1 to 10 carbon atoms that can be substituted with fluorine atoms, -O-, -C(=O)-, -S-, _-SO₂- , -NHCO-, or combinations thereof is preferred. A single bond, a group selected from alkyl groups of 1 to 3 carbon atoms that can be substituted with fluorine atoms, -O-, -C(=O)-, -S-, or _-SO₂- is more preferred. _-CH₂- , -O-, -S-, -SO₂-, -C( _CF₃ ) _{₂- ,} or -C( _CH₃ ) _₂- are even more preferred. * indicates a bonding site with other structures.

As a diamine, specifically, examples include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, and 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4,4'-diaminodibenzophenone or 3,3'-diaminodibenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4, 4’-Diaminobiphenyl, 3,3’-Dimethoxy-4,4’-Diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) phosphate, bis(4-amino-3-hydroxyphenyl) phosphate, 4,4’-diaminobiphenyl, 4,4’-bis(4-amino-3-hydroxyphenyl) Bis[4-(4-aminophenoxy)phenyl] benzox, bis[4-(3-aminophenoxy)phenyl] benzox, bis[4-(2-aminophenoxy)phenyl] benzox, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3’-dimethyl-4,4’-diaminodiphenyl benzox, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3’-diethyl-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane 4,4'-Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)furan, 4,4'-dimethyl-3,3'-diaminodiphenyl ether, 3,3',5,5'-tetramethyl-4, 4'-Diaminodiphenylmethane, 2,4-Diaminocumene and 2,5-Diaminocumene, 2,5-Dimethyl-p-phenylenediamine, acetoguanidine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-Trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-Diaminopyridine, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoniline, esters of diaminobenzoic acid, 1,5-Diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis... (4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethyl)phenyl The diamine selected from at least one of the following: 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfonium, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfonium, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferred.

Alternatively, a diamine having two or more alkyl diol units as described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 on the main chain may also be preferred.

From the viewpoint of the flexibility of the obtained organic membrane, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is a group including an aliphatic hydrocarbon of 1 to 10 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, _-SO₂- , or -NHCO-, or a combination of two or more of the above. Ar is preferably phenyl, and L is preferably an aliphatic hydrocarbon of 1 or 2 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, or _-SO₂- . Here, the aliphatic hydrocarbon is preferably alkyl.

Furthermore, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoints of i-ray transmittance and availability, the divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 11] In formula (51), ^R50 to ^R57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of ^R50 to ^R57 is a fluorine atom, a methyl group, or a trifluoromethyl group. *Each independently represents a bonding site with a nitrogen atom in formula (2). Examples of monovalent organic groups of ^R50 to ^R57 include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [Chemical Formula 12] In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, methyl groups, or trifluoromethyl groups, respectively, and * independently represent the bonding sites with nitrogen atoms in formula (2). Examples of diamines providing the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used.

In formula (2), R ¹¹⁵ represents a tetravalent organic group. As a tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) below is even more preferred. In formula (5) or formula (6), * independently represents the bonding site with other structures. [Chemical Formula 13] In formula (5), R ¹¹² is a single bond or a divalent linker. It is preferred to have a single bond or a group selected from aliphatic hydrocarbons with 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, -S-, -SO _2- and -NHCO-, and combinations thereof. It is even more preferred to have a single bond, a group selected from alkyl groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, -S- and SO _2- , and a divalent group selected from the group including -CH _2- , -C(CF ₃ ) _2- , -C(CH ₃ ) _2- , -O-, -CO-, -S- and -SO _2- .

Regarding R ¹¹⁵ , specifically, examples include the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. Polyimide precursors, as equivalent to R ¹¹⁵ , may contain only one type of tetracarboxylic acid dianhydride residue, or they may contain two or more types of tetracarboxylic acid dianhydride residues. It is preferred that the tetracarboxylic acid dianhydride be represented by the following formula (O). [Chemical Formula 14] In equation (O), R ¹¹⁵ represents a tetravalent organic group. The meaning of the preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in equation (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3’,4,4’-biphenyltetracarboxylic dianhydride, 3,3’,4,4’-diphenyl sulfide tetracarboxylic dianhydride, 3,3’,4,4’-diphenyl sulfide tetracarboxylic dianhydride, 3,3’,4,4’-benzophenone tetracarboxylic dianhydride, 3,3’,4,4’-diphenylmethane tetracarboxylic dianhydride, 2,2’,3,3’-diphenylmethane tetracarboxylic dianhydride, 2,3,3’,4’-biphenyltetracarboxylic dianhydride, 2,3,3’,4’-benzophenone tetracarboxylic dianhydride, 4,4’-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane. Alkane dianhydrides, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydrides, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydrides, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydrides, 1,4,5,6-naphthalenetetracarboxylic acid dianhydrides, 2,2',3,3'-diphenyltetracarboxylic acid dianhydrides, 3,4,9,10-perylenetetracarboxylic acid dianhydrides, 1,2,4,5-naphthalenetetracarboxylic acid dianhydrides, 1,4,5,8-naphthalenetetracarboxylic acid dianhydrides, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydrides, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydrides, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydrides, 1,2,3,4-benzenetetracarboxylic acid dianhydrides, and such alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

Alternatively, the tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can be cited as a better example.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may also have an OH group. More specifically, as R ¹¹¹ , the residual group of a diaminophenol derivative can be cited.

In formula (2), ^R113 and ^R114 independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferable to contain a straight-chain or branched alkyl, cyclic alkyl, aromatic, or polyalkylene alkoxy group. Furthermore, it is preferable that at least one of ^R113 and ^R114 contains a polymerizable group, and even more preferable that both contain polymerizable groups. It is also preferable that at least one of ^R113 and ^R114 contains two or more polymerizable groups. As a polymerizable group, it is a group capable of cross-linking reactions through the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxacyclobutyl, benzoxazolyl, block isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having vinyl unsaturated bonds is preferred. Examples of groups having vinyl unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl), (meth)acrylamide, (meth)acryloxy, and groups represented by formula (III) below, with groups represented by formula (III) below being preferred.

【Chemical Formula 15】

In formula (III), R ²⁰⁰ represents a hydrogen atom, methyl, ethyl, or hydroxymethyl, with a hydrogen atom or methyl being preferred. In formula (III), * indicates a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkyl group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, cycloalkyl group, or polyalkylene group. Examples of preferred R ²⁰¹ include alkyl groups such as ethyl, propyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene; 1,2-butadiyl, 1,3-butadiyl; _-CH₂CH (OH) _CH₂- ; polyalkyleneoxy; alkyl groups such as ethyl and propyl; _-CH₂CH (OH) _CH₂- ; cyclohexyl; and polyalkyleneoxy, alkyl groups such as ethyl and propyl, or polyalkyleneoxy, are even more preferred. In this invention, polyalkyleneoxy refers to a group obtained by directly bonding two or more alkyleneoxy groups. The alkyl groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkylene group contains a plurality of different penecoloxy groups, the arrangement of the penecoloxy groups in the polyalkylene group can be random, block, or alternating. It is preferable that the number of carbon atoms in the aforementioned penecoloxy group (the number of carbon atoms including the substituent when the penecoloxy group has substituents) is 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the aforementioned penecoloxy group can have substituents. Examples of preferred substituents include alkyl, aryl, and halogen atoms. Furthermore, it is preferable that the number of penecoloxy groups contained in the polyalkylene group (the repetition number of the polyalkylene group) is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethoxy, or groups obtained by bonding a plurality of ethyleneoxy groups with a plurality of propyleneoxy groups are preferred as polyvinyloxy or polypropyleneoxy groups, with polyvinyloxy being even more preferred. Among the groups obtained by bonding a plurality of ethyleneoxy groups with a plurality of propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred states of the repetition of ethyleneoxy groups in these groups are as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugated base with a tertiary amine compound having vinyl unsaturated bonds. N,N-dimethylaminopropyl methacrylate is an example of such a tertiary amine compound having vinyl unsaturated bonds.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ can be a polar reversible group such as an acid-degradable group. As an acid-degradable group, there is no particular limitation as long as it decomposes under the action of acid to produce an alkaline soluble group such as a phenolic hydroxyl group or a carboxyl group, but acetal, ketal, silyl alkyl, silyl ether, and tertiary alkyl ester are preferred. From the perspective of exposure sensitivity, acetal or ketal is more preferred. Specific examples of acid-degradable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tertiary butoxycarbonylmethyl, and trimethylsilyl ether. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl are preferred.

Furthermore, it is preferable for polyimide precursors to have fluorine atoms in their structure. A fluorine atom content of 10% by mass or more in the polyimide precursor is preferred, while a fluorine atom content of less than 20% by mass is also preferred.

Furthermore, to improve adhesion to the substrate, polyimide precursors can be copolymerized with aliphatic groups having a silicate structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

It is preferable that the repeating unit represented by formula (2) is a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in this invention is a precursor having a repeating unit represented by formula (2-A). By having the polyimide precursor contain a repeating unit represented by formula (2-A), the exposure tolerance can be widened. Formula (2-A) [Chemical Formula 16] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 represent divalent organic groups independently, ^R113 and ^R114 represent hydrogen atoms or monovalent organic groups independently, and at least one of ^R113 and ^R114 is a group containing polymerizable groups, preferably both of which contain polymerizable groups.

The meanings of ^A1 , ^A2 , ^R111 , ^R113 , and ^R114 are independently the same as those of ^A1 , ^A2 , ^R111 , ^R113 , and ^R114 in equation (2), and the preferred ranges are also the same. The meaning of ^R112 is the same as that of ^R112 in equation (5), and the preferred range is also the same.

Polyimide precursors may contain one or more repeating units represented by formula (2). They may also contain structural isomers of the repeating units represented by formula (2). Furthermore, it is self-evident that polyimide precursors may contain other types of repeating units besides the repeating units of formula (2) mentioned above.

As one embodiment of the polyimide precursor in this invention, an example is that the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. It is more preferable that the total content is 70 mol% or more, even more preferable that it is 90 mol% or more, and even more preferable that it exceeds 90 mol%. There is no particular limitation on the upper limit of the total content, except that all repeating units in the terminal polyimide precursor can be repeating units represented by formula (2).

The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. Furthermore, the number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the above-mentioned polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no specific upper limit to the molecular weight dispersion of the polyimide precursor, but for example, 7.0 or below is preferred, 6.5 or below is more preferred, and 6.0 or below is even more preferred. In this specification, the molecular weight dispersion is a value calculated using weight average molecular weight/number average molecular weight. Furthermore, when the resin composition, as a specific resin, contains multiple polyimide precursors, it is preferred that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyimide precursor are within the above-mentioned ranges. Moreover, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersion calculated when considering the multiple polyimide precursors as a single resin are each within the above-mentioned ranges.

[Polyimide] The polyimide used in this invention can be an alkaline-soluble polyimide or a polyimide soluble in a developing solution primarily composed of an organic solvent. In this specification, alkaline-soluble polyimide refers to polyimide that dissolves at least 0.1 g in 100 g of a 2.38% (w/w) tetramethylammonium aqueous solution at 23°C. From a pattern-forming point of view, dissolving at least 0.5 g of polyimide is preferred, and dissolving at least 1.0 g of polyimide is further preferred. There is no particular upper limit to the above dissolution amount, but less than 100 g is preferred. Furthermore, considering the strength and insulation properties of the resulting organic membrane, polyimides with a plurality of amide structures in the backbone are preferred. In this specification, "backbone" refers to the longest bond in the polymer molecule constituting the resin, and "side chain" refers to all other bond chains.

-Fluorine Atom- From the viewpoint of the membrane strength of the obtained organic membrane, it is preferable that the polyimide has fluorine atoms. It is preferable that the fluorine atom is contained, for example, in R ¹³² or R ¹³¹ of the repeating unit represented by formula (4) described later, and even more preferably as a fluorinated alkyl group in R ¹³² or R ¹³¹ of the repeating unit represented by formula (4) described later. It is preferable that the amount of fluorine atoms relative to the total mass of the polyimide is 5% by mass or more, and preferably 20% by mass or less.

-Silicon Atoms- From the viewpoint of the strength of the obtained organic film, it is preferable that polyimide contains silicon atoms. It is preferable that the silicon atoms are included, for example, in R ¹³¹ of the repeating unit represented by the formula (4) described later, and even more preferably in R ¹³¹ of the repeating unit represented by the formula (4) described later as an organically modified (poly)siloxane structure. Furthermore, the aforementioned silicon atoms or the aforementioned organically modified (poly)siloxane structure may also be included in the side chain of polyimide, but it is preferable that they are included in the main chain of polyimide. It is preferable that the amount of silicon atoms relative to the total mass of polyimide is 1% by mass or more, and even more preferably 20% by mass or less.

-Ethylene Unsaturated Bonds- From the perspective of the film strength of the obtained organic film, it is preferable that polyimide has ethylene unsaturated bonds. Polyimide can have ethylene unsaturated bonds at the main chain end or in the side chain, but it is preferable that it has ethylene unsaturated bonds in the side chain. The aforementioned ethylene unsaturated bonds are preferably free radical polymerizable. It is preferable that the ethylene unsaturated bond is contained in R ¹³² or R 131 of the repeating unit represented by equation (4) described later, and even more preferable that it is contained in R ¹³² or R ¹³¹ of the repeating unit represented by equation (4) described later as a group having an ethylene unsaturated bond. Among these, it is preferable that the ethylene unsaturated bond is contained in R ¹³¹ of the repeating unit represented by equation (4) described later, and even more preferable that it is contained in R ¹³¹ of the repeating unit represented by equation (4) described later as a group having an ethylene ^unsaturated bond. Examples of vinyl groups with vinyl unsaturated bonds include vinyl, allyl, vinylphenyl, vinyl groups that are directly bonded to an aromatic ring and can be substituted, (meth)acrylyl, (meth)acryloxy, and groups represented by the following formula (IV).

【Chemical Formula 17】

In formula (IV), R ²⁰ represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred.

In formula (IV), R ²¹ represents an alkyl group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and especially preferably 2 or 3; a repetition number of 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is especially preferred), or a group formed by combining two or more of these. Furthermore, the alkyl group having 2 to 12 carbon atoms can be any of linear, branched, cyclic, or a combination thereof. Among the alkyl groups having 2 to 12 carbon atoms, alkyl groups having 2 to 8 carbon atoms are preferred, and alkyl groups having 2 to 4 carbon atoms are even more preferred.

Of these, it is preferable that ^R21 is a group represented by any of the following formulas (R1) to (R3), with the group represented by formula (R1) being more preferred. [Chemical Formula 18] In formulas (R1) to (R3), L represents a single bond or a group consisting of an alkyl group having 2 to 12 carbon atoms, a (poly)alkylene group having 2 to 30 carbon atoms, or two or more of these bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with other structures; and ● represents a bonding site with the oxygen atom bonded to R ²¹ in formula (IV). In formulas (R1) to (R3), the preferred state of the alkyl group having 2 to 12 carbon atoms or the (poly)alkylene group having 2 to 30 carbon atoms in L is the same as the preferred state of the alkyl group having 2 to 12 carbon atoms or the (poly)alkylene group having 2 to 30 carbon atoms in R ²¹ described above. In formula (R1), it is preferred that X is an oxygen atom. In formulas (R1) to (R3), the asterisk (*) has the same meaning as in formula (IV), and the preferred state is also the same. The structure represented by formula (R1) is obtained, for example, by reacting a polyimide having hydroxyl groups such as phenolic hydroxyl groups with a compound having isocyanate groups and vinyl unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate). The structure represented by formula (R2) is obtained, for example, by reacting a polyimide having carboxyl groups with a compound having hydroxyl groups and vinyl unsaturated bonds (e.g., ethyl 2-hydroxymethacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having hydroxyl groups such as phenolic hydroxyl groups with a compound having glycidyl groups and vinyl unsaturated bonds (e.g., glycidyl methacrylate).

In formula (IV), * indicates the bonding site with other structures, and the bonding site with the polyimide backbone is preferred.

The preferred content of ethylene unsaturated bonds relative to the total mass of polyimide is 0.0001–0.1 mol/g, and even more preferred content is 0.0005–0.05 mol/g.

- Polymerizable groups other than those with ethylene unsaturated bonds- Polyimide may have polymerizable groups other than those with ethylene unsaturated bonds. Examples of polymerizable groups other than those with ethylene unsaturated bonds include cyclic ether groups such as epoxy and oxycyclobutyl, alkoxymethyl groups such as methoxymethyl, hydroxymethyl, etc. It is preferable that the polymerizable groups other than those with ethylene unsaturated bonds are included, for example, in R ¹³¹ of the repeating unit represented by formula (4) described later. It is preferable that the amount of polymerizable groups other than those with ethylene unsaturated bonds relative to the total mass of polyimide is 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

-Polar Reversible Group- Polyimides can have polar reversible groups such as acid-degrading groups. The acid-degrading groups in polyimides are the same as those described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred forms are also the same. Polar reversible groups are included, for example, in R ¹³¹ , R ¹³² in the repeating unit represented by the following formula (4), the end of the polyimide, etc.

-Acid Value- When polyimide is provided in alkaline developing solutions, from the viewpoint of improving developing properties, an acid value of 30 mg KOH/g or higher is preferred, 50 mg KOH/g or higher is more preferred, and 70 mg KOH/g or higher is even more preferred. Furthermore, an acid value of 500 mg KOH/g or lower is preferred, 400 mg KOH/g or lower is even more preferred, and 200 mg KOH/g or lower is even more preferred. Furthermore, when polyimide is provided in developing solutions using organic solvents as the main component (e.g., "solvent developing" as described below), an acid value of 1–35 mg KOH/g is preferred, 2–30 mg KOH/g is more preferred, and 5–20 mg KOH/g is even more preferred. The acid values mentioned above are determined by well-known methods, such as those described in JIS K 0070:1992. Furthermore, considering both stability and development, acid groups containing acid groups in polyimide with pKa values of 0–10 are preferred, while those with pKa values of 3–8 are even better. pKa is the negative logarithm of the equilibrium constant Ka, expressed in terms of the dissociation reaction that releases hydrogen ions from the acid. Unless otherwise specified in this specification, pKa is assumed to be a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, the values published in the 5th revised edition of the Chemical Handbook of Japan, Basic Chemicals, can be consulted. Furthermore, when the acid group is a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As such an acid group, it is preferable that the polyimide contains at least one group selected from the group consisting of carboxyl and phenolic hydroxyl groups, and more preferably a phenolic hydroxyl group.

-Phenolic hydroxyl group- From the viewpoint of making the developing speed of alkaline developing solution suitable, it is preferable that polyimide has a phenolic hydroxyl group. Polyimide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. It is preferable that the phenolic hydroxyl group is included, for example, in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described later. It is preferable that the amount of phenolic hydroxyl group relative to the total mass of polyimide is 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyimide used in this invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable to contain a repeating unit represented by the following formula (4). [Chemical Formula 19] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When a polymerizable group is present, the polymerizable group can be located on at least one of R ¹³¹ and R ¹³² , as shown in formula (4-1) or formula (4-2) below, or it can be located at the end of the polyimide. Formula (4-1) [Chemical Formula 20] In formula (4-1), R ¹³³ is a polymerizable group, and the meanings of the other groups are the same as in formula (4). Formula (4-2) [Chemical Formula 21] At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and when it is not a polymerizable group, it is an organic group. The meanings of the other groups are the same as those in equation (4).

As a polymerizable group, examples include the groups containing ethylene unsaturated bonds or crosslinking groups other than those containing ethylene unsaturated bonds. R ¹³¹ represents a divalent organic group. As a divalent organic group, examples can be the same as R ¹¹¹ in formula (2), and the preferred range is also the same. Furthermore, as R ¹³¹ , examples can be the diamine residue remaining after removing the amino group of a diamine. As a diamine, examples can be aliphatic, cyclic aliphatic, or aromatic diamines. As a specific example, examples can be given for R ¹¹¹ in formula (2) of polyimide precursors.

From the viewpoint of more effectively suppressing warping during burning, R ¹³¹ is preferably a diamine residue having at least two alkyl diol units in the main chain. More preferably, it is a diamine residue containing a total of two or more ethylene glycol chains or propylene glycol chains in one molecule, and even more preferably, it is a diamine without an aromatic ring.

Examples of diamines comprising two or more ethylene glycol chains or propylene glycol chains in a single molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., but are not limited to these.

R ¹³² represents a tetravalent organic group. As a tetravalent organic group, it can be exemplified as the same as R ¹¹⁵ in equation (2), and the preferred range is also the same. For example, the four bonded elements of the tetravalent organic group exemplified as R ¹¹⁵ bond with the four -C (=O)- parts in the above equation (4) to form a condensation ring.

Furthermore, R ¹³² can be exemplified by the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic acid dianhydride. As a specific example, R ¹¹⁵ in formula (2) of polyimide precursors can be cited. From the viewpoint of the strength of organic membranes, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, as R ¹³¹ , preferred examples include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18), and as R ¹³² , more preferred examples include the above (DAA-1) to (DAA-5).

Furthermore, it is preferable for polyimide to have fluorine atoms in its structure. The fluorine atom content in polyimide is preferably 10% by mass or more, and preferably less than 20% by mass.

Furthermore, to improve adhesion to the substrate, polyimide can be copolymerized with aliphatic groups having a silicate structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

Furthermore, in order to improve the storage stability of resin components, it is preferable to seal the main chain ends of polyimide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochlorodimethylamine compounds, and monoactive ester compounds. Among these, monoamines are preferred. Examples of preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl... -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different terminal groups can be introduced by reacting multiple end-capping agents.

-Lipidification Rate (Ring-Closing Rate)- From the perspective of the obtained organic membrane's strength and insulation, a lipimization rate (also known as "ring-closing rate") of 70% or higher for polyimide is preferred, 80% or higher is even better, and 90% or higher is still preferable. There is no particular upper limit to the above lipimization rate; it only needs to be below 100%. The above lipimization rate can be determined, for example, by the following method: Measure the infrared absorption spectrum of the polyimide and determine the peak intensity P1 near 1377 ^cm⁻¹ , which represents the absorption peak originating from the lipimide structure. Next, after heat-treating the polyimide at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 near 1377 ^cm⁻¹ was determined. Using the obtained peak intensities P1 and P2, the amide ratio of the polyimide can be calculated according to the following formula: Imidization ratio (%) = (Peak intensity P1 / Peak intensity P2) × 100

Polyimide may contain only one type of repeating unit represented by formula (4) above, which includes one ^type of R ¹³¹ or R ¹³² , or it may contain two or more different types of repeating ^units represented by formula (4) above. In addition to the repeating units represented by formula (4) above, polyimide may also contain other types of repeating units. Examples of other types of repeating units include repeating units represented by formula (2) below.

Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with a diamine (with a portion replaced by a monoamine end-capping agent) at low temperature; by reacting tetracarboxylic dianhydride (with a portion replaced by an anhydride, a monochloro compound, or a monoactive ester compound end-capping agent) with a diamine at low temperature; by obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine (with a portion replaced by a monoamine end-capping agent) in the presence of a condensing agent; using... A polyimide precursor is obtained by methods such as reacting a tetracarboxylic acid dianhydride with an alcohol to form a diester, then oxychlorinating the remaining dicarboxylic acid and reacting it with a diamine (with a portion replaced by a monoamine end-capping agent), and then completely oxyimidizing it using a known oxyimidation reaction; or, stopping the oxyimidation reaction midway to introduce a partial oxyimide structure; and introducing a partial oxyimide structure by mixing a fully oxyimidized polymer with the polyimide precursor. Other known methods for synthesizing polyimides are also applicable.

The weight-average molecular weight (Mw) of polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. Setting the weight-average molecular weight to 5,000 or higher improves the folding resistance of the cured film. For obtaining organic films with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or higher is particularly preferred. Furthermore, the number-average molecular weight (Mn) of polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the aforementioned polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no particular upper limit specified for the molecular weight dispersion of the polyimide; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is further preferred. Furthermore, when the resin composition comprises multiple polyimides as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyimide are within the aforementioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersion calculated when the multiple polyimides are treated as a single resin are each within the aforementioned ranges.

[Polybenzoxazole precursor] There are no particular provisions regarding the structure of the polybenzoxazole precursor used in this invention, but it is preferred that it contains repeating units represented by the following formula (3). [Chemical Formula 22] In equation (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ represent hydrogen atoms or monovalent organic groups, respectively.

In formula (3), the meanings of R ¹²³ and R ¹²⁴ are the same as those of R ¹¹³ in formula (2), and the preferred ranges are also the same. That is, it is preferred that at least one of them is a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. As a divalent organic group, it is preferred that the group includes at least one of aliphatic and aromatic groups. As an aliphatic group, a linear aliphatic group is preferred. It is preferred that ^{R 121} is a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As a dicarboxylic acid residue, dicarboxylic acids containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, with dicarboxylic acid residues containing aromatic groups being more preferred. As a dicarboxylic acid containing an aliphatic group, dicarboxylic acids containing straight-chain or branched (preferably straight-chain) aliphatic groups are preferred, and dicarboxylic acids composed of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups are more preferred. The carbon number of the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2-30, more preferably 2-25, further preferably 3-20, further preferably 4-15, and especially preferably 5-10. The straight-chain aliphatic group is preferably an alkyl group. Examples of dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethyl Pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, docosanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

【Chemical Formula 23】 (In the formula, Z is a hydrocarbon with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

As a dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting only of an aromatic group and two -COOH groups are even more preferred.

【Chemical Formula 24】 In the formula, A represents a divalent group selected from the group including _-CH2- , -O-, -S-, _-SO2- , -CO-, -NHCO-, -C( _CF3 ) _2- and -C( _CH3 ) _2- , and * represents the bonding site with other structures independently.

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and phthalic acid.

In equation (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, its meaning is the same as that of R ¹¹⁵ in equation (2) above, and the preferred range is also the same. Groups derived from diaminophenol derivatives are also preferred, such as ^3,3' -diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl tin, 4,4'-diamino-3,3'-dihydroxydiphenyl tin, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These diaminophenols can be used alone or in combination.

Among diaminophenol derivatives, the following diaminophenol derivatives having aromatic groups are preferred.

【Chemical Formula 25】 In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , and -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, with hydrogen atom or alkyl group being preferred, and hydrogen atom or alkyl group being even more preferred. Furthermore, ^R122 is also preferred as the structure represented by the above formula. When R ¹²² has the structure represented by the above formula, it is preferable that any two of the four asterisks and # are bonded to nitrogen atoms in R ¹²² in formula (3) and the other two are bonded to oxygen atoms in R ¹²² in formula (3). It is even better that two asterisks are bonded to oxygen atoms in R ¹²² in formula (3) and two # are bonded to nitrogen atoms in R ¹²² in formula (3), or two asterisks are bonded to nitrogen atoms in R ¹²² in formula (3) and two # are bonded to oxygen atoms in R ¹²² in formula (3). The bonding sites of the oxygen atoms bonded by ¹²² and the two # are more preferably the bonding sites of the nitrogen atoms bonded by ^R in equation (3).

Diaminophenol derivatives represented by formula (As) are also preferred. [Chemical Formula 26]

In formula (As), _R1 is a hydrogen atom, an alkyl group, a substituted alkyl group, -O-, -S-, _-SO₂- , -CO-, -NHCO-, a single bond, or an organic group selected from the group of formulas (A-sc) below. _R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acetoxy group, or a cyclic alkyl group, which may be the same or different. _R3 is any one of a hydrogen atom, a straight-chain or branched alkyl group, an alkoxy group, an acetoxy group, or a cyclic alkyl group, which may be the same or different.

【Chemical Formula 27】 (In formula (A-sc), * indicates an aromatic ring bonded to the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

In the above formula (As), it is considered that the presence of substituents at the position adjacent to the phenolic hydroxyl group, i.e. _R3 , would bring the carbonyl carbon of the amide bond closer to the hydroxyl group, thereby further enhancing the effect of achieving a high cyclization rate during hardening at low temperatures.

Furthermore, in the above formula (As), when _R2 is an alkyl group and _R3 is an alkyl group, it can maintain the effect of high transparency to i-rays and high cyclization rate when hardened at low temperature, which is therefore better.

Furthermore, in the above formula (As), it is even more preferable that _R1 is an alkylene group or a substituted alkylene group. Specific examples of alkylene _groups and substituted alkylene groups of 1 to 8 carbon atoms can be given, such as linear or branched alkyl groups. Among them, -CH2-, -CH(CH3)-, and -C( _{CH3 ) 2-} are more preferred in terms of maintaining high transparency to i-rays and high cyclization rate when curing at low temperatures, and in order to obtain a polybenzoxazole precursor with _a good balance of sufficient solubility in solvents.

As for the method of manufacturing the diaminophenol derivative represented by the above formula (A-s), for example, you can refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, the contents of which are incorporated in this specification.

Specific examples of the structure of a diaminophenol derivative represented by the above formula (A-s) can be found in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, the contents of which are incorporated herein by reference. However, it is not limited to these examples.

In addition to the repeating unit of formula (3) above, polybenzoxazole precursors may also contain other types of repeating units. In terms of suppressing the formation of curl-up associated with ring closure, it is preferable that the polybenzoxazole precursor, as another type of repeating unit, contains a diamine residue represented by formula (SL).

【Chemical Formula 28】 In formula (SL), Z has an a-structure and a b-structure. ^R1s is a hydrogen atom or an hydrocarbon with 1 to 10 carbon atoms, ^R2s is an hydrocarbon with 1 to 10 carbon atoms, at least one of ^R3s , ^R4s , ^R5s , and ^R6s is an aromatic group, and the rest are hydrogen atoms or organic groups with 1 to 30 carbon atoms. These groups can be the same or different. The polymerization of the a-structure and the b-structure can be block polymerization or random polymerization. Regarding the molar percentage of the Z part, the a-structure is 5 to 95 molars, the b-structure is 95 to 5 molars, and a+b is 100 molars.

In formula (SL), Z is preferably represented by ^R5s and ^R6s in structure b being phenyl. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400–4,000, and more preferably 500–3,000. By setting the molecular weight within the above range, the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor can be reduced more effectively, thus achieving both the effect of suppressing warping and improving solvent solubility.

When the diamine residue represented by formula (SL) is used as another type of repeating unit, it is also preferable to further include the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic acid dianhydride as a repeating structural unit. As an example of such a tetracarboxylic acid residue, R ¹¹⁵ in formula (2) can be cited.

The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Furthermore, the number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The molecular weight dispersion of the above-mentioned polybenzoxazole precursor is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no specific upper limit for the molecular weight dispersity of the polybenzoxazole precursor. For example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is further preferred, 2.3 or less is even more preferred, and 2.2 or less is still more preferred. Furthermore, when the resin composition contains multiple polybenzoxazole precursors as a specific resin, it is preferred that the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the above-mentioned ranges. Also, it is preferred that the weight average molecular weight, number average molecular weight, and dispersity calculated when considering the multiple polybenzoxazole precursors as a single resin are each within the above-mentioned ranges.

[Polybenzoxazole] There are no particular limitations on the polybenzoxazole as long as it is a polymeric compound having a benzoxazole ring, but compounds represented by formula (X) are preferred, and compounds represented by formula (X) and having a polymerizable group are even more preferred. As the polymerizable group, a free radical polymerizable group is preferred. Furthermore, compounds represented by formula (X) and having a polar reversible group such as an acid-decomposing group can also be used. [Chemical Formula 29] In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When a polar inversion group, such as a polymerizable or acid-degradable group, is present, the polymerizable or acid-degradable group can be located on at least one of R ¹³³ and R ¹³⁴ , as shown in formula (X-1) or formula (X-2) below, or it can be located at the end of the polybenzoxazole. Formula (X-1) [Chemical Formula 30] In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polar reversal group, such as a polymerizable group or an acid-decomposable group. When it is not a polymerizable group or an acid-decomposable group, it is an organic group. The meanings of the other groups are the same as those in formula (X). Formula (X-2) [Chemical Formula 31] In formula (X-2), R ¹³⁷ is a polar reversal group such as a polymerizable group or an acid-degradable group, and the others are substituents. The meanings of the other groups are the same as those in formula (X).

The meaning of polar reverse groups, such as polymerizable groups or acid-degradable groups, is the same as the meaning of polymerizable groups described in the above-mentioned polyimide precursors.

R ¹³³ represents a divalent organic group. Examples of divalent organic groups include aliphatic or aromatic groups. As a specific example, R ¹²¹ in formula (3) of polybenzoxazole precursors can be cited. Furthermore, a preferred example is the same as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. An example of a tetravalent organic group is R ¹²² in formula (3) of a polybenzoxazole precursor. A preferred example is also R ^122. For example, the four bond atoms of the tetravalent organic group exemplified as R ¹²² bond with the nitrogen and oxygen atoms in formula (X) above to form a condensed ring. For example, when R ¹³⁴ is an organic group as described below, the following structure is formed. In the following structure, * respectively indicates the bonding site with the nitrogen or oxygen atom in formula (X). [Chemical Formula 32]

An oxazolization rate of 85% or higher for polybenzoxazole is preferred, and 90% or higher is even better. There is no specific upper limit; it can be 100%. With an oxazolization rate of 85% or higher, the film shrinkage caused by ring closure during heating-induced oxazolization is reduced, thus more effectively suppressing warping. The aforementioned oxazolization rate is measured, for example, by the following method: The infrared absorption spectrum of polybenzoxazole is measured, and the peak intensity Q1 near 1650 ^{cm⁻¹, representing the absorption peak of the amide structure from the precursor, is determined. Then, it is standardized using the absorption intensity of the aromatic ring found near 1490 cm⁻¹ .} After heat-treating the polybenzoxazole at 350°C for one hour, the infrared absorption spectrum was measured again to determine the peak intensity Q2 near 1650 ^cm⁻¹ , which was then standardized using the absorption intensity of the aromatic ring found near 1490 ^cm⁻¹ . Using the obtained standard values of peak intensities Q1 and Q2, the oxazolization rate of the polybenzoxazole can be calculated according to the following formula: Oxazolization rate (%) = (Standard value of peak intensity Q1 / Standard value of peak intensity Q2) × 100

Polybenzoxazole may contain only repeating units of formula (X) of the above form, which include one type of R ¹³¹ or R ¹³² , or it may contain repeating units of formula (X) of the above form, which include two or more different types of R ¹³¹ or R ^132. In addition to repeating units of formula (X) above, polybenzoxazole may also contain repeating units of other types.

Polybenzoxazole precursors are obtained, for example, by reacting a diaminophenol derivative with a dicarboxylic acid containing ^R133 , or a dicarboxylic acid dichloride selected from the aforementioned dicarboxylic acids, and dicarboxylic acid derivatives, and then oxazolizing it using a known oxazolization reaction. Alternatively, in the case of a dicarboxylic acid, to improve the reaction yield, an active ester-type dicarboxylic acid derivative obtained by pre-reaction of 1-hydroxy-1,2,3-benzotriazole can be used.

The weight-average molecular weight (Mw) of polybenzoxazole is preferably 5,000–70,000, more preferably 8,000–50,000, and even more preferably 10,000–30,000. Setting the weight-average molecular weight to 5,000 or higher improves the folding resistance of the cured film. For organic films with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, when two or more polybenzoxazoles are contained, it is preferable that at least one polybenzoxazole has a weight-average molecular weight within the above range. Furthermore, the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200–14,000, more preferably 8,000–12,000, and even more preferably 9,200–11,200. The molecular weight dispersion of the above-mentioned polybenzoxazole is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no specific upper limit for the molecular weight dispersion of polybenzoxazole; for example, 2.6 or lower is preferred, 2.5 or lower is more preferred, 2.4 or lower is even more preferred, 2.3 or lower is even more preferred, and 2.2 or lower is even more preferred. Furthermore, when the resin composition contains multiple polybenzoxazoles as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility of at least one polybenzoxazole are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility calculated when considering the multiple polybenzoxazoles as a single resin are each within the aforementioned ranges.

[Polyamide-imide precursor] It is preferable that the polyamide-imide precursor contains a repeating unit represented by the following formula (PAI-2). [Chemical Formula 33] In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ can exemplify a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaryl group, or a group obtained by connecting two or more of these groups with a single bond or by linking groups. It is preferred to have a linear aliphatic group with 2 to 20 carbons, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a group obtained by combining two or more of these groups with a single bond or by linking groups. It is even more preferred to have an aromatic group with 6 to 20 carbons, or a group obtained by combining two or more aromatic groups with 6 to 20 carbons with a single bond or by linking groups. As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O) _2- , alkylene, halogenated alkylene, arylene, or a linking group formed by two or more of these bonds is preferred; -O-, -S-, alkylene, halogenated alkylene, arylene, or a linking group formed by two or more of these bonds is even more preferred. As the alkylene group mentioned above, alkylene having 1 to 20 carbon atoms is preferred, alkylene having 1 to 10 carbon atoms is more preferred, and alkylene having 1 to 4 carbon atoms is even more preferred. As the halogenated alkylene group mentioned above, halogenated alkylene having 1 to 20 carbon atoms is preferred, halogenated alkylene having 1 to 10 carbon atoms is even more preferred, and halogenated alkylene having 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned halogenated alkyl groups include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. The aforementioned halogenated alkyl groups may contain hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but substitution with halogen atoms is preferred. Examples of preferred halogenated alkyl groups include (di-trifluoromethyl)methylene. As for the aforementioned aryl groups, phenyl or naphthyl groups are preferred, with phenyl groups being more preferred, and 1,3-phenyl or 1,4-phenyl groups being even more preferred.

Furthermore, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. Chlorination is preferred as the halogenation method. In this invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups in the aforementioned tricarboxylic acid compound can be anhydride-substituted. Examples of halogenable tricarboxylic acid compounds used in the manufacture of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. Only one type of such tricarboxylic acid compound may be used, or two or more types may be used.

Specifically, as a tricarboxylic acid compound, a tricarboxylic acid compound comprising a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more of these groups via a linker is preferred. A tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a linker is even more preferred.

Furthermore, specific examples of tricarboxylic acid compounds include compounds in which 1,2,3-propanetricarboxylic acid, _1,3,5 - _{pentanetricarboxylic} acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride), and benzoic acid are linked by single bonds, -O-, -CH2-, -C( _CH3 ) _2- , -C( _CF3 )2-, _-SO2- , or extended phenyl groups. These compounds can be compounds in which two carboxyl groups are anhydridated (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride chlorohydride).

In formula (PAI-2), the meanings of ^R111 , ^A2 , and ^R113 are the same as those of ^R111 , ^A2 , and ^R113 in formula (2) above, and the better state is also the same.

Polyamide imide precursors may further contain other repeating units. Examples of other repeating units include those represented by formula (2) above and those represented by formula (PAI-1) below. [Chemical Formula 34]

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group. In formula (PAI-1), R ¹¹⁶ can exemplify a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaryl group, or a group obtained by linking two or more of these groups together with a single bond or a linking group. It is preferred to have a linear aliphatic group with 2 to 20 carbons, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a group obtained by linking two or more of these groups together with a single bond or a linking group. It is even more preferred to have an aromatic group with 6 to 20 carbons, or an aromatic group obtained by linking two or more of these groups together with a single bond or a linking group. As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O) _2- , alkylene, halogenated alkylene, arylene, or a linking group formed by two or more of these bonds is preferred; -O-, -S-, alkylene, halogenated alkylene, arylene, or a linking group formed by two or more of these bonds is even more preferred. As the alkylene group mentioned above, alkylene having 1 to 20 carbon atoms is preferred, alkylene having 1 to 10 carbon atoms is more preferred, and alkylene having 1 to 4 carbon atoms is even more preferred. As the halogenated alkylene group mentioned above, halogenated alkylene having 1 to 20 carbon atoms is preferred, halogenated alkylene having 1 to 10 carbon atoms is even more preferred, and halogenated alkylene having 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned halogenated alkyl groups include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. The aforementioned halogenated alkyl groups may contain hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but substitution with halogen atoms is preferred. Examples of preferred halogenated alkyl groups include (di-trifluoromethyl)methylene. As for the aforementioned aryl groups, phenyl or naphthyl groups are preferred, with phenyl groups being more preferred, and 1,3-phenyl or 1,4-phenyl groups being even more preferred.

Furthermore, R ¹¹⁶ is preferably derived from dicarboxylic acid compounds or dicarboxylic acid dihalides. In this invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide. The carboxyl groups in a dicarboxylic acid dihalide only need to be halogenated; for example, chlorination is preferred. That is, a dicarboxylic acid dihalide is preferably a dicarboxylic acid dichloride compound. Examples of halogenable dicarboxylic acid compounds or dicarboxylic acid dihalides that can be used in the manufacture of polyamide imine precursors include linear or branched aliphatic, cyclic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides. Only one type of such dicarboxylic acid compound or dicarboxylic acid dihalide may be used, or two or more types may be used.

Specifically, as a dicarboxylic acid compound or dicarboxylic acid dihalogenate, it is preferred that the dicarboxylic acid compound or dicarboxylic acid dihalogenate contains a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more of these groups via a linker. It is even more preferred that the dicarboxylic acid compound or dicarboxylic acid dihalogenate contains an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more of the aromatic groups having 6 to 20 carbon atoms via a linker.

Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, octanoic acid, dodecafluorooctanoic acid, azelaic acid, sebacic acid, and hexafluorodecanoic acid. Dicarboxylic acids, 1,9-azelaic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, triacontadecanoic acid, triacontadecanoic acid, diethanolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. Specific examples of dicarboxylic acid dihalides include compounds with structures formed by halogenating two carboxyl groups in the above-mentioned dicarboxylic acid compounds.

In formula (PAI-1), the meaning of R ¹¹¹ is the same as that of R ¹¹¹ in formula (2) above, and the better state is also the same.

Furthermore, it is preferable that the polyamide imide precursor has fluorine atoms in its structure. It is preferable that the fluorine atom content in the polyamide imide precursor is 10% by mass or more, and preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, polyamide imine precursors can be copolymerized with aliphatic groups having a silicate structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

As an embodiment of the polyamide imide precursor of the present invention, an example is provided where the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and more than 90 mol% is particularly preferred. There is no particular limitation on the upper limit of the total content; all repeating units in the polyamide imide precursor, except for the terminal units, can be any one of the repeating units represented by formula (PAI-2), formula (PAI-1), and formula (2). Furthermore, as another embodiment of the polyamide-imide precursor of this invention, an example is provided where the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and more than 90 mol% is particularly preferred. There is no particular limitation on the upper limit of the total content; all repeating units in the polyamide-imide precursor, except for the terminal units, can be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Furthermore, the number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no specific upper limit for the molecular weight dispersity of the polyamide-imide precursor, but for example, 7.0 or below is preferred, 6.5 or below is more preferred, and 6.0 or below is even more preferred. Furthermore, when the resin composition comprises multiple polyamide-imide precursors as a specific resin, it is preferred that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyamide-imide precursor are within the above-mentioned ranges. Additionally, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersity calculated when considering the multiple polyamide-imide precursors as a single resin are each within the above-mentioned ranges.

[Polyamide-Imine] The polyamide-imide used in this invention can be an alkaline-soluble polyamide-imide or a polyamide-imide soluble in a developing solution primarily composed of an organic solvent. In this specification, alkaline-soluble polyamide-imide refers to polyamide-imide that dissolves at least 0.1 g in 100 g of a 2.38% (w/w) tetramethylammonium aqueous solution at 23°C. From a pattern-forming point of view, dissolving at least 0.5 g of polyamide-imide is preferred, and dissolving at least 1.0 g of polyamide-imide is further preferred. There is no particular upper limit to the above dissolution amount, but less than 100 g is preferred. Furthermore, considering the strength and insulation properties of the obtained organic membrane, polyamide-propylene imide with a plurality of amide bonds and a plurality of propylene imide structures in the main chain is preferred.

-Fluorine Atom- From the viewpoint of the membrane strength of the obtained organic membrane, it is preferable that the polyamide amide has fluorine atoms. It is preferable that the fluorine atom is contained, for example, in R ¹¹⁷ or R ¹¹¹ of the repeating unit represented by the following formula (PAI-3), and even more preferably, it is contained as a fluorinated alkyl group in R ¹¹⁷ or R ¹¹¹ of the repeating unit represented by the following formula (PAI-3). It is preferable that the amount of fluorine atoms relative to the total mass of the polyamide amide is 5% by mass or more, and preferably 20% by mass or less.

-Ethylene Unsaturated Bonds- From the perspective of the film strength of the obtained organic film, polyamide amide can possess ethylene unsaturated bonds. Polyamide amide can have ethylene unsaturated bonds at the main chain end or in the side chain, but it is preferred that it has ethylene unsaturated bonds in the side chain. The aforementioned ethylene unsaturated bonds are preferably free radical polymerizable. It is preferable that the ethylene unsaturated bond is contained in ^R117 or ^R111 in the repeating unit represented by the formula (PAI-3) described later, and it is even more preferable that the group having the ethylene unsaturated bond is contained in ^R117 or ^R111 in the repeating unit represented by the formula (PAI-3) described later. The preferred state of the group having the ethylene unsaturated bond is the same as the preferred state of the group having the ethylene unsaturated bond in the polyimide described above.

The total mass of ethylene unsaturated bonds relative to polyamide amide is preferably 0.0001–0.1 mol/g, and even more preferably 0.001–0.05 mol/g.

- Polymerizable groups other than ethylene unsaturated bonds- Polyamide amides may have polymerizable groups other than ethylene unsaturated bonds. Examples of polymerizable groups other than ethylene unsaturated bonds in polyamide amides include groups identical to those in the polyamides described above. It is preferable that the polymerizable groups other than ethylene unsaturated bonds are included, for example, in R ¹¹¹ of the repeating unit represented by the formula (PAI-3) described later. It is preferable that the amount of polymerizable groups other than ethylene unsaturated bonds relative to the total mass of the polyamide amide is 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.

-Polar Reversing Group- Polyamide imide can have polar reversing groups such as acid-degrading groups. The acid-degrading groups in polyamide imide are the same as those described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred state is also the same.

