TWI912365B - Resin compositions, cured materials, laminates, manufacturing methods of cured materials, and semiconductor devices - 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 containing the cured product or the laminate, wherein the resin composition comprises a precursor of a cyclized resin and a compound B that generates an alkali by the action of an alkali.

Description

Resin compositions, cured materials, laminates, manufacturing methods of cured materials, and semiconductor devices

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, for example, in the practical installation of semiconductor components, they can be used as insulating films, sealing materials, or protective films. 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 comprising precursors of cyclic resins such as polyimide precursors.

This resin composition is applied to a substrate, for example, by coating, to form a photosensitive film. Then, exposure, development, and heating are performed as needed to harden the material onto the substrate.

The aforementioned cyclized resin precursors, such as polyimide precursors, are cyclized, for example, by heating, and thus become cyclized resins such as polyimide in the cured material.

Resin compositions can be applied using well-known coating methods, thus offering excellent manufacturing adaptability. For example, the design freedom in terms of the shape, size, and application location of the resin composition is high. In addition to the high performance of cyclic resins such as polyimide, considering this excellent manufacturing adaptability, there is increasing anticipation for the industrial application development of these resin compositions.

For example, Patent Document 1 describes a sensitive energy line alkali generator characterized by having a specific amine ester structure.

[Patent Document 1] Japanese Patent Application Publication No. 2007-241205

In this type of resin composition, it is required to improve both the preservation stability of the composition and the elongation at break of the obtained cured product.

The purpose of this invention is to provide a resin composition with excellent preservation stability and elongation at break of the obtained cured product, a cured product obtained 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 a precursor of a cyclized resin and compound B, which produces a base through the action of a base.

<2> The resin composition as described in <1>, wherein the alkali produced from compound B is an amine.

<3> A resin composition as described in <1> or <2>, wherein compound B has an amino ester bond.

<4> A resin composition as described in any of <1> to <3>, wherein compound B is a compound represented by formula (1-1), formula (1-2), or formula (1-3).

[Chemical Formula 1]

In formula (1-1), ^R1 represents a hydrogen atom or a substituted hydrocarbon, ^R2 represents a substituted hydrocarbon, and ^R1 and ^R2 can bond to form a ring structure; in formula (1-2), ^R1 represents a hydrogen atom or a substituted hydrocarbon, ^R2 represents a substituted hydrocarbon, ^R1 and ^R2 can bond to form a ring structure, ^R3 independently represents a hydrogen atom or a substituted hydrocarbon, ^R4 represents a cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) _2R , fluorinated alkyl or halogen atom, and R represents a substituted hydrocarbon; in formula (1-3), ^R1 represents a hydrogen atom or a substituted hydrocarbon, R ² represents a substitutable hydrocarbon. ^R1 and ^R2 can bond to form a ring structure. ^R3 represents a hydrogen atom or a substitutable hydrocarbon independently. Ar represents an aromatic group substituted with at least one group selected from cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) _2R , fluorinated alkyl, and halogen atom. R represents a substitutable hydrocarbon.

<5> The resin composition described in any of <1> to <4> further comprises a thermo-alkali generator or a photo-alkali generator.

<6> The resin composition described in any of <1> to <5> further comprises a heat-generating agent.

<7> The resin composition as described in any of <1> to <6> further comprises a photopolymerization initiator.

<8> The resin composition described in any of <1> to <7> further comprises a polymeric compound.

<9> A hardener formed by hardening any of the resin compositions described in <1> to <8>.

<10> A laminate comprising two or more layers formed of the hardened material described in <9>, and including a metal layer between any of the layers formed of the hardened material.

<11> A method for manufacturing a hardened material, comprising a film-forming step of adapting any one of the resin compositions described in <1> to <8> onto a substrate to form a film.

<12> The method for manufacturing the hardened material as described in <11> includes an exposure step of selectively exposing the film and a development step of developing the film using a developing solution to form a pattern.

<13> The method for manufacturing the hardened material as described in <11> or <12> includes a heating step of heating the film at 50~450°C.

<14> A semiconductor device comprising the hardened material described in <9> or the laminate described in <10>.

According to the present invention, a resin composition exhibiting excellent preservation stability and elongation at break of the resulting cured product is provided; a cured product obtained by curing the resin composition; a laminate comprising the cured product; a method for manufacturing the cured product; and a semiconductor device comprising the cured product or the laminate.

The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

In this specification, the range of values indicated by the "~" symbol represents the range encompassed by the values recorded before and after the "~" as the lower and upper limits, respectively.