-Acid Value- When polyamide amide is provided in alkaline developing, from the viewpoint of improving developing properties, an acid value of 30 mg KOH/g or higher is preferred, 50 mg KOH/g or higher is even better, and 70 mg KOH/g or higher is still preferred. Furthermore, an acid value below 500 mg KOH/g is preferred, below 400 mg KOH/g is even better, and below 200 mg KOH/g is still even better. Furthermore, when polyamide-imide is provided for development using a developing solution primarily composed of an organic solvent (e.g., "solvent development" described below), the acid value of the polyamide-imide is preferably 2–35 mg KOH/g, more preferably 3–30 mg KOH/g, and even more preferably 5–20 mg KOH/g. The above acid value is determined by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, as acid groups contained in polyamide-imide, groups with the same characteristics as the acid groups in polyamide-imide can be cited, and their preferred states are also the same.

-Phenolic Hydroxyl Group- From the viewpoint of making the developing speed of alkaline developing solutions suitable, it is preferable that the polyamide imide has a phenolic hydroxyl group. The polyamide imide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. It is preferable that the phenolic hydroxyl group is included, for example, in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later. It is preferable that the amount of phenolic hydroxyl group relative to the total mass of the polyamide imide is 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyamide amide used in this invention is not particularly limited as long as it is a polymer compound having an amide structure and amide bonds, but it is preferred to contain a repeating unit represented by the following formula (PAI-3). [Chemical Formula 35] In formula (PAI-3), the meanings of R ¹¹¹ and R ¹¹⁷ are the same as those in formula (PAI-2), and the preferred state is also the same. When a polymerizable group is present, the polymerizable group can ^{be located at at least one of R 111 and R 117 , or it} can be located at the end of the polyamide amide.

Furthermore, to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyamide amide imide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochlorodiphenyl compounds, or monoactive ester compounds. The preferred state of the end-capping agent is the same as that of the end-capping agent in the polyamide mentioned above.

-Lipidification Rate (Ring-Closed Rate)- Considering the strength and insulation properties of the resulting organic membrane, a lipimization rate (also known as "ring-closed rate") of 70% or higher for polyamide lipimide is preferred, 80% or higher is even better, and 90% or higher is still preferable. There is no particular upper limit to the above lipimization rate; it only needs to be below 100%. The above lipimization rate is measured using the same method as the ring-closed rate of polyamide.

Polyamide amides may contain only one type of repeating unit represented by formula (PAI-3) of R ¹¹¹ or R ¹¹⁷ , or they may contain two or more different types of repeating units represented by R ¹³¹ or R ¹³² represented by formula (PAI-3). Furthermore, polyamide amides may contain other types of repeating units besides those represented by formula (PAI-3). Examples of other types of repeating units include repeating units represented by formula (PAI-1) or formula (PAI-2).

Polyamide imides can be obtained, for example, by known methods. Polyamide imide precursors can be synthesized by means of methods such as fully imidizing them using known imidization reactions, stopping the imidization reaction midway to introduce a partial imide structure, or introducing a partial imide structure by mixing the fully imidized polymer with its polyamide imide precursor.

The weight-average molecular weight (Mw) of polyamide-imide is preferably 5,000–70,000, more preferably 8,000–50,000, and even more preferably 10,000–30,000. Setting the weight-average molecular weight to 5,000 or higher improves the folding resistance of the cured film. For organic films with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, the number-average molecular weight (Mn) of polyamide-imide is preferably 800–250,000, more preferably 2,000–50,000, and even more preferably 4,000–25,000. The molecular weight dispersion of polyamide-imides is preferably 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no specific upper limit for the molecular weight dispersion of polyamide-imides; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is further preferred. Furthermore, when the resin composition comprises multiple polyamide-imides as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyamide-imide are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersion calculated when considering the multiple polyamide-imides as a single resin are each within the above-mentioned ranges.

[Manufacturing Methods for Polyimide Precursors, etc.] Polyimide precursors, etc., can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine at low temperature; by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamide and then esterifying it using a condensing agent or an alkylating agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol and then reacting it with diamine in the presence of a condensing agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and then reacting it with diamine, etc. Of the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, followed by acid halogenation of the remaining dicarboxylic acid with a halogenating agent and reaction with a diamine is preferred. Examples of the condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroxyquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of halogenating agents include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the manufacturing methods of polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used. As an organic solvent, it can be appropriately determined based on the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the manufacturing method of polyimide precursors, etc., it is preferable to add an alkaline compound during the reaction. The alkaline compound can be one type or two or more types. The alkaline compound can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diacrylbis[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

-End-Capping Agents- In the manufacture of polyimide precursors, etc., it is preferable to seal the resin ends of residual carboxylic anhydrides, anhydride derivatives, or amine groups to further improve storage stability. Examples of end-capping agents include monools, phenols, thiols, thiophenols, and monoamines. Considering reactivity and film stability, monools, phenols, or monoamines are preferred. Preferred compounds for monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc.; secondary alcohols include isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc.; and tertiary alcohols include butanol and adamantyl alcohol. Preferred compounds for phenols include phenols, methoxyphenols, methylphenols, naphth-1-ol, naphth-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds as monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2 The following are preferred end groups: -carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, and 4-aminobenzenethiophenol. Two or more of these can be used, and multiple different end groups can be introduced by reacting multiple end-capping agents. Furthermore, when sealing the amine groups at the ends of resins, compounds with functional groups capable of reacting with amine groups can be used for sealing. Preferred end-capping agents for amine groups include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being even more preferred. Examples of preferred carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Furthermore, preferred compounds for the chloride formation of carboxylic acids include acetyl chloride, acrylamide chloride, propionyl chloride, methacrylamide chloride, neopentyl chloride, cyclohexanemethyl chloride, 2-ethylhexyl chloride, cinnamic acid chloride, 1-draconemethyl chloride, heptafluorobutyric acid chloride, stearyl chloride, and benzoyl chloride.

-Solid Precipitation- The manufacture of polyimide precursors, etc., may include a solid precipitation step. Specifically, after filtering the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, to precipitate the polymer component in solid form. After drying, the polyimide precursor is obtained. To improve purity, the polyimide precursor, etc., may be repeatedly subjected to redissolution, redeposition, and drying. Additionally, the process of removing ionic impurities using ion exchange resins may also be included.

[Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin, or it may contain two or more specific resins. When two or more factors are involved, it is preferable that the total amount falls within the above range.

Furthermore, it is preferable that the resin composition of the present invention contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, and it is preferable that it contains two or more specific resins. When the resin composition of the present invention contains two or more specific resins, it is preferable that it contains, for example, two or more polyimide precursors with different structures (R ¹¹⁵ in the above formula (2)).

<Other Resins> The resin composition of this invention may include the specific resins described above and other resins different from the specific resins (hereinafter also referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, resins containing polysiloxanes or siloxane structures, (meth)acrylate resins, (meth)acrylate amide resins, amine ester resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins. For example, by further adding (meth)acrylate resins, a resin composition with excellent paintability can be obtained, as well as a pattern (cured product) with excellent solvent resistance. For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a (meth)acrylate resin with a high polymerizable group value (e.g., the molar content of polymerizable groups in 1g of resin is 1× ^10⁻³ moles/g or more) with a weight average molecular weight of 20,000 or less can be added to the resin composition, thereby improving the paintability of the resin composition, the solvent resistance of the pattern (cured material), etc.

When the resin composition of the present invention includes other resins, it is preferable that the content of the other resins relative to the total solid content of the resin composition is 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, even more preferably 2% by mass or more, still more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, it is preferable that the content of the other resins in the resin composition of the present invention relative to the total solid content of the resin composition is 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less. Furthermore, as a preferred embodiment of the resin composition of the present invention, it is also possible to design an embodiment with a low content of other resins. In the above-mentioned embodiments, it is preferable that the content of other resins relative to the total solid content of the resin composition is 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. There is no particular limitation on the lower limit of the above content, as long as it is 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or it may contain two or more types. When two or more types are contained, it is preferable that the total amount is within the above-mentioned range.

<Polymerizable Compounds> Preferably, the resin composition of this invention includes polymerizable compounds. Examples of polymerizable compounds include free radical crosslinkers or other crosslinking agents.

[Free Radical Crosslinker] The resin composition of this invention preferably contains a free radical crosslinker. The free radical crosslinker is a compound having a free radical polymerizable group. As a free radical polymerizable group, it is preferable to have a group containing an ethylene unsaturated bond. Examples of such groups containing ethylene unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acrylyl, cis-butenylideneimino, and (meth)acrylamide. Among these, (meth)acrylyl, (meth)acrylamide, and vinylphenyl are preferred as groups containing ethylene unsaturated bonds, and (meth)acrylyl is more preferred from a reactivity point of view.

The free radical crosslinker is preferably a compound having one or more ethylene unsaturated bonds, but more preferably a compound having two or more. The free radical crosslinker may have three or more ethylene unsaturated bonds. Among the compounds having two or more ethylene unsaturated bonds, compounds having 2 to 15 ethylene unsaturated bonds are preferred, compounds having 2 to 10 ethylene unsaturated bonds are more preferred, and compounds having 2 to 6 ethylene unsaturated bonds are even more preferred. Furthermore, from the viewpoint of the film strength of the obtained pattern (cured material), the resin composition of the present invention comprising compounds having two ethylene unsaturated bonds and the aforementioned compounds having three or more ethylene unsaturated bonds is also preferred.

The molecular weight of the free radical crosslinker is preferably below 2,000, even better below 1,500, and further preferably below 900. The lower limit of the molecular weight of the free radical crosslinker is preferably above 100.

Specific examples of free radical crosslinkers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or hydrogen thio groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids, are also preferred. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reactions of unsaturated carboxylic acid esters or amides with deionizing substituents such as halogen groups or toluenesulfonoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. As another example, compounds that can be substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc., can also be used instead of the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

Furthermore, it is preferable that the free radical crosslinker is a compound with a boiling point above 100°C at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trihydroxymethyl ethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl tetramethyl acrylate, neopentyl tetramethyl acrylate, dinepentyl tetramethyl acrylate, dinepentyl tetramethyl acrylate, dinepentyl tetramethyl acrylate, hexaethylene glycol di(meth)acrylate, trihydroxymethyl propane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanate, glycerol, or trihydroxymethyl ethane, which are added to polyfunctional alcohols to form ethylene oxide or propylene oxide, followed by (meth)acrylate addition. Compounds obtained by esterification, such as ethyl aminocarbamates of (meth)acrylate described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, epoxy acrylates as reaction products of epoxy resins and (meth)acrylic acid, and other multifunctional acrylates or methacrylates and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting compounds such as glycidyl (meth)acrylate, which have cyclic ether groups and vinyl unsaturated bonds, with polyfunctional carboxylic acids.

Furthermore, as a preferred free radical crosslinking agent besides those mentioned above, compounds having a ring and having two or more ethylene-unsaturated groups, or cardo resins, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, can also be used.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, can also be used. Additionally, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, those described as photopolymerizable monomers and oligomers in the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference, may also be used more readily.

Furthermore, in Japanese Patent Application Publication No. 10-062986, the following compounds, which are described together with specific examples of formulas (1) and (2), can also be used as free radical crosslinking agents. These compounds are obtained by esterification of (meth)acrylate after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

Furthermore, compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, the contents of which are incorporated in this specification.

As free radical crosslinking agents, dinepentylenetetroxide triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dinepentylenetetroxide tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dinepentylenetetroxide penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), and dinepentylenetetroxide hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH: manufactured by Shin-Nakamura Chemical Co., Ltd.) (Made by Co., Ltd.) and the structure in which the (meth)acrylic acid groups are bonded by ethylene glycol residues or propylene glycol residues is preferred. These oligomer types can also be used.

Commercially available free radical crosslinking agents include, for example, SR-494 (a tetrafunctional acrylate with four ethoxy groups) manufactured by Sartomer Company, Inc.; SR-209, 231, and 239 (difunctional methacrylates with four ethoxy groups) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with a pentenoxy group) manufactured by Nippon Kayaku Co., Ltd.; TPA-330 (a trifunctional acrylate with three isobutoxy groups); ethyl carbamate oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.); NK Ester M-40G, NK Ester 4G, NK Ester M-9300, and NK Ester... A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (NOF CORPORATION), etc.

As free radical crosslinking agents, ethyl carbamate acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and ethyl carbamate compounds with an ethylene oxide backbone as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as a free radical crosslinking agent, compounds having an amino group structure or a sulfide structure within the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

Free radical crosslinkers can be free radical crosslinkers containing acid groups such as carboxyl groups and phosphate groups. It is preferable that the free radical crosslinker containing acid groups is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. It is even more preferable that the free radical crosslinker contains acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of an aliphatic polyhydroxy compound. Particularly preferred are free radical crosslinkers containing acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of an aliphatic polyhydroxy compound, in which the aliphatic polyhydroxy compound is a neopentyl tetrol or dinepentyl tetrol. Commercially available examples include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD., such as M-510 and M-520.

The preferred acid value for free radical crosslinkers containing acid groups is 0.1–300 mg KOH/g, with a particularly preferred value of 1–100 mg KOH/g. As long as the acid value of the free radical crosslinker is within the above range, the manufacturing process is excellent, resulting in excellent developing properties. Furthermore, it exhibits good polymerizability. The above acid values are determined according to JIS K 0070:1992.

From the perspectives of pattern resolution and membrane stretchability, it is preferable to use difunctional methacrylates or acrylates in the resin composition. Specific compounds that can be used include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol dimethacrylate. Acrylic esters, dihydroxymethyltricyclodecane diacrylate, dihydroxymethyltricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, difunctional acrylates having other ethyl carbamate bonds, and difunctional methacrylates having ethyl carbamate bonds. Two or more of these can be mixed as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain molecular weight of approximately 200. Regarding the resin composition of this invention, from the viewpoint of suppressing warping by controlling the elastic modulus accompanying the pattern (cured material), a monofunctional free radical crosslinker can be preferably used as the free radical crosslinker. As a monofunctional free radical crosslinking agent, preferably used are n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactone, and alkenyl glycidyl ethers. As a monofunctional free radical crosslinking agent, compounds with a boiling point above 100°C at ambient pressure are also preferred to suppress pre-exposure volatilization. Besides these, examples of allyl compounds, such as diallyl phthalate and triallyl trimellitate, are examples of free radical crosslinking agents with two or more functions.

In the presence of a free radical crosslinker, it is preferable that its content relative to the total solid content of the resin composition of the present invention is more than 0% by mass and less than 60% by mass. A lower limit of 5% by mass or more is more preferable. An upper limit of 50% by mass or less is more preferable, and 30% by mass or less is even more preferable.

Free radical crosslinking agents can be used alone or in combination of two or more. When using two or more, it is preferable that their total amount be within the range mentioned above.

[Other Crosslinking Agents] It is preferable that the resin composition of this invention includes other crosslinking agents different from the aforementioned free radical crosslinking agents. In this invention, other crosslinking agents refer to crosslinking agents other than the aforementioned free radical crosslinking agents. Preferably, the compound has a plurality of groups within its molecule that, upon photosensitization by the aforementioned photoacid or photoalkali generator, promote the formation of covalent bonds between it and other compounds in the composition or their reaction products. Preferably, the compound has a plurality of groups within its molecule that, upon the action of an acid or alkali, promote the formation of covalent bonds between it and other compounds in the composition or their reaction products. It is also preferable that the compound has a plurality of groups within its molecule that, upon the action of an acid or alkali, promote the formation of covalent bonds between it and other compounds in the composition or their reaction products. The aforementioned acid or alkali is preferably generated from a photoacid generator or a photoalkali generator during the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of acetomethyl, hydroxymethyl, and alkoxymethyl are preferred; compounds having a structure in which at least one group selected from the group consisting of acetomethyl, hydroxymethyl, and alkoxymethyl is directly bonded to a nitrogen atom are even more preferred. As other crosslinking agents, examples include compounds having a structure in which the hydrogen atom of the aforementioned amine group is replaced by acetomethyl, hydroxymethyl, or alkoxymethyl groups through a reaction of formaldehyde or formaldehyde and an alcohol with melamine, glycourea, urea, alkyl urea, benzoguanamine, or other amine-containing compounds. The method for manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, the compound can also be an oligomer formed by the self-condensation of the hydroxymethyl groups of these compounds. Crosslinking agents using melamine as the above-mentioned amino-containing compounds are called melamine-based crosslinking agents; crosslinking agents using glycourea, urea, or alkylurea are called urea-based crosslinking agents; crosslinking agents using alkylurea are called alkylurea-based crosslinking agents; and crosslinking agents using benzoguanidine are called benzoguanidine-based crosslinking agents. Of these, it is preferable that the resin composition of the present invention comprises at least one compound selected from the group consisting of urea-based crosslinkers and melamine-based crosslinkers, and even more preferably, it comprises at least one compound selected from the group consisting of glycourea-based crosslinkers and melamine-based crosslinkers described below.

As a compound containing at least one of the alkoxymethyl and acetoxymethyl groups of the present invention, examples of compounds in which the alkoxymethyl or acetoxymethyl group is directly substituted on the nitrogen atom or trianode of the aromatic group or the urea structure described below are provided as structural examples. Preferably, the alkoxymethyl or acetoxymethyl group in the above-mentioned compound has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. Preferably, the total number of alkoxymethyl and acetoxymethyl groups in the above-mentioned compound is 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. Preferably, the molecular weight of the above-mentioned compound is 1500 or less, and preferably 180 to 1200.

【Chemical Formula 36】

R ₁₀₀ represents an alkyl or acetyl group. R ₁₀₁ and R ₁₀₂ each represent a monovalent organic group and can bond with each other to form a ring.

As compounds in which alkoxymethyl or acetomethyl groups are directly substituted on an aromatic group, examples of compounds with the following general formula can be cited.

【Chemical Formula 37】

In the formula, X represents a single bond or a divalent organic group. Each R ₁₀₄ independently represents an alkyl or acetyl group. R ₁₀₃ represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under acid to produce an alkaline soluble group (e.g., a group that decomposes under acid, or a group represented by -C(R ⁴ ) _2COOR ⁵ (R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a group that decomposes under acid). R ₁₀₅ independently represents an alkyl or alkenyl group. a, b, and c are 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Regarding groups that decompose under the action of acid to produce an alkaline soluble group, groups that are desorbed under the action of acid, ^{and R5} in groups represented by -C( ^R4 ) _2COOR5 , examples include -C( _R36 )( _R37 )( _R38 ), -C(R36)( _R37 )( _OR39 ), and -C( _R01 )( _R02 )( _OR39 ). In the formula, _R36 to _R39 independently represent alkyl, cycloalkyl, aryl, aralkyl, or _alkenyl groups. _R36 and _R37 can be bonded to each other to form a ring. As the above-mentioned alkyl groups, alkyl groups with 1 to 10 carbon atoms are preferred, and alkyl groups with 1 to 5 carbon atoms are even more preferred. The alkyl group can be either linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is even more preferred. The cycloalkyl group can have a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon having 6 to 30 carbon atoms, and a phenyl group is even more preferred. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferred, and an aralkyl group having 7 to 16 carbon atoms is even more preferred. The aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred states of such alkyl and aryl groups are the same as the preferred states of the alkyl and aryl groups described above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and an alkenyl group having 3 to 16 carbon atoms is even more preferred. Furthermore, these groups may have known substituents to the extent that the effects of the present invention can be obtained.

R ₀₁ and R ₀₂ represent hydrogen atoms, alkyl, cycloalkyl, aryl, aralkyl or alkenyl groups, respectively.

The groups that decompose to produce alkali-soluble groups by the action of acid or that are released by the action of acid are preferably trialkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, they are trialkyl ester groups or acetal groups.

Specifically, the following structures can be cited as compounds having an alkoxymethyl group. Regarding compounds having an acetoxymethyl group, compounds in which the alkoxymethyl group of the following compounds is replaced with an acetoxymethyl group can be cited. As compounds having an alkoxymethyl group or an acetoxymethyl group within the molecule, the following compounds can be cited, but are not limited to these.

【Chemical Formula 38】

【Chemical Formula 39】

For compounds containing at least one of alkoxymethyl and acetoxymethyl groups, commercially available compounds or those synthesized by known methods may be used. From a heat resistance perspective, compounds in which the alkoxymethyl or acetoxymethyl group is directly substituted onto the aromatic ring or trihalomethane ring are preferred.

Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

Specific examples of urea crosslinking agents include monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetramethoxymethylated glycourea, monoethoxymethylated glycourea, diethoxymethylated glycourea, triethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea, etc. Urea crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea, Aldehyde crosslinking agents including monohydroxymethylated or dihydroxymethylated ethoxylated ... 1,3-Di(methoxymethyl)4,5-dihydroxy-2-imidazolidineone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone, etc.

Specific examples of benzoguanidine crosslinking agents include monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

In addition, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups, it is also preferable to use a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include benzyl glycol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxybenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenyl ether. Ketones, methoxymethylbenzoic acid methoxymethylphenyl ester, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

Other crosslinking agents can also be used, and some preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

Furthermore, it is preferable that the resin composition of the present invention includes at least one compound selected from the group consisting of epoxides, cyclobutanes and benzoxazines as other crosslinking agents.

-Epoxy Compounds (Compounds Containing Epoxy Groups)- As epoxy compounds, compounds with two or more epoxy groups per molecule are preferred. Epoxy groups undergo cross-linking reactions below 200°C and do not produce dehydration reactions caused by cross-linking, thus minimizing film shrinkage. Therefore, the presence of epoxy compounds is effective in inhibiting low-temperature curing and warping of the resin composition of this invention.

The presence of polyethylene oxide in the epoxy compound is preferred. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide refers to ethylene oxide with 2 or more repeating units, with 2 to 15 repeating units being preferred.

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and other alkyl glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polyalkylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; and epoxy-epoxy silicones such as polymethyl (glycidyloxypropyl)siloxane, but are not limited to these. Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, and EPICL. ON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, DIC) (manufactured by CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, ADEKA) (manufactured by CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, Daicel) (Manufactured by Nippon Kayaku Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Furthermore, the following compounds may also be used more favorably.

【Chemical Formula 40】

In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

Among the above structures, considering both heat resistance and elongation improvement, n of 1 to 2 and m of 3 to 7 are preferred.

-Oxycyclobutane compounds (compounds containing oxycyclobutyl groups)- Examples of oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl] ester, etc. As a concrete example, the ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (e.g., OXT-121, OXT-221) is a better choice, and two or more of these can be used alone or in combination.

-Benzoxazine compounds (compounds containing a benzoxazole group)- Because of the crosslinking reaction caused by ring-opening addition, benzooxazine compounds do not undergo degassing during hardening, thus further reducing thermal shrinkage and inhibiting warping, making them preferable.

Preferred examples of benzo[a]oxa compounds include P-d type benzo[a]oxa, F-a type benzo[a]oxa (these are product names, manufactured by Shikoku Chemicals Corporation), benzo[a]oxa adducts of polyhydroxystyrene resins, and phenolic varnish-type dihydrobenzo[a]oxa compounds. These can be used alone or in combination of two or more.