In this instruction manual, the term "step" refers not only to an independent step, but also to steps that cannot be clearly distinguished from other steps, provided that the intended effect of the step is achieved.

Regarding the designation of group names in this specification, the designations for unsubstituted and unsubstituted groups include both unsubstituted and substituted group names. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

In this instruction manual, 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 light from mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet light (EUV light), X-rays, and photochemical rays or radiation such as electron beams.

In this specification, "(meth)acrylate" means either "acrylate" or "methacrylate," "(meth)acrylic acid" means either "acrylic acid" or "methacrylic acid," and "(meth)acrylyl" means either "acrylyl" or "methacrylyl."

In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

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 all components other than the solvent relative to the total mass of the composition.

In this instruction manual, 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, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ 4000, 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 eluent. In cases where THF is unsuitable as an eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise specified, the detection in GPC assays uses a UV (ultraviolet) detector with a wavelength of 254 nm.

In this specification, when referring to 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 reference layer among the plurality of layers in question. That is, a third layer or element may be sandwiched between the reference layer and the other layers mentioned above, and the reference layer does not need to be in contact with the other layers. Furthermore, unless otherwise stated, the direction in which layers are gradually stacked on the substrate is referred to as "upper," or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, this up-down orientation is for ease of explanation of this instruction manual. In actual practice, the "up" direction in this instruction manual may differ from "vertically upward."

In this specification, unless otherwise stated, each component included in 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 stated, the temperature in this manual is 23°C, the pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

In this instruction manual, the combination of preferred samples is referred to as the better sample.

(Resin components)

The resin composition of this invention comprises a precursor of a cyclized resin (hereinafter, also referred to as "the specific resin") and compound B (hereinafter, also referred to as "compound B"), which generates a base through the action of a base.

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 developing.

In this invention, negative development refers to the removal of unexposed areas by developing during exposure and development, while positive development refers to the removal of exposed areas by developing.

The exposure method, the developing solution, and the developing method described above can be, for example, the exposure method described in the exposure step of the explanation of the method for manufacturing the cured material described later, and the developing solution and developing method described in the developing step.

The resin composition of this invention exhibits excellent preservation stability and the resulting cured product demonstrates superior elongation at break.

While the mechanism by which these effects are achieved is not yet clear, it is speculated to be as follows.

Previously, research has focused on resin compositions containing cyclic resin precursors and alkali-generating agents. In cyclic resin precursors such as polyimide precursors, cyclization reactions such as amide formation are carried out by the action of an alkali. Utilizing this property, a film containing a resin composition containing a cyclic resin precursor and an alkali-generating agent is formed, followed by high-temperature heating treatment, thereby obtaining a cured cyclic resin containing high heat resistance and high mechanical properties.

On the other hand, it is known that trace amounts of alkaline compounds are generated in the liquid composition during storage, which sometimes leads to the cyclization reaction of cyclized resin precursors within the composition.

This leads to problems such as reduced solvent solubility of the precursors of cyclized resins and precipitation of the aforementioned resins in the composition. These cyclized resin precursors promote cyclization under alkaline conditions; therefore, cyclization is sometimes inhibited by adjusting the composition to an acidic state.

However, even when the composition is prepared in an acidic environment, the presence of a large amount of alkali during storage can promote cyclization within the composition due to the alkali's effect. Therefore, simply adjusting the composition to an acidic environment is sometimes insufficient to achieve the stability required for storage (also known as the storage stability of the composition).

In this invention, by using compound B, which generates an alkali through the action of an alkali, it is possible to achieve a high degree of balance between the preservation stability of the resin composition and the mechanical properties (elongation at break) of the obtained hardened film.

In the resin composition, compound B exhibits high stability and is not prone to alkali formation during storage, thus ensuring high storage stability. Furthermore, it is believed that during hardening processes such as heat treatment, compound B rapidly decomposes and releases a sufficient amount of alkali due to the thermal decomposition of a portion of itself or from alkali-generating agents attached to the resin composition. Therefore, it is believed that sufficient cyclization reactions in the precursors of cyclized resins can achieve high mechanical properties (elongation at break).

Patent document 1 does not describe a resin composition comprising a precursor of a cyclized resin and compound B.

The components contained in the resin composition of this invention will be described in detail below.

<Specific resin>

The resin composition of this invention includes a precursor of a cyclized resin (a specific resin).

Cyclic resins contain amide ring structures or... Resins with an azole ring structure are preferred.

In this invention, the main chain refers to the relatively longest bond chain in the resin molecule.

Examples of cyclic resins include polyimide and polybenzo[a]pyrene. Zyrazole, polyamide, amide, etc.

Precursors to cyclized resins are resins that undergo chemical structural changes due to 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 precursors for cyclic resins include polyimide precursors and polybenzo[a]pyrene precursors. Azole precursors, polyamide-imide precursors, etc.

That is, the resin composition of the present invention comprises selected from polyimide precursors, polyphenylene oxides, etc. At least one resin (specific resin) from the group consisting of azole precursors and polyamide imide precursors is preferred as the specific resin.

The resin composition of this invention preferably includes a polyimide precursor as a specific resin.

Furthermore, it is preferable for a particular resin to have polymerizable groups, and even more preferable if it contains free radical polymerizable groups.

In cases where a particular resin possesses free radical polymerizable groups, it is preferable that the resin composition of the present invention includes the free radical polymerization initiator described later; more preferably, it includes both the free radical polymerization initiator and the free radical crosslinker described later. Furthermore, as needed, it can include the sensitizer described later. Such a resin composition of the present invention can, for example, be used to form a negative photosensitive film.

Furthermore, certain resins can possess polar switching groups such as acid-degrading groups.

In cases where a particular resin possesses acid-degrading groups, it is preferable that the resin composition of the present invention includes the photoacid generator described later. Such a resin composition of the present invention can be used to form, for example, a chemically amplified positive or negative photosensitive film.

[Polyimide precursors]

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).

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 represent oxygen atoms or -NH- respectively, with oxygen atoms being preferred.

In formula (2), R ¹¹¹ 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 linear or branched aliphatic groups can be substituted by groups whose hydrocarbon groups contain heteroatoms, and the cyclic aliphatic groups and aromatic groups can be substituted by groups whose hydrocarbon groups contain heteroatoms. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, with the group represented by -Ar-L-Ar- being particularly preferred. Wherein, Ar is independently an aromatic group, and L is a group comprising a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be substituted with fluorine atoms, -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 may be used.

Specifically, diamines comprising 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 comprising aromatic groups (6-20 carbon atoms) are even more preferred. The aforementioned linear or branched aliphatic groups can be substituted by groups containing heteroatoms in the hydrocarbon group of the chain, and the aforementioned cyclic aliphatic and aromatic groups can be substituted by groups containing heteroatoms in the hydrocarbon group of the ring member. Examples of groups comprising aromatic groups are as follows.

In the formula, A represents a single bond or a divalent linker group, preferably selected from a single bond or a group of 1 to 10 carbon atoms that can be substituted by a fluorine atom, such as an aliphatic hydrocarbon group, -O-, -C(=O)-, -S-, -SO _2- , -NHCO-, or combinations thereof. It is more preferred to select a single bond, a group of 1 to 3 carbon atoms that can be substituted by a fluorine atom, such as an alkyl group, -O-, -C(=O)-, -S-, or -SO _2- . -CH _2- , -O-, -S-, -SO _2- , -C(CF ₃ ) _2- , or -C(CH ₃ ) _2- are even more preferred.

In the formula, * indicates a bonding location 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, 4,4'-diamino-3,3'- Dimethylcyclohexylmethane 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'-diamino-p-terphenyl, 4,4'-bis(4 1,4-bis(4-aminophenoxy)phenyl]benzene, bis[4-(3-aminophenoxy)phenyl]benzene, bis[4-(2-aminophenoxy)phenyl]benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenoxy)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylbenzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl Methane, 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 sulfonium, 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 At least one diamine selected from the following: phenoxy)biphenyl, 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 0030-0031 of International Patent Application Publication No. 2017/038598 are also preferred.

Alternatively, a diamine comprising two or more alkyl diol units as described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 on the main chain can 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, it is preferable that R ¹¹¹ is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, the divalent organic group represented by formula (61) is even more preferable.

Equation (51)

In formula (51), R ⁵⁰ ~ R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ ~ R ⁵⁷ is a fluorine atom, a methyl or a trifluoromethyl atom, and * independently represents the bonding site with the nitrogen atom in formula (2).

Examples of monovalent organic groups, such as R ⁵⁰ to R ⁵⁷ , 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).

In formula (61), R ⁵⁸ and R ⁵⁹ are fluorine atoms, methyl or trifluoromethyl atoms, respectively, and * 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 the group represented by formula (5) or formula (6) below is even more preferred.

In equation (5) or (6), * independently represents the bonding location with other structures.