The content of other crosslinking agents relative to the total solid content of the resin composition of the present invention is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, further preferably 0.5-15% by mass, and especially preferably 1.0-10% by mass. The other crosslinking agents may be contained in only one type or in two or more types. When two or more other crosslinking agents are contained, it is preferable that their total content falls within the above range.

[Polymerization Initiator] The resin composition of this invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. Particularly, it is preferred to contain a photopolymerization initiator. The polymerization initiator is preferably a free radical polymerization initiator. There are no particular limitations on the free radical polymerization initiator, and it can be appropriately selected from known free radical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitizing to light in the ultraviolet to visible region is preferred. Furthermore, an active agent that generates active free radicals by interacting with a photosensitive agent may also be used.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 L· ^mol⁻¹ · ^cm⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). The molar absorptivity of the compound can be determined using known methods. For example, it is preferable to determine it using a UV-Vis spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) with ethyl acetate solvent at a concentration of 0.01 g/L.

As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (such as compounds with a trihalomethane skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethane skeleton, etc.), acetylphosphine compounds such as acetylphosphine oxides, hexaaryl diimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron-aromatic hydrocarbon complexes. For details regarding these contents, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015/199219, which are incorporated herein by reference. Furthermore, examples can be found in paragraphs 0065-0111 of Japanese Patent Application Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, and the MATERIAL STAGE. The peroxide-based photopolymerization initiators described in 37–60p, vol.19, No.3, 2019, the photopolymerization initiators described in International Publication No. 2018/221177, the photopolymerization initiators described in International Publication No. 2018/110179, the photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313 are also incorporated herein by reference.

As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated in this specification, may be cited. KAYACURE-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) may also be preferred in commercially available products.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and amide phosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators as described in Japanese Patent Application Publication No. 10-291969 and amide phosphine oxide-based initiators as described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369 and IRGACURE 379 (all manufactured by BASF) can be used.

As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, which have extremely high absorption wavelengths and are matched with light sources of wavelengths such as 365 nm or 405 nm, can also be used, and this content is incorporated into this specification.

Examples of acetylated phosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Additionally, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins B.V.), IRGACURE-819, or IRGACURE-TPO (all manufactured by BASF) can be used.

Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

Oxime compounds are a better example of photoradical polymerization initiators. Using oxime compounds allows for a more effective increase in exposure tolerance. Oxime compounds are particularly advantageous because they offer a wider exposure tolerance (exposure margin) and also act as photocuring accelerators.

Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science and... Compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Publication No. 2000-066385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent Application Publication No. 6065596, and international publication No. 2 The compounds described in 015/152153, the compounds described in International Publication No. 2017/051680, the compounds described in Japanese Patent Application Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, and the compounds described in International Publication No. 2013/167515 are included in this specification.

Preferred oxime compounds include, for example, compounds with the following structures: 3-benzoxylidene-iminobutane-2-one, 3-acetoxylidene-iminobutane-2-one, 3-propoxylidene-iminobutane-2-one, 2-acetoxylidene-iminopentane-3-one, 2-acetoxylidene-1-phenylpropane-1-one, 2-benzoxylidene-1-phenylpropane-1-one, 3-(4-toluenesulfonoxy)iminobutane-2-one, and 2-ethoxycarbonyloxylidene-1-phenylpropane-1-one. In the resin composition of the present invention, the use of oxime compounds (oxime-based photoradical polymerization initiators) as photoradical polymerization initiators is particularly preferred. Oxime-based photoradical polymerization initiators have a linker group >C=N-O-C(=O)- within the molecule.

【Chemical Formula 41】

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF) and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, the photoradical polymerization initiator 2 disclosed in Japanese Patent Application Publication No. 2012-014052) are also suitable. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLSNCI-730, NCI-831, and ADEKA ARKLSNCI-930 (manufactured by ADEKA Corporation) are also suitable. Furthermore, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Also, oxime compounds with the following structure can be used. [Chemical Formula 42]

Oxime compounds with cyclohexane can also be used as photoradical polymerization initiators. Specific examples of oxime compounds with cyclohexane include the compound described in Japanese Patent Application Publication No. 2014-137466 and the compound described in Japanese Patent No. 06636081, the contents of which are incorporated herein by reference.

As a photoradical polymerization initiator, oxime compounds having at least one benzene ring in the carbazole ring forming a naphthalene ring skeleton can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013/083505, which is incorporated herein by reference.

Furthermore, oxime compounds containing fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, the contents of which are incorporated in this specification.

As a photopolymerization initiator, oxime compounds containing nitro groups can be used. It is also preferable to use oxime compounds containing nitro groups as dimers. Specific examples of oxime compounds containing nitro groups include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007 to 0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLSNCI-831 (manufactured by ADEKA Corporation) is another example of an oxime compound containing nitro groups.

Oxime compounds with a benzofuran skeleton can also be used as photoradical polymerization initiators. For example, OE-01 to OE-75 are described in International Publication No. 2015/036910.

As a photoradical polymerization initiator, it can also be used in oxime compounds with hydroxyl substituents bonded to the carbazole skeleton. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055, the contents of which are incorporated herein by reference.

As a photopolymerization initiator, an oxime compound having an aromatic cycloalcoholic group Ar ^OX1 (hereinafter also referred to as an oxime compound OX) can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cycloalcoholic Ar ^OX1 include vinyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfinyl, arylsulfinyl, and cyano groups. Vinyl and nitro groups are preferred, and vinyl is even more preferred considering its ease of forming films with excellent lightfastness, while benzoyl is further preferred. Benzyl may have substituents. As substituents, halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthio, arylthio, acetyl, or amino are preferred, alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthio, arylthio, or amino are even more preferred, and alkoxy, alkylthio, or amino are even more preferred.

The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and formula (OX2), with the compound represented by formula (OX2) being more preferred. [Chemical Formula 43] In the formula, ^RX1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetyl, acetoxy, amino, phosphinyl, aminomethyl, or aminosulfonyl; ^RX2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetoxy, or amino; and ^RX3 to ^RX14 each independently represent a hydrogen atom or a substituent. At least one of ^RX10 to ^RX14 is an electron-withdrawing group.

In the above formula, ^RX12 is an electron-withdrawing group, and ^RX10 , ^RX11 , ^RX13 , and ^RX14 are preferably hydrogen atoms.

As a specific example of an oxime compound OX, the compound described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 is cited, the contents of which are incorporated in this specification.

Examples of the best oxime compounds include those with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 or those with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061, the contents of which are incorporated herein by reference.

From the perspective of exposure sensitivity, photoradical polymerization initiators are preferably selected from the group consisting of trihalomethane trihalomethane compounds, benzyl dimethyl ketone compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetophosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onmium salts, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethanediazole compounds, and 3-aryl-substituted coumarin compounds.

A further preferred photoradical polymerization initiator is a trihalomethane trihalomethane compound, an α-aminoketone compound, an acetophosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. It is even more preferred to select at least one compound from the group consisting of trihalomethane trihalomethane compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. It is even more preferred to use a metallocene compound or an oxime compound.

Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenones; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-methylpheninylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-methylpheninyl-acetone-1; quinones formed by condensation of aromatic rings with alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkyl benzoin; and benzyl derivatives such as benzyl dimethyl ketone. Additionally, compounds represented by the following formula (I) can also be used.

【Chemical Formula 44】

In formula (I), ^RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, at least one of which is a substituted phenyl or biphenyl group. ^RI01 is a group represented by formula (II) or is the same group as ^RI00 . ^RI02 to ^RI04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

【Chemical Formula 45】

In the formula, ^RI05 to ^RI07 are the same as ^RI02 to ^RI04 in the above formula (I).

Furthermore, the photoradical polymerization initiator can also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015/125469, which is incorporated in this specification.

As photoradical polymerization initiators, difunctional or trifunctional or higher photoradical polymerization initiators can also be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Furthermore, when using compounds with asymmetrical structures, crystallinity decreases while solubility in solvents and the like increases, making them less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functions include dimers of oxime compounds described in Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2011-524436, International Publication No. 2015/004565, paragraphs 0407 to 0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017/033680; and compounds (E) and ( ) described in Japanese Patent Application Publication No. 2013-522445. G), Cmpd1 to 7 as described in International Publication No. 2016/034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators as described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) as described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators as described in Japanese Patent Application Publication No. 6469669, etc., are incorporated herein by reference.

When a photopolymerization initiator is included, its content relative to the total solid content of the resin composition of the present invention is preferably 0.1–30% by mass, more preferably 0.1–20% by mass, even more preferably 0.5–15% by mass, and still more preferably 1.0–10% by mass. The photopolymerization initiator may be one type or two or more types. When two or more photopolymerization initiators are included, the total amount is preferably within the above range. Furthermore, since the photopolymerization initiator sometimes also functions as a thermal polymerization initiator, crosslinking based on the photopolymerization initiator is sometimes carried out by heating in an oven or heating plate.

[Sensitizers] Resin components may contain sensitizers. Sensitizers absorb specific active radiation to become electronically excited. These excited sensitizers then come into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. Consequently, the thermal free radical polymerization initiators and photofree radical polymerization initiators undergo chemical changes and decompose, generating free radicals, acids, or bases. As usable sensitizers, compounds such as benzophenone, milchnerone, oxanaphthone, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzylene, oxocyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthrene, pyrrolopyrazole methylene azo, phthalocyanine, benzopiperanone, and indigo compounds can be used. Examples of sensitizers include milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylenepropanedihydroindene, and p-dimethylamino Benzylene dihydroindone, 2-(p-dimethylaminophenylbenzylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylene)acetone, 1,3-bis(4'-diethylaminobenzylene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated-7-dimethylaminocoumarin, 3-ethoxy Carbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-methyl-3-pyrophyllylbenzophenone, isoamyl dimethylaminobenzoate, diethylamine Isoamyl benzoate, 2-phenylbenzimidazole, 1-phenyl-5-phenyltetrazolium, 2-phenylbenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetylamine, benzoaniline, N-methylacetylaniline, 3',4'-dimethylacetylaniline, etc. Also, other sensitizing dyes can be used. For detailed information on sensitizing dyes, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solid content of the resin composition is preferably 0.01–20% by weight, more preferably 0.1–15% by weight, and even more preferably 0.5–10% by weight. A single sensitizer may be used alone, or two or more may be used in combination.

[Chain Transfer Agent] The resin composition of this invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the 3rd edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds containing -SS-, -SO-, _-S- , -NO-, SH, PH, SiH, and GeH within the molecule, as well as dithiobenzoic acid, trithiocarbonate, dithiocarbamate, xanthate compounds, etc., with thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can generate free radicals by donating hydrogen to low-activity free radicals or by deprotonation after oxidation. In particular, it allows for better use of thiol compounds.

Furthermore, the chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, which is incorporated in this specification.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solid content of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, it is preferable that their total content is within the above-mentioned range.

[Photosensitive Acid Generator] The resin composition of this invention preferably contains a photosensitive acid generator. The photosensitive acid generator refers to a compound that produces at least one of Brinzyl acid and Lewis acid upon irradiation with light of 200 nm to 900 nm. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, the photosensitive acid generator is preferably capable of producing acid by photosensitivity. Examples of the acids produced include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfenamides.

Examples of photoacid generators used in the resin composition of this invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organoborate compounds, disulfonate compounds, and onmium salt compounds. From the viewpoints of sensitivity and storage stability, organohalogen compounds, oxime sulfonate compounds, and onmium salt compounds are preferred; from the viewpoints of the mechanical properties of the formed film, oxime esters are preferred.

Examples of quinone diazonium compounds include those obtained by attaching a quinone diazonium sulfonate bond to a monovalent or polyvalent hydroxyl group, those obtained by attaching a quinone diazonium sulfonate sulfonamide bond to a monovalent or polyvalent amine group, and those obtained by attaching a quinone diazonium sulfonate bond and/or a sulfonamide bond to a polyhydroxy polyamine compound. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinone diazonium, but it is preferable that at least 40 mol% of the total functional groups are substituted with quinone diazonium on average. By using this quinone diazide compound, it is possible to obtain a resin composition that is photosensitive to i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) of a mercury lamp, which is a typical ultraviolet light source.

As hydroxyl compounds, specifically, examples include phenols, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, terbutanol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, and BisRS- 26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (These are product names, Honshu) The products include, but are not limited to, BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), phenolic varnish resins, etc.

As an amino compound, examples include aniline, methylaniline, diethylamine, butylamine, 1,4-epenylphenyldiamine, 1,3-epenylphenyldiamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, etc., but are not limited to these.

Furthermore, examples of polyhydroxy polyamine compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but they are not limited to these.

Among these, phenolic compounds and esters containing a 4-naphthoquinone diazidesulfonate group are preferred as quinone diazide compounds. This allows for higher sensitivity and resolution for i-ray exposure.

The content of the quinone diazonium compound used in the resin composition of this invention is preferably 1 to 50 parts by weight per 100 parts by weight of the resin, and more preferably 10 to 40 parts by weight. By setting the content of the quinone diazonium compound within this range, the contrast between the exposed and unexposed areas can be obtained, thereby achieving higher sensitivity, which is therefore preferable. Furthermore, sensitizers, etc., can be added as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compound"). There are no particular restrictions on the presence of an oxime sulfonate group, but oxime sulfonate compounds represented by the following formula (OS-1), the formula described later (OS-103), formula (OS-104), or formula (OS-105) are preferred.

【Chemical Formula 46】

In formula (OS-1), ^X3 represents an alkyl, alkoxy, or halogen atom. When there are multiple ^X3 atoms, they may be the same or different. The alkyl and alkoxy atoms in ^X3 may have substituents. As the alkyl group in ^X3 , a straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in ^X3 , a straight-chain or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in ^X3 , a chlorine or fluorine atom is preferred. In formula (OS-1), m3 represents an integer from 0 to 3, with 0 or 1 being preferred. When m3 is 2 or 3, the multiple ^X3 atoms may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl or aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group that can be substituted with W, a naphthyl group that can be substituted with W, or an anthracene group that can be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), m3 is 3, ^X3 is methyl, ^X3 is substituted at an ortho position, and ^R34 is preferably a straight-chain alkyl group with 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorcanylmethyl or p-tolyl.

As specific examples of oxime sulfonate compounds represented by formula (OS-1), the following compounds described in paragraphs 0064 to 0068 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0158 to 0167 of Japanese Patent Application Publication No. 2015-194674 are examples, and these contents are incorporated herein by reference.

【Chemical Formula 47】

In formulas (OS-103) to (OS-105), ^Rs1 represents an alkyl, aryl, or heteroaryl group; sometimes there are multiple ^Rs2, each independently representing a hydrogen atom, alkyl, aryl, or halogen atom; sometimes there are multiple ^Rs6, each independently representing a halogen atom, alkyl, alkoxy, sulfonic acid group, aminosulfonyl, or alkoxysulfonyl group; Xs represents O or S; ns represents 1 or 2; and ms represents an integer from 0 to 6. In formulas (OS-103) to (OS-105), the alkyl (preferably with 1 to 30 carbons), aryl (preferably with 6 to 30 carbons), or heteroaryl (preferably with 4 to 30 carbons) represented by ^Rs1 may have known substituents within the range that allows the effects of the present invention to be obtained.

In formulas (OS-103) to (OS-105), ^Rs2 is preferably a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms), or an aryl group (preferably with 6 to 30 carbon atoms), with a hydrogen atom or alkyl group being more preferred. In compounds where two or more Rs2 ^groups are present, it is preferred that one or two are alkyl, aryl, or halogen atoms, more preferred that one is an alkyl, aryl, or halogen atom, and especially preferred that one is an alkyl group and the remainder are hydrogen atoms. The alkyl or aryl group represented by ^Rs2 may have known substituents within the range that allows the effects of the present invention to be obtained. In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, with O being preferred. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a member is a 5-member ring or a 6-member ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns being 1 is preferred, and when Xs is S, ns being 2 is preferred. In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have substituents. In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, with integers from 0 to 2 being preferred, 0 or 1 being more preferred, and 0 being particularly preferred.

Furthermore, the compound represented by formula (OS-103) is preferably represented by formula (OS-106), formula (OS-110), or formula (OS-111); the compound represented by formula (OS-104) is preferably represented by formula (OS-107); and the compound represented by formula (OS-105) is preferably represented by formula (OS-108) or formula (OS-109). [Chemical Formula 48]

In formulas (OS-106) to (OS-111), ^Rt1 represents an alkyl, aryl, or heteroaryl group; ^Rt7 represents a hydrogen atom or a bromine atom; ^Rt8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl, or chlorophenyl group; ^Rt9 represents a hydrogen atom, a halogen atom, a methyl or methoxy group; and ^Rt2 represents a hydrogen atom or a methyl group. In formulas (OS-106) to (OS-111), ^Rt7 represents a hydrogen atom or a bromine atom, with a hydrogen atom being preferred.

In formulas (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group. It is preferred that the alkyl group having 1 to 8 carbon atoms or a halogen atom or a phenyl group has 1 to 8 carbon atoms, even more preferred, and alkyl group having 1 to 6 carbon atoms is even more preferred. Methyl is particularly preferred.

In formulas (OS-106) to (OS-111), ^Rt9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, with a hydrogen atom being preferred. ^Rt2 represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime can be any one of them or a mixture thereof. As specific examples of oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674 are examples, and these contents are incorporated herein by reference.

As a preferred alternative to oxime sulfonate compounds containing at least one oxime sulfonate group, compounds represented by the following formulas (OS-101) and (OS-102) can be cited.

【Chemical Formula 49】

In formula (OS-101) or (OS-102), ^Ru9 represents a hydrogen atom, alkyl, alkenyl, alkoxy, alkoxycarbonyl, acetyl, aminomethyl, aminosulfonyl, sulfonyl, cyano, aryl, or heteroaryl. It is preferred that ^Ru9 is cyano or aryl, and it is further preferred that ^Ru9 is cyano, phenyl, or naphthyl. In formula (OS-101) or (OS-102), ^Ru2a represents an alkyl or aryl group. In formula (OS-101 ^{) or (OS-102), Xu represents -O-, -S-, -NH-, -NRu5-, -CH2-, -CRu6H-, or CRu6Ru7-, where Ru5 to Ru7 each independently} _represent ^an alkyl or aryl group.

In formula (OS-101) or formula (OS-102), ^Ru1 to ^Ru4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a amide group, a sulfonyl group, a cyano group, or an aryl group. Two of ^Ru1 to ^Ru4 can be bonded together to form a ring. In this case, the ring can undergo ring condensation to form a condensed ring together with the benzene ring. Preferably, ^Ru1 to ^Ru4 are hydrogen atoms, halogen atoms, or alkyl groups, and it is also preferable that at least two of ^Ru1 to ^Ru4 are bonded together to form an aryl group. Preferably, all of ^Ru1 to ^Ru4 are hydrogen atoms. All of the above substituents can further have substituents.

The compound represented by formula (OS-101) is preferably represented by formula (OS-102). Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring can be either one or a mixture thereof. Specific examples of compounds represented by formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674, the contents of which are incorporated herein by reference. Among the above-mentioned compounds, b-9, b-16, b-31, and b-33 are preferred. [Chemical Formula 50] Commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

Furthermore, a better example can be given by a compound represented by the following structural formula: [Chemical Formula 51]

As for organic halogenated compounds, specific examples include Wakabayashi et al.'s "Bull Chem. Soc Japan" 42,2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication Nos. 46-4605, 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, and M.P. Hutt's "Jurnal of Heterocyclic Compounds described in Chemistry 1 (No. 3), (1970), etc., are incorporated herein by reference. In particular, oxazole compounds substituted with trihalomethanes, such as symmetrical trihalomethane compounds, are preferred examples. More preferably, symmetrical trihalomethane derivatives formed by the bonding of at least one mono, di, or trihalomethane-substituted methyl group with a symmetrical trihalomethane ring are examples. Specifically, examples include 2,4,6-tris(monochloromethyl)-symmetrical trihalomethane, 2,4,6-tris(dichloromethyl)-symmetrical trihalomethane, 2,4,6-tris(trichloromethyl)-symmetrical trihalomethane, 2-methyl-4,6-bis(trichloromethyl)-symmetrical trihalomethane, and 2-n-propyl-4,6-bis(trichloromethyl)-symmetrical trihalomethane. Tris(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-symmetric tri ... [Phenyl]-2,4-butadienyl]-4,6-bis(trichloromethyl)-symmetric tris(trichloromethyl)-2-styryl-4,6-bis(trichloromethyl)-symmetric tris(trichloromethyl)-2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-symmetric tris(trichloromethyl)-2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-symmetric tris(trichloromethyl)-2-(p-tolyl)-4,6-bis(trichloromethyl)-symmetric tris(trichloromethyl)-2-(4-naphthoxy) Naphthyl)-4,6-bis(trichloromethyl)-symmetric tris(trichloromethyl), 2-phenylthio-4,6-bis(trichloromethyl)-symmetric tris(trichloromethyl), 2-benzylthio-4,6-bis(trichloromethyl)-symmetric tris(trichloromethyl), 2,4,6-tris(dibromomethyl)-symmetric tris(trichloromethyl)-symmetric tris(trichloromethyl), 2-methyl-4,6-bis(tribromomethyl)-symmetric tris(trichloromethyl), 2-methoxy-4,6-bis(tribromomethyl)-symmetric tris(trichloromethyl), etc.

Examples of organoborate compounds include, for instance, Japanese Patent Application Publication No. 62-143044, Japanese Patent Application Publication No. 62-150242, Japanese Patent Application Publication No. 9-188685, Japanese Patent Application Publication No. 9-188686, Japanese Patent Application Publication No. 9-188710, Japanese Patent Application Publication No. 2000-131837, Japanese Patent Application Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Publication No. 2002-116539, and Kunz, Martin, “Rad Tech’98. Proceeding April”. The organoborates described in "Chicago" etc., Japanese Patent Application Publication Nos. 6-157623, 6-175564, and 6-175561, and the organoboronium complexes or organoboronoxystrontium complexes described in Japanese Patent Application Publication Nos. 6-175554 and 6-175553, etc. Specific examples include organoboronium complexes described in Japanese Patent Application Publication No. 9-188710, and organoboronium transition metal coordination complexes such as Japanese Patent Application Publication No. 6-348011, Japanese Patent Application Publication No. 7-128785, Japanese Patent Application Publication No. 7-140589, Japanese Patent Application Publication No. 7-306527, and Japanese Patent Application Publication No. 7-292014, the contents of which are incorporated herein by reference.

Examples of disulfide compounds include compounds described in Japanese Patent Application Publication No. 61-166544 and Japanese Patent Application No. 2001-132318, as well as diazonium compounds.

Examples of such onium salt compounds include S.I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), and T.S. Bal et al. Diazo salts as described in al, Polymer, 21,423 (1980), ammonium salts as described in U.S. Patent No. 4,069,055, Japanese Patent Application Publication No. 4-365049, phosphonium salts as described in the specifications of U.S. Patent Nos. 4,069,055 and 4,069,056, European Patent Nos. 104,143, 339,049 and 410,201, tin salts as described in Japanese Patent Application Publication Nos. 2-150848 and 2-296514, European Patent Nos. 370,693 and 39 The strontium salts described in the specifications of J.V. Crivello's patents 0,214, 233,567, 297,443, 297,442, 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, 2,904,626, 3,604,580, and 3,604,581, and J.V. Crivello's patents. Selenium salts described in J.V. Crivello et al., Macromolecules, 10(6), 1307(1977), and arsenic salts, pyridinium salts, etc. described in C.S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) are included in this specification.

Examples of onium salts represented by the following general formulas (RI-I) to (RI-III) can be cited. [Chemical Formula 52] In formula (RI-I), Ar ₁₁ represents an aryl group having 1 to 6 substituents with 20 or fewer carbon atoms. Examples of preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, alkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 2 to 12 carbon atoms, alkylamide groups of alkyl groups having 1 to 12 carbon atoms, or arylamide groups of aryl groups having 6 to 20 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z ₁₁ ^- indicates a monovalent anion, which can be a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, or sulfate ion. From a stability perspective, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinic acid ion are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ independently represent aryl groups with 1 to 20 carbon atoms that may have 1 to 6 substituents. Examples of preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 1 to 12 carbon atoms of each alkyl group, alkylamide or arylamide groups with 1 to 12 carbon atoms of an alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. Z ₂₁ ^- indicates a monovalent anion, which can be a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, or sulfate ion. Considering stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, or carboxylic acid ion are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ independently represent aryl, alkyl, alkenyl, or alkynyl groups with 6 to 20 carbon atoms that can have 1 to 6 substituents. Preferably, aryl groups are preferred in terms of reactivity and stability. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms in each alkyl group, alkylamide or arylamide groups having 1 to 12 carbon atoms in an alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z ₃₁ ^- indicates a monovalent anion, which can be a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, or sulfate ion. Considering stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, or carboxylic acid ion are preferred.

Specific examples of better photosensitive acid generators include the following: [Chemical Formula 53] 【Chemical Formula 54】 【Chemical Formula 55】 【Chemical Formula 56】

The photoacid generator is preferably used at 0.1–20% by mass relative to the total solids content of the resin composition, more preferably at 0.5–18% by mass, further preferably at 0.5–10% by mass, even more preferably at 0.5–3% by mass, and still more preferably at 0.5–1.2% by mass. The photoacid generator can be used alone or in combination with other agents. When used in combination with other agents, the total amount within the above-mentioned ranges is preferred. Furthermore, it is preferable to use it in combination with a sensitizer to impart photosensitivity to the desired light source.

<Alkali Generator> The resin composition of the present invention may contain an alkali generator. The alkali generator is a compound capable of generating alkali through physical or chemical action. Preferred alkali generators for the resin composition of the present invention include thermo-alkali generators and photo-alkali generators. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali generator. By incorporating a thermal alkali generator into the resin composition, such as one that promotes the cyclization reaction of precursors through heating, the cured material exhibits excellent mechanical properties or chemical resistance. For example, its performance as an interlayer insulating film for rewiring layers in semiconductor packaging is improved. The alkali generator can be either ionic or nonionic. Examples of alkalis generated from the alkali generator include, for instance, secondary and tertiary amines. There are no particular limitations on the alkali generator used in this invention; known alkali generators can be used. Commonly known alkali-generating agents include, for example, aminomethyloxime compounds, aminomethylhydroxylamine compounds, carbamic acid compounds, methylamine compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonic acid amide compounds, imidazole derivative compounds, aminoimine compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimine compounds, phthalimine derivative compounds, and acetoimine compounds. Specific compounds that are nonionic alkali-generating agents include those represented by formulas (B1), (B2), or (B3). [Chemical Formula 57]

In formulas (B1) and (B2), ^Rb1 , ^Rb2 , and ^Rb3 are independently organic groups, halogen atoms, or hydrogen atoms that do not possess a tertiary amine structure. ^Rb1 and ^Rb2 do not simultaneously constitute hydrogen atoms. Furthermore, ^Rb1 , ^Rb2 , and ^Rb3 do not possess a carboxyl group. Moreover, in this specification, a tertiary amine structure refers to a structure where all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, it is not limited to the case where the bonded carbon atoms are carbon atoms forming a carbonyl group, i.e., when they form a amide group together with the nitrogen atom.

In formulas (B1) and (B2), it is preferable that at least one of ^Rb1 , ^Rb2 , and ^Rb3 contains a cyclic structure, and it is even more preferable that at least two contain a cyclic structure. The cyclic structure can be either a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring formed by the condensation of two monocyclic rings. It is preferable that the monocyclic ring is a 5-membered or 6-membered ring, with a 6-membered ring being more preferred. It is preferable that the monocyclic ring is a cyclohexyl ring or a benzene ring, with a cyclohexyl ring being more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably with 1-24 carbon atoms, more preferably with 2-18 carbon atoms, and even more preferably with 3-12 carbon atoms), alkenyl groups (preferably with 2-24 carbon atoms, more preferably with 2-18 carbon atoms, and even more preferably with 3-12 carbon atoms), aryl groups (preferably with 6-22 carbon atoms, more preferably with 6-18 carbon atoms, and even more preferably with 6-10 carbon atoms), or aralkyl groups (preferably with 7-25 carbon atoms, more preferably with 7-19 carbon atoms, and even more preferably with 7-12 carbon atoms). These groups may have substituents within the scope of achieving the effects of the present invention. ^Rb1 and ^Rb2 may bond to each other to form a ring. A nitrogen-containing heterocycle with 4-7 members is preferred as the formed ring. In particular, Rb ¹ and Rb ² are preferably straight-chain, branched or cyclic alkyl groups (preferably with 1 to 24 carbons, more preferably with 2 to 18 carbons, and even more preferably with 3 to 12 carbons) that may have substituents, and are preferably cycloalkyl groups (preferably with 3 to 24 carbons, more preferably with 3 to 18 carbons, and even more preferably with 3 to 12 carbons) that may have substituents, and are even more preferably cyclohexyl groups that may have substituents.

Examples of Rb ³ include alkyl groups (preferably with 1-24 carbons, more preferably with 2-18 carbons, and even more preferably with 3-12 carbons), aryl groups (preferably with 6-22 carbons, more preferably with 6-18 carbons, and even more preferably with 6-10 carbons), alkenyl groups (preferably with 2-24 carbons, more preferably with 2-12 carbons, and even more preferably with 2-6 carbons), and aralkyl groups (preferably with 7-23 carbons, more preferably with 7-19 carbons, and even more preferably with 7-12 carbons). The preferred carbon groups are aryl (preferably 8-24 carbons, more preferably 8-20, and even more preferably 8-16 carbons), alkoxy (preferably 1-24 carbons, more preferably 2-18, and even more preferably 3-12 carbons), aryloxy (preferably 6-22 carbons, more preferably 6-18, and even more preferably 6-12 carbons), or arylalkoxy (preferably 7-23 carbons, more preferably 7-19, and even more preferably 7-12 carbons). Cycloalkyl (preferably 3-24 carbons, more preferably 3-18, and even more preferably 3-12 carbons), aryl, and arylalkoxy are preferred. ^Rb3 may also have substituents within the scope of the invention's effects.

The compound represented by formula (B1) is preferably represented by formula (B1-1) or formula (B1-2) below. [Chemical Formula 58]

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² have the same meanings as Rb ¹ and Rb ² in formula (B1), respectively. Rb ¹³ is an alkyl group (preferably with 1 to 24 carbons, more preferably with 2 to 18 carbons, and even more preferably with 3 to 12 carbons), an alkenyl group (preferably with 2 to 24 carbons, more preferably with 2 to 18 carbons, and even more preferably with 3 to 12 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 12 carbons), or an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 12 carbons). Substituents may be present within the scope of achieving the effects of the present invention. Among them, it is preferred that Rb ¹³ is an aralkyl group.

Rb ³³ and Rb ³⁴ are respectively independently hydrogen atoms, alkyl groups (preferably with 1 to 12 carbons, more preferably with 1 to 8 carbons, and even more preferably with 1 to 3 carbons), alkenyl groups (preferably with 2 to 12 carbons, more preferably with 2 to 8 carbons, and even more preferably with 2 to 3 carbons), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), aralkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), and hydrogen atoms are preferred.

Rb ³⁵ is alkyl (preferably 1-24 carbons, more preferably 1-12, and even more preferably 3-8 carbons), alkenyl (preferably 2-12 carbons, more preferably 2-10, and even more preferably 3-8 carbons), aryl (preferably 6-22 carbons, more preferably 6-18, and even more preferably 6-12 carbons), aralkyl (preferably 7-23 carbons, more preferably 7-19, and even more preferably 7-12 carbons), with aryl being preferred.

Furthermore, it is preferable that the compound represented by formula (B1-1) is also represented by formula (B1-1a). [Chemical Formula 59]

The meanings of Rb ¹¹ and Rb ¹² are the same as those of Rb ¹¹ and Rb ¹² in formula (B1-1). Rb ¹⁵ and Rb ¹⁶ are preferably hydrogen atoms, alkyl groups (preferably with 1 to 12 carbons, more preferably with 1 to 6 carbons, and even more preferably with 1 to 3 carbons), alkenyl groups (preferably with 2 to 12 carbons, more preferably with 2 to 6 carbons, and even more preferably with 2 to 3 carbons), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), aralkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), hydrogen atoms, or methyl groups. Rb ¹⁷ is an alkyl group (preferably with 1 to 24 carbons, more preferably with 1 to 12 carbons, and even more preferably with 3 to 8 carbons), an alkenyl group (preferably with 2 to 12 carbons, more preferably with 2 to 10 carbons, and even more preferably with 3 to 8 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 12 carbons), or an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 12 carbons), wherein an aryl group is preferred.

【Chemical Formula 60】

In formula (B3), L represents an hydrocarbon group, which is a divalent hydrocarbon group with a saturated hydrocarbon on the path of the linking chain connecting adjacent oxygen and carbon atoms, and the number of atoms on the linking chain is three or more. Furthermore, ^RN1 and ^RN2 each independently represent a monovalent organic group.

In this specification, "linkage chain" refers to an atomic chain that connects two atoms or groups of atoms in the shortest possible (smallest number of atoms) path. For example, in a compound represented by the following formula, L is composed of phenyl-ethyl groups and has ethyl groups as saturated hydrocarbons, the linkage chain consists of four carbon atoms, and the number of atoms in the linkage chain path (i.e., the number of atoms constituting the linkage chain, hereinafter also referred to as "linkage chain length") is 4. [Chemical Formula 61]

The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linker chain) is preferably 3 to 24. An upper limit of 12 or less is more preferred, 10 or less is even more preferred, and 8 or less is particularly preferred. A lower limit of 4 or more is more preferred. Considering the need for rapid intramolecular cyclization reactions, the upper limit of the linker chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferred 5 or less. In particular, a linker chain length of 4 or 5 is preferred, with 4 being optimal. Preferred compounds as alkali-generating agents include, for example, those described in paragraphs 0102 to 0168 of International Publication No. 2020/066416 and those described in paragraphs 0143 to 0177 of International Publication No. 2018/038002.

Furthermore, it is preferable that the alkali-generating agent contains a compound represented by the following formula (N1). [Chemical Formula 62]

In formula (N1), ^RN1 and ^RN2 independently represent monovalent organic groups, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linker, preferably a divalent organic group. A linker chain length of 1 or more is preferred, and 2 or more is even better. As an upper limit, 12 or less is preferred, 8 or less is even better, and 5 or less is even better. The linker chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

In formula (N1), ^RN1 and ^RN2 independently represent monovalent organic groups (preferably with 1-24 carbons, more preferably with 2-18, and even more preferably with 3-12 carbons) and hydrocarbon groups (preferably with 1-24 carbons, more preferably with 1-12, and even more preferably with 1-10 carbons). Specifically, aliphatic hydrocarbon groups (preferably with 1-24 carbons, more preferably with 1-12, and even more preferably with 1-10) or aromatic hydrocarbon groups (preferably with 6-22 carbons, more preferably with 6-18, and even more preferably with 6-10 carbons) are preferred. If aliphatic hydrocarbon groups are used as ^RN1 and ^RN2 , the resulting base is highly basic, and therefore preferred. Furthermore, aliphatic and aromatic hydrocarbons can have substituents, and they can have oxygen atoms in the aliphatic hydrocarbon chain, the aromatic ring, or the substituents. In particular, examples of aliphatic hydrocarbons having oxygen atoms in the hydrocarbon chain can be illustrated.

Examples of aliphatic hydrocarbons constituting ^RN1 and ^RN2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of linear and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. Linear or branched chain alkyl groups with 1 to 24 carbon atoms are preferred, 2 to 18 are more preferred, and 3 to 12 are even more preferred. Examples of linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, dibutyl, tributyl, isopentyl, neopentyl, tripentyl, and isohexyl. Cyclic alkyl groups are preferably composed of 3 to 12 carbon atoms, with 3 to 6 being more preferred. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. Groups relating to the combination of cyclic and chain alkyl groups are preferably composed of 4 to 24 carbon atoms, with 4 to 18 being more preferred, and 4 to 12 being even more preferred. Examples of groups relating to the combination of cyclic and chain alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl. Alkyl groups having an oxygen atom in the chain are preferably composed of 2 to 12 carbon atoms, with 2 to 6 being more preferred, and 2 to 4 being even more preferred. The alkyl group containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight or branched. From the viewpoint of increasing the boiling point of the alkali produced by decomposition (described later), ^RN1 and ^RN2 are preferably alkyl groups with 5 to 12 carbon atoms. In formulations where adhesion to metals (e.g., copper) is important, cyclic alkyl groups or alkyl groups with 1 to 8 carbon atoms are preferred.

^RN1 and ^RN2 can be linked together to form a ring structure. When forming a ring structure, oxygen atoms or the like can be present in the chain. Furthermore, the ring structure formed by ^RN1 and ^RN2 can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As for the formed ring structure, a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1) is preferred. Examples include pyrrole ring, imidazole ring, pyrazole ring, pyrrolidine ring, imidazoleidine ring, pyrazoleidine ring, piperidine ring, piperidine ring, and oxymeta-line ring. Pyrrole ring, pyrridine ring, piperidine ring, piperidine ring, and oxymeta-line ring are preferred.

R ^C1 represents a hydrogen atom or a protecting group, with a hydrogen atom being preferred.

As a protective group, a protective group that can be decomposed by the action of acid or alkali is preferred, and a good example is a protective group that can be decomposed by acid.

Specific examples of protecting groups include chain-like or cyclic alkyl groups or chain-like or cyclic alkyl groups having an oxygen atom in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tributyl, and cyclohexyl. Examples of chain-like alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methoxymethyl (MOM) and ethoxyethyl (EE) groups. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxocyclobutyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

There are no particular limitations on the linking group constituting the divalent L, but an hydrocarbon group is preferred, and an aliphatic hydrocarbon group is even more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group having an oxygen atom in the chain is preferred; groups relating to aliphatic hydrocarbons, aromatic hydrocarbons, or combinations of divalent aliphatic hydrocarbons and aromatic hydrocarbons having an oxygen atom in the chain are even more preferred; and divalent aliphatic hydrocarbons having an oxygen atom in the chain are even more preferred. It is preferable that these groups do not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. Groups related to the combination of divalent aliphatic and divalent aromatic hydrocarbons (e.g., arylalkyl groups) preferably have 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

As a linking group L, specifically, linear or branched chain-like alkylene groups, cyclic alkylene groups, groups relating to combinations of linear and cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, linear or branched chain-like alkenyl groups, cyclic alkenyl groups, aryl groups, and arylalkylene groups are preferred. Cirral or branched chain-like alkylene groups having 1 to 12 carbon atoms are preferred, 2 to 6 are more preferred, and 2 to 4 are even more preferred. Cyclic alkylene groups having 3 to 12 carbon atoms are preferred, and 3 to 6 are more preferred. The groups relating to combinations of chain-like and cyclic alkyl groups preferably have 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkyl group having an oxygen atom in the chain can be chain-like or cyclic, and can be straight or branched. The alkyl group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

The linear or branched chain-like alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds in the linear or branched chain-like alkenyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The number of C=C bonds in the cyclic alkenyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. The aryl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylalkyl group having 7 to 23 carbon atoms is preferred, 7 to 19 is more preferred, and 7 to 11 is even more preferred. Among these, chain-like arylalkyl groups, cyclic arylalkyl groups, arylalkyl groups having oxygen atoms in the chain, chain-like alkenyl groups, arylalkyl groups, arylalkyl groups, and arylalkyl groups are preferred; 1,2-arylethyl, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylyl (especially cis-arylethyl), phenyl (1,2-arylphenyl), phenylmethylene (especially 1,2-arylphenylmethylene), and oxyethylyl (especially 1,2-ethyleneoxy-1,2-arylethyl) are more preferred.

Examples of alkali-producing agents include the following, but the invention is not to be construed as such.

【Chemical Formula 63】

For nonionic thermal alkali generators, a molecular weight of 800 or less is preferred, 600 or less is even better, and 500 or less is still preferred. As a lower limit, a molecular weight of 100 or more is preferred, 200 or more is even better, and 300 or more is still even better.

Preferred compounds as ionic base generators include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of ammonium salts include the following compounds, but the invention is not limited to these. [Formula 64]

Specific examples of imine salts include the following compounds, but the invention is not limited to these. [Formula 65]

When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent relative to 100 parts by weight of the resin composition of the present invention is preferably 0.1 to 50 parts by weight. A lower limit of 0.3 parts by weight or more is more preferred, and 0.5 parts by weight or more is further preferred. An upper limit of 30 parts by weight or less is more preferred, 20 parts by weight or less is further preferred, 10 parts by weight or less is even more preferred, and it can be 5 parts by weight or less, or even 4 parts by weight or less. One or more alkali-generating agents can be used. When two or more are used, the total amount within the above range is preferred.

<Soluble> It is preferable that the resin composition of this invention contains a solvent. Any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, monoxides, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetic acid, ethyl alkoxyacetic acid, butyl alkoxyacetic acid (e.g., methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, ethyl 3-ethoxypropionic acid). Alkyl esters of 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

As ethers, examples of preferred choices include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

Among the ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydroglucanone are good examples.

As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are good examples.

As for ionoids, dimethyl ionoids can be cited as a better example.

Among the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N-methoxy-N,N-dimethylpropionic acid, N-methoxy-N-acety-N-propionic acid, and N-acety-N-propionic acid are considered as better choices.

Among ureas, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone are considered better options.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

Regarding solvents, from the perspective of improving coating properties, it is better to mix two or more forms.

In this invention, solvents selected from one or more of the following are preferred: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl solvent acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, L-glucanone, and dihydroglucanone. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate, is particularly preferred.

From a coatability perspective, it is preferable to set the solvent content to 5-80% by mass of the total solids concentration of the resin composition of the present invention, more preferably 5-75% by mass, further preferably 10-70% by mass, and even more preferably 20-70% by mass. The solvent content can be adjusted according to the desired film thickness and coating method.

The resin composition of the present invention may contain only one solvent or two or more solvents. When it contains two or more solvents, it is preferable that the total amount is within the above range.

<Metal Adhesion Modifier> The resin composition of this invention preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesives, titanium-based adhesives, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[Silane Coupling Agents] Examples of silane coupling agents include, for example, the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062-0073 of Japanese Patent Application Publication No. 2014-191002, the compounds described in paragraphs 0063-0071 of International Publication No. 2011/080992, and Japanese Patent Application Publication No. 2014-191252. The compounds described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 2014-041264, paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014/097594, and paragraphs 0067-0078 of Japanese Patent Application Publication No. 2018-173573 are incorporated herein by reference. Furthermore, as described in paragraphs 0050-0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Also, it is preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

【Chemical Formula 66】

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-piperylpropylmethyldimethoxysilane, 3-piperylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based bonding aids] Examples of aluminum-based bonding aids include aluminum tri(ethyl acetate)aluminum, aluminum tri(acetyl acetone)aluminum, and aluminum diisopropanol for ethyl acetate.

Furthermore, as other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are incorporated in this specification.

The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting the content above the lower limit above, the adhesion between the pattern and the metal layer becomes good; by setting the content below the upper limit above, the heat resistance and mechanical properties of the pattern become good. The metal adhesion modifier may be a single type or two or more types. When using two or more types, it is preferable that their total content is within the above range.

<Migration Inhibitor> It is preferable that the resin composition of this invention also contains a migration inhibitor. By including the migration inhibitor, the transfer of metal ions from the metal layer (metal wiring) into the membrane can be effectively inhibited.

There are no particular limitations on its role as a migration inhibitor. Examples of such inhibitors include compounds with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridoxazole ring, pyrimidine ring, pyridoxazole ring, piperidine ring, piperidine ring, morpholinium ring, 2H-pyran ring and 6H-pyran ring, tripyranium ring), compounds with thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acehydrazine derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, as well as tetraazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole, can be used more effectively.

Alternatively, ion trapping agents that capture anions such as halogen ions can be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015/199219, etc., can be used, and these contents are incorporated in this specification.

The following compounds can be cited as examples of migration inhibitors.

【Chemical Formula 67】

When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the above range.

<Polymerization Inhibitor> The resin composition of this invention preferably includes a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metallic compounds.

Specific compounds used as polymerization inhibitors include, preferably, p-hydroquinone, ortho-hydroquinone, ortho-methoxyphenol, p-methoxyphenol, di-tertiary butyl-p-cresol, gallnutol, p-tertiary butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), and 2,2'-methylenebis(4-methyl-6-tertiary butylphenol). Butylphenol), N-nitrosophenylhydroxylamine monocerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2- Nitrosamino-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-triterpenoid)phenylmethane, 1,3,5-tris(4-triterpenoid-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris(1H,3H)-2,4,6-(1H,3H) The following compounds are permitted: (5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 2,2,6,6-tetramethylpiperidine 1-oxy radical, phenthiazolinone, phenoxazolinone, 1,1-diphenyl-2-pyrrolidinehydrazine, dibutyldithiocopper(II), nitrobenzene, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitroso-N-phenylhydroxyamine ammonium salt, etc. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 may also be used, and these contents are incorporated herein by reference.

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

The polymerization inhibitor may be one type or two or more types. When there are two or more polymerization inhibitors, it is preferable that their total amount is within the above range.

<Acid Scavenger> To reduce performance changes caused by the time elapsed between exposure and heating, the resin composition of this invention preferably contains an acid scavenger. The acid scavenger refers to a compound that can capture acid-producing compounds by being present in the system; compounds with low acidity and high pKa are preferred. As an acid scavenger, compounds with an amino group are preferred, including primary amines, secondary amines, tertiary amines, ammonium salts, and tertiary amides; primary amines, secondary amines, tertiary amines, and ammonium salts are preferred, with secondary amines, tertiary amines, and ammonium salts being even more preferred. As acid scavengers, preferred examples include compounds with imidazole, diazabicyclic, onium, trialkylamine, aniline, or pyridine structures; alkylamine derivatives with hydroxyl and/or ether bonds; and aniline derivatives with hydroxyl and/or ether bonds. In the case of an onium structure, the acid scavenger is preferably a salt having a cation selected from ammonium, diazo, monazine, strontium, phosphonium, or pyridinium, and an anion of an acid with a lower acidity than that produced by the acid generator.

Examples of acid scavengers with an imidazole structure include imidazole, 2,4,5-triphenylimidazolium, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers with a diazabicyclic structure include 1,4-diazabicyclic[2,2,2]octane, 1,5-diazabicyclic[4,3,0]non-5-ene, and 1,8-diazabicyclic[5,4,0]undec-7-ene. Examples of acid scavengers with a tunica structure include tetrabutylammonium hydroxide, triarylstromium hydroxide, benzylmethylstromium hydroxide, strom hydroxides with a 2-oxoalkyl group, specifically triphenylstromium hydroxide, tris(tri-butylphenyl)stromium hydroxide, bis(tri-butylphenyl)monium hydroxide, benzylmethylthiophenonium hydroxide, and 2-oxopropylthiophenonium hydroxide. Examples of acid scavengers with a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers with an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers with a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives with hydroxyl and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives with hydroxyl and/or ether bonds include N,N-bis(hydroxyethyl)aniline.

Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecane), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyl Dicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, succinyltriamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminopyroline, aminoalkylpyroline, etc.

These acid scavenging agents can be used alone or in combination of two or more. The composition of this invention may contain an acid scavenging agent or may not contain an acid scavenging agent. However, when it does contain an acid scavenging agent, the content of the acid scavenging agent is based on the total solid content of the composition, typically 0.001 to 10% by mass, preferably 0.01 to 5% by mass.

The optimal ratio of acid generator to acid scavenger is 2.5 to 300 (molar ratio). That is, from the perspective of sensitivity and resolution, a molar ratio of 2.5 or higher is preferable; from the perspective of suppressing the decrease in resolution caused by the thickening of the relief pattern over time from exposure to heat treatment, a ratio below 300 is preferable. A molar ratio of 5.0 to 200 is more preferred, and 7.0 to 150 is even more desirable.

<Other Additives> The resin composition of this invention can be combined with various additives as needed, within the scope of achieving the effects of this invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-coagulants, phenolic compounds, other polymers, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the physical properties of the membrane can be adjusted. Regarding these components, please refer to paragraphs 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of the specification of U.S. Patent Application Publication No. 2013/0034812) and paragraphs 0101-0104, 0107-0109, etc., in Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein. When incorporating these additives, it is preferable that their total amount be 3% by weight or less of the solid content of the resin composition of the present invention.

[Surfactants] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

By including a surfactant in the photosensitive resin composition of this invention, the liquid properties (especially flowability) during preparation as a coating liquid are further improved, thereby further improving the uniformity or liquid-saving properties of the coating thickness. That is, when forming a film using a coating liquid containing a surfactant composition, the interfacial tension between the coated surface and the coating liquid is reduced, improving the wetting of the coated surface and thus enhancing the coating properties. Therefore, it is possible to better form films with small, uniform thicknesses despite uneven thickness.

Examples of fluorinated surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (manufactured by 3M Japan Limited), and Surflon. S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (the above is ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. Fluorinated surfactants may also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, the contents of which are incorporated herein by reference. Block polymers may also be used as fluorinated surfactants; for example, compounds described in Japanese Patent Application Publication No. 2011-89090 may be cited, the contents of which are incorporated herein by reference. Fluorinated surfactants can also preferably use fluorinated polymers comprising repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propenoxy). Examples of fluorinated surfactants used in this invention include the following compound: [Chemical Formula 68]

The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Fluoropolymers with vinyl unsaturated groups on their side chains can also be used as fluorine surfactants. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Commercially available examples include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.

Fluorinated surfactants are preferably composed of 3–40% by mass, more preferably 5–30% by mass, and especially preferably 7–25% by mass. Fluorinated surfactants with fluorine content within this range are effective in terms of uniformity of coating thickness and liquid-saving properties, and also exhibit good solubility in the composition.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

Examples of hydrocarbon surfactants include PIONIN A-76, Newkalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FAT CO.,LTD.).

Examples of nonionic surfactants include glycerol, trihydroxymethylpropane, trihydroxymethylethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO.,LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

As cationic surfactants, examples include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co)polymers Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co.,LTD.), and W001 (manufactured by Yusho Co.,Ltd.).

As anionic surfactants, examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

A single surfactant can be used, or two or more can be used in combination. The surfactant content relative to the total solids of the composition is preferably 0.001–2.0% by mass, and more preferably 0.005–1.0% by mass.

[Higher Fatty Acid Derivatives] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoylamine can be added to the resin composition of the present invention, thereby causing them to exist unevenly on the surface of the resin composition of the present invention during the drying process after coating.

Furthermore, higher fatty acid derivatives may also use compounds described in paragraph 0155 of International Publication No. 2015/199219, which is incorporated in this specification.

When the resin composition of the present invention contains higher fatty acid derivatives, the content of higher fatty acid derivatives relative to the total solid content of the resin composition of the present invention is preferably 0.1% to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above-mentioned range.

[Thermal Polymerization Initiator] The resin composition of this invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the resin and polymerizable compound can also undergo polymerization, thus further improving solvent resistance. Furthermore, the aforementioned photopolymerization initiator also has the function of initiating polymerization through heat, and can be added as a thermal polymerization initiator.

As a thermal free radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the contents of which are incorporated in this specification, can be cited.

When a thermal polymerization initiator is included, its content relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[Inorganic Particles] The resin composition of this invention may contain inorganic particles. Specifically, these inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

The preferred average particle size for the aforementioned inorganic particles is 0.01–2.0 μm, more preferably 0.02–1.5 μm, further preferably 0.03–1.0 μm, and exceptionally preferably 0.04–0.5 μm. The aforementioned average particle size for the inorganic particles refers to the primary particle size and the volume average particle size. The volume average particle size can be determined using dynamic light scattering based on the Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In cases where the above determination is difficult, it can also be determined using centrifugal sedimentation transmission, X-ray transmission, or laser diffraction/scattering methods.

[Ultraviolet Absorber] The composition of this invention may include an ultraviolet absorber. As an ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used. Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Furthermore, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-isobutylphenyl)-5-chlorobenzotriazole. Butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

Examples of acrylonitrile-based UV absorbers that can replace cyano-3,3-diphenylacrylate include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triterpenoid-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triterpenoid, 2-[4-[(2-hydroxy-3-tetrazoloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -Bis(2,4-dimethylphenyl)-1,3,5-tris(hydroxyphenyl) compounds, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris(hydroxyphenyl) compounds, etc.; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tris(hydroxyphenyl) compounds, 2,4-Bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-tris(2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tris(2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tris(2,4-bis(2-hydroxy-4-)) Tris(hydroxyphenyl)tris(2,4-dibutoxyphenyl)-1,3,5-tris(2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-tris(2,4,6-tris(2-hydroxyphenyl)tris(2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(2,4,6-tris(2-hydroxyphenyl) ...-hydroxyphenyl)tri

In this invention, the aforementioned ultraviolet absorbers can be used individually or in combination of two or more. The composition of this invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber relative to the total solid content of the composition of this invention is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

[Organic Titanium Compounds] The resin composition of this embodiment may contain organic titanium compounds. Because the resin composition contains organic titanium compounds, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

As usable organic titanium compounds, those in which the organic group is bonded to titanium atoms via covalent or ionic bonds can be cited. Specific examples of organic titanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelate compounds with two or more alkoxy groups are preferred, as they exhibit excellent resin composition stability and yield good curing patterns. Specific examples include diisopropoxide bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, diisopropoxide bis(tetramethylheptanedione) titanium, and diisopropoxide bis(ethyl acetoacetate) titanium, etc. II) Tetraalkoxytitanium compounds: Examples include tetra(n-butanol)titanium, tetraethanoltitanium, tetra(2-ethylhexanol)titanium, tetraisobutanoltitanium, tetraisopropanoltitanium, tetraethanoltitanium, tetramethoxypropanoltitanium, tetramethylphenyloxytitanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyltitanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc. III) Titanium diacene compounds: Examples include pentamethylcyclopentadienyltrimethylamine titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium. IV) Monoalkoxy titanium compounds: Examples include tris(dioctyl phosphate)isopropanol titanium and tris(dodecanephenyl sulfonate)isopropanol titanium. V) Titanium oxide compounds: Examples include titanium bis(pentanedione), titanium bis(tetramethylheptanedione), and titanium phthalocyanine oxide. VI) Tetraacetone titanium compounds: Examples include tetraacetone titanium. VII) Titanium ester coupling agents: for example, isopropyltris(2-dodecylbenzenesulfonate) titanium salt, etc.

Among these, from the viewpoint of exhibiting better drug resistance, it is preferable to select at least one compound from the group consisting of I) titanium chelates, II) tetraalkoxy titanium compounds and III) titanium dicene compounds. In particular, diisopropanol bis(ethyl acetoacetate)titanium, tetra(n-butanol)titanium and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium are preferred.

When incorporating organotitanium compounds, the amount of these compounds relative to 100 parts by weight of a specific resin is preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 2 parts by weight. When the amount of these compounds is 0.05 parts by weight or more, the resulting curing pattern exhibits better heat resistance and chemical resistance. On the other hand, when the amount of these compounds is 10 parts by weight or less, the composition exhibits better storage stability.

[Antioxidant] The composition of this invention may include an antioxidant. By including an antioxidant as an additive, the elongation properties and adhesion to metal materials of the cured film can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds are examples. Compounds having a substituent at the site (orthoside) adjacent to the phenolic hydroxyl group are preferred. As the aforementioned substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both phenolic and phosphite groups within the same molecule are also preferred as antioxidants. Furthermore, phosphorus-based antioxidants can be used more effectively as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxanephosphine-heptacyclohepta-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiary butyldibenzo[d,f][1,3,2]dioxanephosphine-heptacyclohepta-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tertiary butyl-6-methylphenyl) phosphite. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, and Adekastab AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants may also include compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, which are incorporated herein by reference. Additionally, the composition of this invention may contain potential antioxidants as needed. As potential antioxidants, compounds whose antioxidant activity is achieved by the removal of the protective group at the site of antioxidant action can be cited, and which exert their antioxidant activity by heating at 100–250°C or at 80–200°C in the presence of an acid/base catalyst to remove the protective group. Compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Application Publication No. 2017-008219 are examples of potential antioxidants, which are incorporated herein by reference. Commercially available products that are potential antioxidants include ADEKA ARKLSGPA-5001 (manufactured by ADEKA CORPORATION). Examples of better antioxidants include 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-di-tertiary butylphenol, and compounds represented by formula (3).

【Chemical Formula 69】

In general formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and ^R6 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). ^R7 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), or an organic group containing at least one of oxygen and nitrogen atoms in a 1 to 4 valence. k represents an integer from 1 to 4.

The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic and phenolic hydroxyl groups in the resin. Furthermore, it can inhibit metal oxidation by preventing rust on metal materials.

It can act on both resins and metal materials simultaneously, therefore, k being an integer from 2 to 4 is preferred. Examples of ^R7 include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and may further have substituents. Among these, alkyl ether and -NH- are preferred from the viewpoint of solubility in the developing solution and metal adhesion; -NH- is more preferred from the viewpoint of interaction with resin and metal adhesion during metal complex formation.

For compounds represented by general formula (3), examples can be given, but are not limited to the following structures.

【Chemical Formula 70】

【Chemical Formula 71】

【Chemical Formula 72】

【Chemical Formula 73】

The optimal amount of antioxidant added relative to the resin is 0.1 to 10 parts by weight, with 0.5 to 5 parts by weight being more preferred. By setting the addition amount to 0.1 parts by weight or more, it is easy to obtain effects that improve elongation properties or adhesion to metal materials, even in high-temperature and high-humidity environments. Conversely, by setting the addition amount to 10 parts by weight or less, the sensitivity of the resin composition can be improved, for example, through interaction with photosensitizers. Only one type of antioxidant may be used, or two or more may be used. When using two or more antioxidants, the total amount within the above-mentioned range is preferred.

[Anti-coagulant] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

In this invention, the anti-coagulant can be used alone or in combination with two or more types. The composition of this invention may or may not contain an anti-coagulant, but when it does, the content of the anti-coagulant relative to the total solid content of the composition of this invention is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.

[Phenolic Compounds] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, BisRS-26X (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION).

In this invention, a single phenolic compound may be used alone, or two or more may be used in combination. The composition of this invention may or may not contain phenolic compounds. However, when phenolic compounds are included, the content of the phenolic compounds relative to the total solid content of the composition of this invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

[Other Polymer Compounds] Other polymer compounds include silicone resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, phenolic varnish resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modifiers incorporating cross-linking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

In this invention, one or more other polymeric compounds may be used alone or in combination. The composition of this invention may or may not contain other polymeric compounds. However, when other polymeric compounds are included, it is preferable that the content of these other polymeric compounds relative to the total solid content of the composition of this invention is 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

<Characteristics of the Resin Composition> The viscosity of the resin composition of this invention can be adjusted by the concentration of the solid component of the resin composition. From the viewpoint of coating film thickness, 1,000 ^mm² /s to 12,000 ^mm² /s is preferred, 2,000 ^mm² /s to 10,000 ^mm² /s is more preferred, and 2,500 ^mm² /s to 8,000 ^mm² /s is even more preferred. As long as it is within the above range, a coating film with high uniformity can be easily obtained. If the thickness is 1,000 ^mm² /s or higher, it is easy to apply a coating with the thickness required, for example, as an insulation film for rewiring. If the thickness is 12,000 ^mm² /s or lower, a coating with excellent surface finish can be obtained.

<Limitations Regarding the Content of Substances in the Resin Composition> The moisture content of the resin composition of this invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. A moisture content less than 2.0% improves the storage stability of the resin composition. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the storage container.

From an insulation point of view, it is preferable that the metal content of the resin composition of the present invention is less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained as complexes of organic compounds and metals. When multiple metals are included, it is preferable that the total amount of these metals is within the above-mentioned range.

Furthermore, as a method to reduce the metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials for constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention using a filter; and lining the device with polytetrafluoroethylene or the like to carry out distillation under conditions that suppress contamination as much as possible.

Considering the application of the resin composition of this invention as a semiconductor material, from the viewpoint of wiring corrosion, a halogen atom content of less than 500 ppm by mass is preferable, less than 300 ppm by mass is more preferable, and less than 200 ppm by mass is even more preferable. Among these, a halogen ion content of less than 5 ppm by mass is preferable, less than 1 ppm by mass is more preferable, and less than 0.5 ppm by mass is even more preferable. Examples of halogen atoms include chlorine and bromine atoms. It is preferable that the total number of chlorine and bromine atoms, or chlorine and bromine ions, falls within the above-mentioned ranges. As a method for adjusting the halogen atom content, ion exchange treatment is a preferred example.

As a container for the resin composition of the present invention, previously known containers can be used. Furthermore, as a container, in order to suppress the contamination of impurities into the raw materials or the resin composition of the present invention, it is preferable to use a multi-layered bottle with an inner wall composed of six layers of six different resins, or a bottle with a seven-layered structure of the six resins. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

<Curing Compound of Resin Composition> A cured compound of the resin composition of the present invention can be obtained by curing the resin composition of the present invention. The cured compound of the present invention is a cured compound obtained by curing the resin composition of the present invention. Curing of the resin composition is preferably carried out by heating, preferably within the range of 120°C to 400°C, further preferably within the range of 140°C to 380°C, and particularly preferably within the range of 170°C to 350°C. The morphology of the cured compound of the resin composition is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In the present invention, the cured compound is preferably in film form. Furthermore, by pattern processing of the resin composition, the shape of the cured material can be selected according to applications such as forming a protective film on the wall surface, creating beer halls for conductivity, adjusting impedance or electrostatic capacitance or internal stress, and imparting heat dissipation. The film thickness of the cured material (including the cured film) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate during curing of the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula. Shrinkage rate [%] = 100 - (Volume after hardening ÷ Volume before hardening) × 100

<Characteristics of the Cured Resin Composition> The amide reaction rate of the cured resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and further preferably 90% or higher. A rate of 70% or higher sometimes results in a cured product with excellent mechanical properties. The elongation at break of the cured resin composition of the present invention is preferably 30% or higher, more preferably 40% or higher, and further preferably 50% or higher. The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and further preferably 230°C or higher.

<Preparation of Resin Composition> The resin composition of this invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out using previously known methods. Mixing can be performed using methods such as mixing with stirring blades, mixing with ball milling, or mixing by rotating the container itself. The mixing temperature is preferably 10–30°C, and more preferably 15–25°C.

Furthermore, to remove foreign matter such as dust or particulate matter from the resin composition of this invention, filtration using a filter is preferable. Examples of filter pore sizes include, for instance, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is preferred. The filter can be pre-cleaned with an organic solvent. Multiple filters can also be connected in series or parallel during the filtration process. When using multiple filters, filters with different pore sizes or materials can be used in combination. For example, a connection could be made by first connecting a 1μm pore size HDPE filter in series, and then connecting a 0.2μm pore size HDPE filter in series as a second stage. Furthermore, various materials can be filtered multiple times. Multiple filtrations can constitute circulating filtration. Alternatively, filtration can be performed after pressurization. When pressurization and filtration are performed, the pressurization pressure can be, for example, 0.01 MPa or higher and 1.0 MPa or lower, preferably 0.03 MPa or higher and 0.9 MPa or lower, more preferably 0.05 MPa or higher and 0.7 MPa or lower, and even more preferably 0.05 MPa or higher and 0.5 MPa or lower. In addition to filtration using a filter, impurity removal can also be performed using adsorption materials. A combination of filter filtration and impurity removal using adsorption materials can also be used. Known adsorption materials can be used. Examples include inorganic adsorption materials such as silicone and zeolite, and organic adsorption materials such as activated carbon. Alternatively, the resin composition in the bottle can be degassed under reduced pressure after filtration using a filter.

(Method for Manufacturing Cured Material) The method for manufacturing cured material of the present invention preferably includes a film formation step of applying a resin composition to a substrate to form a film. Furthermore, the method for manufacturing cured material of the present invention preferably includes the above-described film formation step, an exposure step of selectively exposing the film formed by the film formation step, and a developing step of using a developing solution to develop a pattern on the film exposed by the exposure step. The method for manufacturing cured material of the present invention preferably includes at least one of the above-described film formation step, the above-described exposure step, the above-described developing step, a heating step of heating the pattern obtained by the developing step, and a post-developing exposure step of exposing the pattern obtained by the developing step. Furthermore, the manufacturing method of this invention, including the aforementioned film formation step and the step of heating the aforementioned film, is also preferred. The details of each step are explained below.

<Film Formation Steps> The resin composition of this invention can be used in a film formation step adapted to form a film on a substrate. A preferred method for manufacturing the cured material of this invention includes a film formation step in which the resin composition is adapted to a substrate to form a film.

[Substrate] The type of substrate can be appropriately set according to the application, but there are no particular limitations. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any substrate formed of metal and substrates with metal layers formed by electroplating or vapor deposition); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In this invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and mold substrates being even more preferred. Furthermore, a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS) or similar materials may be provided on the surface of these substrates. Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular. Regarding the dimensions of the substrate, if it is circular, the diameter is, for example, 100–450 mm, preferably 200–450 mm. If it is rectangular, the length of the shorter side is, for example, 100–1000 mm, preferably 200–700 mm. Furthermore, a plate-shaped substrate (substrate) may be used, for example, preferably a panel-shaped substrate.

Furthermore, in cases where a film is formed by applying a resin composition to the surface of a resin layer (e.g., including a layer of hardener) or a metal layer, the resin layer or metal layer becomes the substrate.

As a method for applying the resin composition of the present invention to a substrate, coating is preferred.

Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the perspective of film thickness uniformity, spin coating, slit coating, spray coating, or inkjet coating are preferred. From the perspectives of film thickness uniformity and productivity, spin coating and slit coating are more advantageous. By adjusting the solid content concentration of the resin composition or the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred; for rectangular substrates, slit coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500–3,500 rpm can be used for approximately 10 seconds to 3 minutes. Also, a method of transferring a coating pre-applied to a dummy support using the above-described application method can be applied to the substrate. Regarding the transfer method, the present invention can also preferably utilize the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592. Furthermore, a step of removing excess film from the ends of the substrate can be performed. Examples of such steps include edge bead rinsing (EBR) and back rinse. Also, a pre-wetting step can be used, in which various solvents are applied to the substrate to improve its wettability before applying the resin composition to the substrate.

<Drying Step> The above-mentioned film is provided in a drying step (drying step) after the film formation step (layer formation step) to remove solvent from the formed film (layer). That is, the method for manufacturing the cured material of the present invention may include a drying step, which dries the film formed by the film formation step. Furthermore, it is preferable that the above-mentioned drying step is performed after the film formation step and before the exposure step. The drying temperature of the film in the drying step is preferably 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. Also, drying can be performed by depressurization. As for drying time, 30 seconds to 20 minutes, 1 minute to 10 minutes is better, and 2 minutes to 7 minutes is even better.

<Exposure Step> The above-mentioned film can be provided in the exposure step of selectively exposing the film. That is, the method for manufacturing the cured material of the present invention may include an exposure step that selectively exposes the film formed by the film forming step. Selective exposure means exposing a portion of the film. Furthermore, by selective exposure, exposed areas (exposed portions) and unexposed areas (non-exposed portions) are formed on the film. Regarding the exposure amount, there is no particular limitation as long as it is sufficient to cure the resin composition of the present invention; for example, an exposure energy equivalent to 50 to 10,000 mJ/ ^cm² at a wavelength of 365 nm is preferred, and 200 to 8,000 mJ/ ^cm² is more preferred.

The exposure wavelength can be appropriately set within the range of 190–1,000 nm, with 240–550 nm being the optimal range.

Regarding the exposure wavelength, if we explain it in terms of its relationship with the light source, we can cite (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm) as examples. (etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, (7) YAG lasers with a second harmonic of 532nm and a third harmonic of 355nm, etc. Regarding the resin composition of the present invention, exposure to high-pressure mercury lamps is particularly preferred, among which exposure to i-rays is preferred. This allows for exceptionally high exposure sensitivity. Furthermore, the exposure method is not particularly limited, as long as it exposes at least a portion of the film containing the resin composition of this invention. Examples include exposure using a photomask and exposure based on direct laser imaging.

<Post-exposure heating step> The above-described film can be provided for a heating step following exposure (post-exposure heating step). That is, the method for manufacturing the cured material of the present invention may include a post-exposure heating step, which heats the film exposed by the exposure step. The post-exposure heating step can be performed after the exposure step and before the developing step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, a rate of 1–12°C/min from the initial heating temperature to the maximum heating temperature is preferred, 2–10°C/min is more preferred, and 3–10°C/min is even better. Furthermore, the heating rate can be appropriately varied during the heating process. There are no particular limitations on the heating mechanism used in the post-exposure heating step; known heating plates, ovens, infrared heaters, etc., can be used. Furthermore, it is also preferable to conduct the process in a low-oxygen environment by allowing inert gases such as nitrogen, helium, or argon to flow through during heating.

<Developing Step> The exposed film can be used in a developing step to form a pattern by developing it with a developing solution. That is, the method for manufacturing the cured material of the present invention may include a developing step in which a developing solution is used to develop the film exposed in the exposure step to form a pattern. By performing development, one of the exposed and unexposed portions of the film is removed to form the pattern. The development that removes the unexposed portions of the film in the developing step is called negative development, and the development that removes the exposed portions of the film in the developing step is called positive development.

[Developer] Developers used in the developing process include those containing alkaline solutions or organic solvents.

When the developing solution is an alkaline aqueous solution, the alkaline compounds that can be contained in an alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, and tetraethylammonium hydroxide. The preferred compounds are tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, with TMAH being even more preferred. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

When the developing solution contains organic solvents, the organic solvents preferably include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3-alkoxy...). Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate) Methyl ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone; examples of cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of iones include, for example, dimethyl iones; examples of alcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol; and examples of amides include, for example, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the developing solution contains an organic solvent, one or more organic solvents may be used. In this invention, it is particularly preferred that the developing solution contains at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone; it is even more preferred that the developing solution contains at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide; and the developing solution containing cyclopentanone is the most preferred.

When the developing solution contains organic solvents, the content of organic solvents relative to the total mass of the developing solution is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and especially preferably 90% by mass or more. Furthermore, the above content can be 100% by mass.

Developer solutions may further contain other ingredients. These other ingredients include, for example, well-known surfactants and well-known defoamers.

[Developer Supply Method] Regarding the developer supply method, there are no particular limitations as long as the desired pattern can be formed. Methods include immersing the substrate with the film formed in the developer, using a nozzle to supply the developer to the film formed on the substrate for swirling immersion development, or continuously supplying the developer. There are no particular limitations on the type of nozzle; examples include straight nozzles, spray nozzles, and mist nozzles. From the perspectives of developer penetration, non-image area removal, and manufacturing efficiency, using a vertical nozzle to supply developer or using a continuous spray nozzle is preferable. From the perspective of developer penetration into the image area, using a spray nozzle is even better. Furthermore, a process can be adopted where, after continuously supplying developer using a vertical nozzle, the substrate is rotated to remove the developer, and after drying, the substrate is again continuously supplied using a vertical nozzle, and then rotated to remove the developer. This process can be repeated multiple times. Furthermore, as a method for supplying the developer in the developing step, methods can include continuously supplying the developer to the substrate, maintaining the developer in a substantially static state on the substrate, vibrating the developer on the substrate using ultrasound or the like, and combinations thereof.

The optimal development time is 10 seconds to 10 minutes, with 20 seconds to 5 minutes being even better. There is no particular limitation on the temperature of the developing solution during development, but it is best to perform the process at 10 to 45°C, and even better at 18 to 30°C.

In the developing step, after treatment with developer, the pattern can be further cleaned (rinsed) using rinsing solution. Alternatively, rinsing solution can be supplied before the developer in contact with the pattern is completely dry.

[Rinse Solution] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer can be used as the rinsing solution (e.g., water, or an organic solvent different from the organic solvent contained in the developer).

When the rinsing solution contains organic solvents, the organic solvents, preferably esters, include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3-alkoxy...). Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate) Methyl ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone; examples of cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of iones include, for example, dimethyl iones; examples of alcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol; and examples of amides include, for example, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the rinsing solution contains organic solvents, one or more organic solvents may be used, or a mixture of two or more may be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are even more preferred, and cyclohexanone and PGMEA are further preferred.

When the rinsing solution contains organic solvents, it is preferable that 50% or more by mass of the rinsing solution is an organic solvent, more preferably 70% or more by mass, and even more preferably 90% or more by mass. Alternatively, 100% by mass of the rinsing solution may also be an organic solvent.

Rinsing solutions may further contain other ingredients. Examples of these other ingredients include, for example, well-known surfactants and well-known defoamers.

[Rinsing Solution Supply Method] Regarding the rinsing solution supply method, there are no particular limitations as long as the desired pattern can be formed. Methods include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate via a liquid tray, supplying the rinsing solution to the substrate via spraying, and continuously supplying the rinsing solution to the substrate via a mechanism such as a straight nozzle. From the perspectives of rinse fluid penetration, removal of non-image areas, and manufacturing efficiency, there are various methods for supplying rinse fluid, including spray nozzles, straight nozzles, and mist nozzles. Continuous supply via a mist nozzle is preferable, and from the perspective of rinse fluid penetration into the image area, a mist nozzle is even better. There are no particular limitations on the type of nozzle; examples include straight nozzles, spray nozzles, and mist nozzles. That is, it is preferable that the rinsing step involves supplying or continuously supplying the rinsing solution to the exposed film using a straight nozzle, and even better that it is supplied using a spray nozzle. Furthermore, as a method for supplying the rinsing solution in the rinsing step, methods such as continuously supplying the rinsing solution to the substrate, keeping the rinsing solution substantially still on the substrate, vibrating the rinsing solution on the substrate using ultrasound or the like, and combinations thereof can be used.

The preferred rinsing time is 10 seconds to 10 minutes, and even better is 20 seconds to 5 minutes. There is no particular limitation on the temperature of the rinsing solution, but it is best to carry out the rinsing at 10 to 45°C, and even better at 18 to 30°C.

<Heating Step> The pattern obtained by the developing step (or, in the case of a rinsing step, the rinsed pattern) can be provided to the heating step that heats the pattern obtained by the aforementioned developing step. That is, the method for manufacturing the cured material of the present invention may include a heating step that heats the pattern obtained by the developing step. Furthermore, the method for manufacturing the cured material of the present invention may include a heating step that heats a pattern obtained by other methods without a developing step, or a film obtained by a film forming step. In the heating step, resins such as polyimide precursors are cyclized to form polyimide resins. Furthermore, crosslinking of unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins is also performed. The heating temperature (maximum heating temperature) in the heating step is preferably 50–450°C, more preferably 150–350°C, further preferably 150–250°C, even more preferably 160–250°C, and particularly preferably 160–230°C.

The heating step is preferable to promote the cyclization reaction of the polyimide precursor within the above pattern by heating and utilizing the action of the alkali produced from the above-mentioned alkali generator.

Regarding the heating process, it is preferable to increase the temperature from the initial heating temperature to the maximum heating temperature at a rate of 1–12 °C/min. A rate of 2–10 °C/min is more preferable, and 3–10 °C/min is even more preferable. Setting the heating rate to 1 °C/min or higher ensures productivity and prevents excessive volatilization of acid or solvent, while setting the heating rate to 12 °C/min or lower helps to mitigate residual stress in the hardened material. Furthermore, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the initial heating temperature to the maximum heating temperature at a rate of 1–8 °C/sec, more preferable at 2–7 °C/sec, and even more preferable at 3–6 °C/sec.

The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the heating begins and reaches the maximum heating temperature. For example, after applying the resin composition of the present invention to a substrate and allowing it to dry, it is the temperature of the dried film (layer), preferably starting the heating from a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, even better is 10 to 300 minutes, and even better is 15 to 240 minutes.

In particular, when forming multilayered bodies, from the perspective of interlayer adhesion, a heating temperature of 30°C or higher is preferred, 80°C or higher is even better, 100°C or higher is further preferred, and 120°C or higher is exceptionally preferred. The upper limit of the above heating temperatures is preferably below 350°C, even better below 250°C, and further preferred below 240°C.

Heating can be performed in stages. For example, the following steps can be taken: increase the temperature from 25°C to 120°C at a rate of 3°C/min and hold at 120°C for 60 minutes, then increase the temperature from 120°C to 180°C at a rate of 2°C/min and hold at 180°C for 120 minutes. Alternatively, as described in U.S. Patent No. 9159547, it is preferable to perform the treatment while irradiating the membrane with ultraviolet light. This pretreatment step can improve the membrane's properties. The pretreatment step can be performed in a short time, approximately 10 seconds to 2 hours, with 15 seconds to 30 minutes being more ideal. Pretreatment can consist of two or more steps. For example, the first pretreatment step can be performed at a temperature range of 100–150°C, followed by a second pretreatment step at a temperature range of 150–200°C. Furthermore, cooling can be performed after heating, with a cooling rate of 1–5°C/min being preferable.

To prevent the decomposition of certain resins, it is preferable to conduct the heating process in a low-oxygen environment by passing inert gases such as nitrogen, helium, or argon under reduced pressure. An oxygen concentration of 50 ppm (by volume) or less is preferred, and 20 ppm (by volume) or less is even better. The heating mechanism used in the heating process is not particularly limited, but examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

<Post-development exposure step> The pattern obtained by the development step (or the pattern after rinsing if a rinsing step is performed) can replace the heating step described above, or can be provided in a post-development exposure step other than the heating step described above, in order to provide the pattern after the exposure and development step. That is, the method for manufacturing the cured material of the present invention may include a post-development exposure step, which exposes the pattern obtained by the development step. The method for manufacturing the cured material of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. In the post-development exposure step, reactions such as cyclization of polyimide precursors by photoalkali generators or desorption of acid-degrading groups by photoacid generators can be promoted. In the post-development exposure step, it is sufficient to expose at least a portion of the pattern obtained in the development step, but exposing the entire pattern is preferable. The exposure amount in the post-development exposure step is preferably 50–20,000 mJ/ ^cm² , more preferably 100–15,000 mJ/ ^cm² , based on the exposure energy at the wavelength where the photosensitive compound is sensitive. The post-development exposure step can be performed using the light source described in the exposure step above, with broadband light being preferable.

<Metal Layer Formation Step> The pattern obtained by the developing step (preferably a pattern provided to at least one of the heating step and the post-development developing step) can be provided to the metal layer formation step in which a metal layer is formed on the pattern. That is, the method for manufacturing the cured material of the present invention preferably includes a metal layer formation step, which forms a metal layer on the pattern obtained by the developing step (preferably a pattern provided to at least one of the heating step and the post-development exposure step).

As a metal layer, there are no particular limitations; existing metal types can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being preferred, and copper being even more preferred.

There are no particular limitations on the method for forming the metal layer, and existing methods can be used. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), peeling, electrolytic electroplating, electroless electroplating, etching, printing, and combinations thereof can be considered. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. As a preferred example of electroplating, electroplating using copper sulfate or copper cyanide plating solutions can be cited.

As for the thickness of the metal layer, it is preferable for the thickest part of the wall to be 0.01 to 50 μm, and even better if it is 1 to 10 μm.

<Applications> Examples of applications applicable to the manufacturing method of the cured material of this invention or to the cured material of this invention include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress-relief films. Other applications include sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or patterns formed by etching insulating films used for practical installation purposes as described above. For information on these applications, please refer to, for example, Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimides,” April 2008; Masaaki Kakimoto, supervised; CMC Technical Library, “Basic and Development of Polyimide Materials,” November 2011; and Japan Polyimide/Aromatic Polymer Research Association, ed., “Latest Polyimide Basics and Applications,” NTS, August 2010, etc.

Furthermore, the method for manufacturing the cured material of the present invention or the cured material of the present invention can also be used in the manufacture of offset printing plates or screen printing plates, for etching and forming components, and in the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

(Laminated Body and Method for Manufacturing the Laminated Body) The laminated body of the present invention refers to a structure having a plurality of layers comprising the hardened material of the present invention. The laminated body of the present invention comprises two or more layers containing hardened material, and may also be a laminated body consisting of three or more layers. At least one of the two or more layers containing hardened material in the aforementioned laminated body is a layer containing the hardened material of the present invention. From the viewpoint of suppressing the shrinkage of the hardened material or the deformation of the hardened material accompanying the shrinkage, it is also preferable that all the layers containing hardened material in the aforementioned laminated body are layers containing the hardened material of the present invention.

That is, it is preferable that the method of manufacturing the laminate of the present invention includes the method of manufacturing the hardened material of the present invention, and it is even more preferable that the method of manufacturing the hardened material of the present invention is repeated several times.

The laminate of the present invention comprises two or more layers including a hardened material, and preferably includes a metal layer between any of the aforementioned layers including the hardened material. The metal layer is preferably formed by the aforementioned metal layer forming step. That is, the method for manufacturing the laminate of the present invention preferably includes a metal layer forming step of forming a metal layer on the layers including the hardened material during the plurality of hardened material manufacturing steps. The preferred form of the metal layer forming step is as described above. As an example of the aforementioned laminate, a preferred embodiment is a laminate comprising at least three layers sequentially stacked: a first layer including a hardened material, a metal layer, and a second layer including a hardened material. Preferably, both the first and second layers including a hardened material are layers containing the hardened material of the present invention. The resin composition used to form the first layer including the hardened film and the resin composition used to form the second layer including the hardened film can be of the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as a rewiring layer or other metal wiring.

<Lamination Steps> The method for manufacturing the laminate of the present invention preferably includes a lamination step. The lamination step includes a series of steps comprising performing, on the surface of a pattern (resin layer) or metal layer, at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a developing step, (d) a heating step, and a post-development exposure step. Alternatively, it may be possible to repeat at least one of (a) the film formation step and (d) the heating step and the post-development exposure step. Furthermore, it may be possible to include (e) the metal layer formation step after at least one of (d) the heating step and the post-development exposure step. It goes without saying that the aforementioned drying steps can be appropriately included in the lamination process.

If a further layering step is performed after the layering step, a surface activation treatment step can be performed after the exposure step, the heating step, or the metal layer formation step described above. Plasma treatment can be cited as an example of a surface activation treatment. Details of the surface activation treatment will be described later.

Performing the above lamination steps 2 to 20 times is preferred, and 2 to 9 times is even better. For example, in a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer configuration, having 2 or more but less than 20 resin layers is preferred, and having 2 or more but less than 9 layers is even more preferred. The composition, shape, and film thickness of each of the above layers can be the same or different.

In this invention, it is particularly preferred that the hardened resin composition (resin layer) of the present invention is formed by further covering the metal layer after the metal layer is applied. Specifically, examples include repeating at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step and post-development exposure step, and (e) metal layer formation step in sequence, or repeating at least one of (a) film formation step, (d) heating step and post-development exposure step, and (e) metal layer formation step in sequence. By alternately performing the lamination steps of the resin composition layer (resin layer) and the metal layer formation step of the present invention, it is possible to alternately laminate the resin composition layer (resin layer) and the metal layer of the present invention.

(Surface Activation Treatment Step) The method for manufacturing the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the aforementioned metal layer and resin composition layer. The surface activation treatment step is usually performed after the metal layer formation step, but it can also be performed after the aforementioned development step (preferably after at least one of the heating step and the post-development exposure step), after performing the surface activation treatment step on the resin composition layer, followed by the metal layer formation step. Regarding the surface activation treatment, it can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. It is preferable to perform surface activation treatment on at least a portion of the metal layer, and it is preferable to perform surface activation treatment on a portion or all of the area of the metal layer where the resin composition layer is formed on the surface. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on its surface can be improved. Furthermore, it is preferable to also perform surface activation treatment on a portion or all of the exposed resin composition layer (resin layer). Thus, by surface-activating the surface of the resin composition layer, the adhesion between the resin composition layer and the metal layer disposed on the surface-activated surface can be improved. In particular, when the resin composition layer hardens due to processes such as negative development, it is less susceptible to damage from the surface treatment, thereby easily improving adhesion. As a surface activation treatment, specifically, plasma treatment using various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixture, argon/oxygen mixture, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, immersion treatment after removing the oxide film in hydrochloric acid aqueous solution and then immersion in an organic surface treatment agent containing at least one amine group and thiol group, and mechanical roughening treatment using a brush are preferred, especially oxygen plasma treatment using oxygen as the raw material gas. When performing corona discharge treatment, an energy of 500–200,000 J/ ^m² is preferred, 1,000–100,000 J/ ^m² is even better, and 10,000–50,000 J/ ^m² is optimal.

(Method for Manufacturing Semiconductor Devices) Furthermore, this invention also discloses semiconductor devices containing the cured material or the laminate of this invention. Furthermore, this invention also discloses a method for manufacturing semiconductor devices including a method for manufacturing the cured material or the laminate of this invention. As a specific example of a semiconductor device using the resin composition of this invention in the formation of an interlayer insulating film for a redistribution layer, please refer to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and Figure 1, the contents of which are incorporated herein by reference. [Examples]

The following examples provide a more detailed description of the invention. The materials, quantities, proportions, processing methods, and steps shown in the following examples can be appropriately modified as long as they do not depart from the spirit of the invention. Therefore, the scope of the invention is not limited to the specific examples shown below. Unless otherwise stated, "parts" and "%" are quality standards.

<Synthesis of Compound B-1> [Synthesis of B-1a] 50.0 g (0.338 mol) of phthalic anhydride, 66.4 g (0.51 mol) of 2-hydroxyethyl methacrylate, 250 mg of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor, and 2.1 g of dimethylaminopyridine (DMAP) were added. The mixture was heated to 65°C and stirred for 2 hours. After the reaction was complete, it was cooled to 25°C and poured into 550 ml of water, 55.2 g of sodium bicarbonate, and 200 ml of ethyl acetate. After stirring for 30 minutes, the organic phase was removed. The aqueous phase was extracted with 150 ml of ethyl acetate to remove the ethyl acetate solution, and the same operation was repeated. 500 ml of ethyl acetate was added to the obtained aqueous phase, and the solution was adjusted to an acidic pH of 2-3 with concentrated hydrochloric acid before separation. The ethyl acetate phase was washed three times with saturated brine (200 ml) and dried with anhydrous sodium sulfate. 250 mg of MEHQ was added to the ethyl acetate solution, and the ethyl acetate was concentrated under reduced pressure to obtain 120 g of a colorless, transparent oily substance as the target compound B-1a, with a yield of 100%.

[Synthesis of B-1] 55.0 g (0.2 mol) of B-1 and 300 mL of acetonitrile were added to a three-necked round-bottom flask. The mixture was cooled to -5°C and stirred. 24.2 g (0.24 mol) of triethylamine was then added. After cooling the solution to below 5°C, 27.5 g (0.24 mol) of methanesulfonyl chloride was added dropwise. After the addition was complete, the mixture was stirred at 0°C for 30 minutes. Then, 39.0 g (0.30 mol) of 2-hydroxyethyl methacrylate and 6.1 g of DMAP were added. After cooling the solution to below 10°C, 24.2 g (0.24 mol) of triethylamine was added dropwise. After the addition was complete, the mixture was stirred at 25°C for 3 hours, then heated to 75°C and stirred for 10 minutes. The reaction solution was cooled to 25°C and poured into 1200ml of water while stirring. 10ml of concentrated hydrochloric acid was added to adjust the pH to approximately 3-4. Extraction was performed with 500ml of ethyl acetate, followed by washing with saturated brine. The ethyl acetate solution was then washed twice with 400ml of water, followed by washing with anhydrous sodium bicarbonate solution (20g dissolved in 500ml of water). The ethyl acetate solution was dried with anhydrous sodium sulfate and concentrated under reduced pressure at an external temperature of 40°C. The residue was dissolved in 50 ml of a chloroform/n-hexane mixture (1:2), and purified by column chromatography (support: silicone, eluent: n-hexane/ethyl acetate = 3:1). The obtained solution was distilled off under reduced pressure to obtain 50.7 g of the target compound B-1 as an oil, with a yield of 64.7%. The ^¹H -NMR results for compound B-1 are as follows: 7.74 (2H), 7.71 (2H), 6.15 (2H), 5.59 (2H), 4.56 (4H), 4.46 (4H) [Formula 74]

<Synthesis of Compound B-2> [Synthesis of B-2a] 50.0 g (0.26 mol) of trimellitic anhydride, 45.3 g (0.39 mol) of 2-hydroxyethyl acrylate, and 0.5 g of dibutylhydroxytoluene (BHT) as a polymerization inhibitor were added to 45 mL of N,N-dimethylacetamide (DMAc), and the mixture was stirred at 25 °C. 1.83 g (0.013 mol) of dimethylaminopyridine (DMAP) was added to the solution, and the mixture was heated to 60 °C and stirred for 6 hours. After the reaction was complete, the solution was poured into 400 mL of water, and 200 mL of ethyl acetate was added for extraction. After removing the ethyl acetate, 400 mL of ethyl acetate was added to the aqueous phase, and concentrated hydrochloric acid was added dropwise while stirring to adjust the pH to acidic 2–3. The aqueous phase was removed, and the ethyl acetate solution was washed three times with saturated brine. After drying the ethyl acetate solution with anhydrous sodium sulfate, 0.5 g of BHT was added, and concentration was carried out under reduced pressure. The white crystals were filtered and dried at 60°C for 8 hours to obtain 76.0 g of B-2a as the target compound, with a yield of 94.7%.

[Synthesis of B-2b] 120 g (1.03 mol) of 2-hydroxyethyl acrylate and 115 g (1.14 mol) of triethylamine were added to 350 mL of ethyl acetate. The mixture was cooled to -5 °C and stirred. While keeping the solution below 10 °C, 124 g (1.08 mol) of chloride methanesulfonic acid was added dropwise. After the addition was complete, the mixture was stirred at 0 °C for 1 hour, followed by stirring at room temperature for 2 hours. After the reaction was complete, 400 mL of water and 200 mL of ethyl acetate were added, and extraction was performed. 1.0 g of dibutylhydroxytoluene (BHT) as a polymerization inhibitor was added to an ethyl acetate solution, and concentration was carried out under reduced pressure to obtain 196 g of an oily product of the target compound B-2b, with a yield of 97.6%.

[Synthesis of B-2] 70.0 g (0.227 mol) of B-2a, 73.7 g (0.59 mol) of diisopropylethylamine, 2.0 g of BHT, and 350 ml of DMAc were added to a three-necked round-bottom flask, and the internal temperature was heated to 80°C. After 30 minutes, 106 g (0.55 mol) of B-2b was added dropwise to the solution. After the addition was complete, the mixture was heated and stirred at 80°C for 5 hours. After the reaction was complete, it was cooled to 25°C and poured into 1500 ml of water while stirring. Extraction was performed by adding 750 ml of ethyl acetate. The ethyl acetate solution was washed three times with saturated brine and dried with anhydrous sodium sulfate. 1.0 g of BHT was added to an ethyl acetate solution, and concentration was carried out under reduced pressure. The residue was dissolved by adding 600 ml of a chloroform/n-hexane (2/1) mixed solvent, and then purified by column chromatography (support: silicone, eluent: n-hexane/ethyl acetate (4/1)). 70 mg of 4-methoxyphenol was added to the obtained ethyl acetate solution, and concentration was carried out under reduced pressure to obtain 85.4 g of the target compound B-2, with a yield of 74.5%. The ^¹H -NMR results of compound B-2 are as follows: 8.42 (¹H), 8.23 (¹H), 7.79 (¹H), 6.46 (³H), 6.16 (³H), 5.88 (³H), 4.57 (⁶H), 4.48 (⁶H) [Formula 75]

<Synthesis of Compound B-3> [Synthesis of B-3a] 9.31 g (0.030 mol) of 4,4'-oxydiphthalic anhydride, 11.71 g (0.090 mol) of 2-hydroxyethyl methacrylate, 35 mg of 4-methoxyphenol as a polymerization inhibitor, and 0.61 g (5 mmol) of N,N-dimethylaminopyridine (DMAP) were added to a three-necked round-bottom flask and stirred at 60–65 °C for 2.5 hours. The reaction solution was dissolved in 300 mL of ethyl acetate, and 30 g of sodium bicarbonate was added to an aqueous solution of 300 mL of water. The mixture was stirred at 25 °C for 30 minutes. The organic phase was separated and then extracted with a saturated sodium bicarbonate aqueous solution. The aqueous phase was collected, and the pH was adjusted to below 3 while adding concentrated hydrochloric acid, resulting in the separation of the oil. The oil was extracted with 200 ml of ethyl acetate, dried with magnesium sulfate, and then concentrated under reduced pressure to obtain 12.52 g of B-3a as the target compound. This oil was not purified and was used in the next reaction step.

[Synthesis of B-3b] 26.03 g (0.200 mol) of 2-hydroxyethyl methacrylate, 23.78 g (0.235 mol) of triethylamine, 0.75 g of 4-methoxyphenol, and 85 mL of ethyl acetate were added to a three-necked round-bottom flask. 24.51 g (0.214 mol) of formaldehyde chloride was added dropwise at 5–15 °C under ice-cold conditions. After returning to room temperature and allowing the reaction to proceed for 2 hours, 85 mL of water was added and the mixture was stirred for 30 minutes. After the reaction was complete, the organic phase was separated and washed with 200 mL of saturated brine, then with 2N (2 mol/L) hydrochloric acid, and finally twice more with 200 mL of saturated brine. After drying the extracted organic phase with sodium sulfate, it was concentrated under reduced pressure to obtain 41.42 g of the target compound B-3a, with a yield of 99.6%.

[Synthesis of B-3] 62.5 g of dimethacryloxy-4,4'-oxydiphthalate diester B-3a, 82.93 g (600 mmol) of potassium carbonate, 8.30 g (0.050 mol) of potassium iodide, and 200 ml of N,N-dimethylacetamide (DMAc) were added to a three-necked round-bottom flask. 41.42 g (0.199 mol) of B-3a was then added at 25 °C. The mixture was stirred for 4.5 hours at an internal temperature of 50 °C. After the reaction was complete, the reaction solution was poured into 500 ml of ethyl acetate, washed four times with 300 ml of saturated sodium bicarbonate solution, washed once with 300 ml of saturated brine, dried with sodium sulfate, concentrated under reduced pressure, and then subjected to column chromatography (support: silicone, eluent: n-hexane/ethyl acetate = 3/1), yielding 49.31 g of target compound B-3, with a yield of 62.3%. The ^1H -NMR results of compound B-3 are as follows. 7.84 (2H), 7.28 (2H), 7.14 (2H), 6.10 (4H), 5.59 (4H), 4.54 (8H), 4.44 (8H), 1.95 (12H) [Chemical Formula 76]

<Synthesis of Compound B-4> [Synthesis of B-4a] 4.44 g (0.010 mol) of 4,4'-(hexafluoroisopropyl)oxophthalic anhydride, 34.84 g (0.300 mol) of 2-hydroxyethyl acrylate, 100 mg of dibutylhydroxytoluene (BHT) as a polymerization inhibitor, 0.61 g (5 mmol) of N,N-dimethylaminopyridine (DMAP), and 18.5 ml of N,N-dimethylacetamide (DMAc) were added to a three-necked round-bottom flask and stirred at 55 °C for 4 hours. The reaction solution was dissolved in 400 ml of ethyl acetate, and 20 g of sodium bicarbonate was added to an aqueous solution of 400 ml of water. The mixture was stirred at 25 °C for 30 minutes. The aqueous phase was separated, and the sample was washed four times with 200 ml of ethyl acetate. While adjusting the pH to below 3 with concentrated hydrochloric acid, the oil was separated. The oil was extracted with 1000 ml of ethyl acetate, dried with magnesium sulfate, and concentrated under reduced pressure to obtain 78.0 g of B-4a as the target compound. This oil was not purified and was used in the next reaction step.

[Synthesis of B-4] 78.0 g of diallyloxy-4,4'-(hexafluoroisopropyl)diphthalate B-4a, 82.93 g (600 mmol) of potassium carbonate, 8.30 g (0.050 mol) of potassium iodide, and 200 ml of N,N-dimethylacetamide (DMAc) were added to a three-necked round-bottom flask. 46.61 g (0.240 mol) of B-2b was added at 25 °C. After stirring at an internal temperature of 55 °C for 30 minutes, the mixture was stirred at an internal temperature of 80 °C for 5 hours. After the reaction was complete, the reaction solution was cooled to 25°C, poured into 600 ml of ethyl acetate, washed twice with 300 ml of saturated sodium bicarbonate solution, washed once with 300 ml of saturated brine, dried with sodium sulfate, concentrated under reduced pressure, and subjected to column chromatography (support: silicone, eluent: n-hexane/ethyl acetate = 2/1). 59.59 g of B-4 was obtained as the target compound, with a yield of 68.2%. The ^1H -NMR results of compound B-4 are as follows. 7.83 (2H), 7.74 (2H), 7.50 (2H), 6.44 (4H), 6.12 (4H), 5.87 (4H), 4.57 (8H), 4.47 (8H) [Chemical Formula 77]

<Synthesis of Compound B-5> Compound B-5 was synthesized by referring to the method described in Japanese Patent Publication No. 45-20787. [Chemical Formula 78]

<Synthesis of Compounds B-6 to B-8> Compounds B-6 to B-8 were synthesized by means of the same method as that used for the synthesis of compound B-1, with appropriate modifications to the starting materials. Compounds B-6 to B-8 have the following structures: [Chemical Formula 79]

<Synthetic Example 1> [Synthesis of a polyimide precursor (A-1: a polyimide precursor without free radical polymerizability groups) from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and benzyl alcohol] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 °C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone and dried using a molecular sieve. The suspension was heated at 100 °C for 3 hours. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of _SOCl₂ was added over 10 minutes while maintaining the temperature at -10 ± 4°C. The viscosity increased during the addition of _SOCl₂ . After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution obtained by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was adjusted to a temperature range of -5 to 0°C and added dropwise to the reaction mixture over 20 minutes. The reaction mixture was then reacted at 0°C for 1 hour, followed by the addition of 70 g of ethanol, and stirred overnight at room temperature. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, and the mixture was stirred again in 4 liters of water for 30 minutes and filtered again. The obtained polyimide precursor was then dried at 45°C for 3 days under reduced pressure. The weight-average molecular weight of the polyimide precursor was 18,000. [Chemical Formula 80]

<Synthetic Example 2> [Synthesis of a polyimide precursor (A-2: a polyimide precursor with free radical polymerizability group) from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of pyromellitic dianhydride and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with _SOCl2 and then converted to a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1. The polyimide precursor had a weight-average molecular weight of 19,000. [Chemical Formula 81]

<Synthetic Example 3> [Synthesis of a polyimide precursor (A-3: a polyimide precursor with free radical polymerizability group) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of dimethyl methacrylate were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with _SOCl2 and then converted to a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1. The polyimide precursor had a weight-average molecular weight of 18,000. [Chemical Formula 82]

<Synthetic Example 4> [Synthesis of a polyimide precursor (A-4: a polyimide precursor with free radical polymerizable groups) from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (bi-toluidine) and 2-hydroxyethyl methacrylate] A diester of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with _SOCl2 and then converted to a polyimide precursor using 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1. The polyimide precursor had a weight-average molecular weight of 19,000. [Chemical Formula 83]

<Synthetic Example 5> [Synthesis of polybenzoxazole precursor (A-5) from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl chloride] 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 100 mL of N-methyl-2-pyrrolidone and stirred until dissolved. Then, while maintaining the temperature at 0–5 °C, 11.21 g of 4,4'-oxydibenzoyl chloride was added dropwise over 10 minutes, followed by stirring for another 60 minutes. Next, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred at 5000 rpm for 15 minutes. The polybenzoxazole precursor was removed by filtration, and the mixture was stirred again in 6 liters of water for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor was dried at 45°C for 3 days under reduced pressure. The weight-average molecular weight of the polybenzoxazole precursor was 15,000. [Chemical Formula 84]

<Synthesis Example 6> [Synthesis of a polyimide precursor (A-6: a polyimide precursor with free radical polymerizability groups) from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate] 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was added to a separable flask, along with 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone. While stirring at room temperature, 79.1 g of pyridine was added to obtain the reaction mixture. After the exothermic reaction concluded, the mixture was cooled to room temperature and then allowed to stand for 16 hours.

Next, while stirring, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while still chilled. Then, while stirring, a suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added over 60 minutes. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and the mixture was stirred for 1 hour. Finally, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, thus obtaining the reaction solution.

The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate composed of crude polymer. The crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer. The precipitate was filtered and then vacuum dried to obtain polymer A-6 in powder form. The weight average molecular weight (Mw) of polymer A-6 was measured to be 20,000.

<Synthesis Example 7> [Synthesis of a polyimide precursor (A-7: a polyimide precursor with free radical polymerizability groups) from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate] In Synthesis Example 7, 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride. Otherwise, the reaction was carried out in the same manner as described in Synthesis Example 6, thereby obtaining polymer A-7. The weight-average molecular weight (Mw) of polymer A-7 was measured to be 22,000. <Synthetic Example 8 (A-8: Synthesis of Polyimide)> 2.370 kg (5.33 moles) of 4,4'-(hexafluoroisopropylidene)bis(phthalic anhydride) was added to a solution of 1-(4-aminophenyl)-1,3,3-trimethylindane-5-amine (also known as 4,4'-[1,4-epenylphenyl-bis(1-methylepenylethyl)]bisphenylamine (DAPI)) in 9.86 kg of NMP at 25 °C. The reaction mixture was heated to 40 °C and reacted for 6 hours. Then, acetic anhydride (1.125 kg) and pyridine (0.219 kg) were added, and the reaction mixture was heated to 100 °C and reacted for 12 hours. The reaction mixture was cooled to room temperature and transferred to a larger container equipped with a mechanical stirrer. The reaction solution was diluted with ethyl acetate and washed with water for 1 hour (first wash). After stirring was stopped, the mixture was allowed to stand. After phase separation, the aqueous phase was removed. The organic phase was diluted with a combination of ethyl acetate and acetone and washed twice with water (second and third washes). The amounts of organic solvent (ethyl acetate and acetone) and water used in the first to third washes are shown in Table 1. [Table 1] 1st time 2nd time 3rd Ethyl acetate (kg) 20.5 4.1 4.1 Acetone (kg) - 2.3 2.3 Water (kg) 22.0 26.0 26.0

GBL (γ-butyrolactone, 10 kg) was added to the cleaned organic phase, and the solution was concentrated under reduced pressure distillation to obtain a polymer solution. The polymer solution was dried using a vacuum dryer to obtain polyimide (A-8).

<Examples and Comparative Examples> In each embodiment, the components listed in the following tables were mixed to obtain various resin compositions. Similarly, in each comparative example, the components listed in the following tables were mixed to obtain comparative compositions. Specifically, the content of components listed in columns other than "Soluble" in the tables is set to the amount listed in "Parts by Mass" in the tables, and the content of components listed in the "Soluble" column of the tables is set to the amount of solid content of the composition as listed in the tables. Furthermore, for example, the "I-1/I-2" "80/20" designation in the "Soluble" column of the tables indicates that the mass ratio of I-1 to I-2 is I-1:I-2=80:20. The obtained resin compositions and comparative compositions were pressure filtered through a polytetrafluoroethylene filter with a pore width of 0.8 μm. Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding component.

Table 2 Implementation Examples 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Solid content (mass %) 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Cyclic resins or their precursors Kind A-3 A-3 A-3 A-3 A-3 A-3 A-3 A-3 A-1 A-2 A-4 A-5 A-3 A-3 mass 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 Compound A Kind B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-1 B-1 B-1 B-1 B-1 B-1 mass 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 polymeric compounds Kind - - - - - - - - - - - - - - mass - - - - - - - - - - - - - - Polymerization initiator Kind D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-2 D-1 mass 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 Alkali-producing agents Kind E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-2 mass 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 Polymerization inhibitors Kind F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 mass 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 Migration inhibitors Kind G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 mass 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 Metal adhesion modifier Kind H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 mass 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 solvent Kind I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 mass 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 Additives Kind - - - - - - - - - - - - - -- mass - - - - - - - - - - - - - Evaluation results Analytical B B B B B B B B B B B B B B Drug resistance A A A A B A A B B B B B A A

Table 3 Implementation Examples Comparative example 15 16 17 18 19 20 twenty one 1 2 3 Solid content (mass %) 42 42 42 42 42 42 40 40 40 40 Cyclic resins or their precursors Kind A-3 A-3 A-3 A-3 A-3 A-8 A-6 /A-7 A-6 /A-7 A-6 /A-7 A-6 /A-7 mass 80.74 80.74 80.74 80.74 80.74 80.74 40/40 40/40 40/40 40/40 Compound A Kind B-1 B-1 B-1 B-1 B-1 B-1 B-1 - - - mass 12.12 12.12 12.12 6.06 6.06 6.06 3.75 - - - polymeric compounds Kind - - - C-1 C-1 C-1 C-1 C-1 C-1 C-2 mass - - - 6.06 6.06 6.06 3 7.8 7.8 7.8 Polymerization initiator Kind D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 mass 2.83 2.83 2.83 2.83 2.83 2.83 3.1 3.1 3.1 3.1 Alkali-producing agents Kind E-1 E-1 E-1 E-1 E-1 E-2 - - - - mass 2.26 2.26 2.26 2.26 2.26 2.26 - - - - Polymerization inhibitors Kind F-2 F-1 F-1 F-1 F-1 F-1 F-3 F-3 F-3 F-3 mass 0.16 0.16 0.16 0.16 0.16 0.16 0.05 0.05 0.05 0.05 Migration inhibitors Kind G-1 G-2 G-1 G-1 G-1 G-1 G-2 /G-3 G-2 /G-3 G-2 /G-3 G-2 /G-3 mass 0.28 0.28 0.28 0.28 0.28 0.28 0.15 / 0.15 0.15 / 0.15 0.15 / 0.15 0.15 / 0.15 Metal adhesion modifier Kind H-1 H-1 H-2 H-1 H-1 H-1 H-2 H-2 H-2 H-2 mass 1.61 1.61 1.61 1.61 1.61 1.61 0.5 0.5 0.5 0.5 solvent Kind I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-3 / I-4 I-3 / I-4 I-3 / I-4 I-3 / I-4 mass 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 Additives Kind - - - - J-1 /J-2 J-1 /J-2 J-1 /J-2 - J-1 /J-2 J-1 /J-2 mass - - - - 5.5 /1 5.5 /1 5.5 /1 - 5.5 /1 5.5 /1 Evaluation results Analytical B B B A A A A C D D Drug resistance A A A B B B B D D D

The detailed information of each component recorded in the table is as follows.

[Cycated resins or their precursors] ･A-1～A-8: A-1～A-8 synthesized in the above manner

[Compound A] ·B-1～B-8: B-1～B-8 synthesized in the above manner

[Polymerizable Compounds] • C-1: Compounds with the following structure • C-2: M-327 (TOAGOSEI CO.,LTD., a 3-molar modified caprolactone product of ethylene oxide-modified triacrylate triisocyanate [Chemical Formula 85])

[Additives] • J-1: N-Phenylonamine (manufactured by Tokyo Chemical Industry Co., Ltd.) • J-2: Compounds with the following structure [Chemical Formula 86]

[Photopolymerization initiators] ･D-1 and D-2: Compounds with the following structure [Chemical Formula 87]

[Alkali generators] ･E-1～E-2: Compounds with the following structures [Chemical Formula 88]

[Polymerization Inhibitors] • F-1 to F-3: Compounds with the following structure • F-3: 2-Nitrosino-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) [Chemical Formula 89]

[Migration Inhibitors] G-1 to G-3: Compounds with the following structures. [Chemical Formula 90]

[Metal adhesion modifier] ･H-1～H-3: Compounds with the following structure [Chemical Formula 91]

[Solubilizers] I-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) I-2: Dimethyl sulfoxide (manufactured by FUJIFILM Wako Pure Chemical Corporation) I-3: N-Methyl-2-pyrrolidone (manufactured by Ashland) I-4: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Evaluation> [Preparation of the Cured Material] In each embodiment and comparative example, a resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer with the above-mentioned resin layer was dried on a heating plate at 100°C for 4 minutes, forming a resin composition layer with a uniform thickness of 20 μm on the silicon wafer. A broadband exposure machine (USHIO INC., UX-1000SN-EH01) was used to expose the resin composition layer on a silicon wafer at an exposure energy of 400 mJ/ ^cm² . Under a nitrogen atmosphere, the exposed resin composition layer was heated at a rate of 5°C/min until it reached 180°C, where it was held for 2 hours. The heated resin composition layer and the silicon wafer were then immersed in a 3% (w/w) hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled off from the silicon wafer. This peeled-off heated resin composition layer was used as a cured material.

[Chemical Resistance] The obtained hardened material was immersed in the following solution under the following conditions, and the dissolution rate was calculated. Solution: A mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution in a 90:10 (mass ratio) ratio. Evaluation Conditions: The hardened material was immersed in the solution at 75°C for 15 minutes. The film thickness before and after immersion was compared, and the dissolution rate (nm/min) was calculated. For film thickness measurement, an elliptical polarimeter (Foothill KT-22) was used to measure the film thickness at 10 points on the coating surface, and the average value was used as the arithmetic mean to determine the film thickness. Evaluation was conducted according to the following criteria, and the evaluation results are recorded in the "Chemical Resistance" column of the table. The lower the dissolution rate value, the better the chemical resistance of the hardened material. -Evaluation Criteria- A: Dissolution rate less than 200 nm/min. B: Dissolution rate greater than 200 nm/min but less than 350 nm/min. C: Dissolution rate greater than 350 nm/min but less than 500 nm/min. D: Dissolution rate greater than 500 nm/min.

[Lithography (Resolution) Evaluation] In each embodiment and comparative example, a resin composition or a comparative composition was spin-coated onto a silicon wafer to form a resin composition layer. The silicon wafer with the resin layer formed was dried on a heated plate at 100°C for 4 minutes, forming a uniform resin composition layer with a thickness of 20 μm on the silicon wafer. The resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) to obtain the exposed resin composition layer. Exposure was performed using i-rays, with the exposure dose set to 400 mJ/ ^cm² at a wavelength of 365 nm. Furthermore, exposure was performed using a mask with lines and spatial patterns ranging from 5μm to 25μm, each marked with a 1μm scale. The exposed resin composition layer was developed using cyclopentanone for 60 seconds. The developed resin composition layer (line pattern) was observed using a scanning electron microscope (SEM) to determine the minimum linewidth. Evaluation was conducted according to the following criteria, and the results are recorded in the "Resolution" column of the table. Generally, a smaller minimum linewidth indicates better lithography (resolution). -Evaluation Criteria- A: Minimum linewidth less than 10μm. B: Minimum linewidth 10μm or more but less than 15μm. C: Minimum linewidth 15μm or more but less than 20μm. D: Patterns with a minimum line width of 20μm or more, or where it is impossible to obtain a line width with edge sharpness.

The results above show that the resin composition of this invention, containing resin and compound A, exhibits excellent resolution. The resin compositions of Comparative Examples 1 and 2 do not contain compound A. Therefore, the resolution of these Comparative Examples 1 and 2 is relatively poor. Furthermore, the results above show that the resin composition of this invention, containing resin and compound A, exhibits excellent drug resistance to the cured material. The resin compositions of Comparative Examples 1 and 2 do not contain compound A. Therefore, the drug resistance of these Comparative Examples 1 and 2 to the cured material is relatively poor.

<Example 101> The resin composition used in Example 1 was applied in a layered manner to the surface of a copper thin layer on a resin substrate having a copper thin layer formed thereon by spin coating. After drying at 100°C for 4 minutes to form a photosensitive film with a thickness of 20 μm, exposure was performed using a stepper (manufactured by Nikon Co., Ltd., NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-space pattern and a linewidth of 10 μm). After exposure, heating at 100°C for 4 minutes was performed. Following heating, development with cyclohexanone for 2 minutes and washing with PGMEA for 30 seconds were performed to obtain the layer pattern. Next, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C/min, reaching 230°C, and then maintained at 230°C for 120 minutes, thereby forming an interlayer insulating film for the redistribution layer. This interlayer insulating film for the redistribution layer exhibits excellent insulation properties. Furthermore, semiconductor devices were fabricated using these interlayer insulating films for the redistribution layer, and normal operation was confirmed.

Claims (11)

A resin composition comprising: compound A, which is a compound represented by formula (1-1) and has a molecular weight of less than 1000; and at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor, wherein the polyimide precursor comprises a repeating unit represented by formula (2), the polybenzoxazole precursor comprises a repeating unit represented by formula (3), and the polyamideimide precursor comprises a repeating unit represented by formula (PAI-2): In formula (1-1), ^R1 , ^R2 , and ^R3 independently represent organic groups having a monovalent oxidation state of (meth)acryloxy, (meth)acrylamino, vinylphenyl, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxacyclobutyl, benzoxazolyl, block isocyanate, or amino. In formula (2), ^A1 and ^A2 independently represent oxygen atoms or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 independently represent hydrogen atoms or monovalent organic groups. In equation (3), ^R121 represents a divalent organic group, ^R122 represents a tetravalent organic group, and ^R123 and ^R124 independently represent a hydrogen atom or a monovalent organic group, respectively. In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A2 represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group. The content of the aforementioned compound A is 0% by mass or more and 60% by mass or less relative to the total solid content of the aforementioned resin composition, and the content of the aforementioned resin is 20% by mass or more and 99.5% by mass or less relative to the total solid content of the aforementioned resin composition. The resin composition as described in claim 1 further contains a free radical polymerization initiator. The resin composition as described in claim 1, wherein the aforementioned resin contains the aforementioned polyimide precursor. The resin composition as described in claim 1, wherein at least one of R ¹¹³ and R ¹¹⁴ in the aforementioned formula (2) contains a free radical polymerizable group. The resin composition as described in claim 1 is used to form an interlayer insulating film for a redistribution layer. A hardened material comprising a resin composition as described in any one of claims 1 to 5. A laminate comprising two or more layers of a hardened material as described in claim 6, wherein a metal layer is included between any of the aforementioned hardened material layers. A method for manufacturing a cured material, comprising a film forming step of adapting a resin composition described in any one of claims 1 to 5 onto a substrate to form a film. The method for manufacturing a cured material as described in claim 8 includes an exposure step of selectively exposing the aforementioned film and a developing step of developing the aforementioned film using a developing solution to form a pattern. The method for manufacturing the cured material as described in claim 8 includes a heating step of heating the aforementioned film at a temperature of 50-450°C. A semiconductor device comprising the hardened material described in claim 6.