In formula (5), R ¹¹² is a single bond or a divalent linker, preferably selected from a single bond or a group of 1 to 10 carbon atoms that can be substituted by a fluorine atom, such as aliphatic hydrocarbons, -O-, -CO-, -S-, -SO _2- and -NHCO-, and combinations thereof. It is more preferably selected from a single bond, a group of 1 to 3 carbon atoms that can be substituted by a fluorine atom, such as alkyl groups, -O-, -CO-, -S- and -SO _2- . It is even more preferably selected from a divalent 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 the anhydride group is removed from tetracarboxylic acid dianhydride. As a structure corresponding to R ¹¹⁵ , polyimide precursors may contain only one type of tetracarboxylic acid dianhydride residue, or they may contain two or more types.

Tetracarboxylic dianhydrides are preferably represented by the following formula (O).

In equation (O), R ¹¹⁵ represents a tetravalent organic group. 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’-oxophthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane. Dihydrides, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-paracetamoltetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and such alkyl groups having 1 to 6 carbon atoms 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 can also have an OH group. More specifically, as R ¹¹¹ , the residual group of a diaminophenol derivative can be cited.

In formula (2), R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferable to include a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene group. Furthermore, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and even more preferable that both contain polymerizable groups. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ 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 with ethylene-unsaturated bonds, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxobutyl, and benzo[a] group. Azolium group, block isocyanate group, amine group. As a free radical polymerizable group for polyimide precursors, groups with ethylene unsaturated bonds are 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.

In formula (III), R ²⁰⁰ represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred.

In equation (III), * indicates a bonding location with other structures.

In formula (III), R ²⁰¹ represents an alkyl group with 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, cycloalkyl group or polyalkylene group.

Examples of preferred R ²⁰¹ include alkylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH ₂ CH(OH)CH _2- , polyalkylene, alkylene, propylene, -CH ₂ CH(OH)CH _2- , cyclohexylene, polyalkylene, and alkylene, propylene, or polyalkylene are preferred.

In this invention, a polyalkylene group refers to an alkylene group directly bonded to two or more groups. The alkylene groups within the plurality of alkylene groups contained in a polyalkylene group may be the same or different.

When a polyalkoxy group contains multiple alkoxy groups with different alkyl groups, the arrangement of the alkoxy groups in the polyalkoxy group can be random, block-shaped, or alternating.

The number of carbon atoms in the aforementioned alkyl group (including the number of carbon atoms containing the substituent if the alkyl group has substituents) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is even more preferred, 2 to 5 is further preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is the best.

Furthermore, the aforementioned alkyl groups may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

Furthermore, the number of alkoxy groups contained in the polyalkoxy group (the repetition number of the polyalkoxy group) is preferably 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, polytetramethethyleneoxy, or groups obtained by bonding a plurality of ethyleneoxy groups with a plurality of propoxy groups are preferred as polyvinyloxy groups. Polyvinyloxy or polypropyleneoxy groups are more preferred, and polyvinyloxy groups are even more preferred. In the groups obtained by bonding a plurality of ethyleneoxy groups with a plurality of propoxy groups, the ethyleneoxy and propoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred states of repeated 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 an ethylene unsaturated bond. N,N-dimethylaminopropyl methacrylate is an example of such a tertiary amine compound having an ethylene unsaturated bond.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, there is no particular limitation as long as it is an alkaline soluble group such as a phenolic hydroxyl group or a carboxyl group that decomposes under the action of acid. However, acetal, ketal, silyl, silyl ether, and tertiary alkyl ester groups are preferred. From the perspective of exposure sensitivity, acetal or ketal groups are more preferred.

Specific examples of acid-degrading groups include tributoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tributoxycarbonylmethyl, and trimethylsilyl ether. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

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

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

The repeating unit represented by formula (2) is preferably the 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 the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the exposure tolerance can be further increased.

Equation (2-A)

In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 independently represent divalent organic groups, ^R113 and ^R114 independently represent hydrogen atoms or monovalent organic groups, and at least one of ^R113 and ^R114 is a group containing polymerizable groups, preferably both of which are groups containing polymerizable groups.

^A1 , ^A2 , ^R111 , ^R113 and ^R114 are independently equivalent to ^A1 , ^A2 , ^R111 , ^R113 and ^R114 in formula (2), and their preferred ranges are also the same.

R ¹¹² has the same meaning as R ¹¹² 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).

As one embodiment of the polyimide precursor of this invention, an example is provided where the content of 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 especially preferred. There is no particular upper limit to the total content; all repeating units in the polyimide precursor, except for the terminal units, can also be the 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 aforementioned 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 specified for the molecular weight dispersion of the polyimide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is even more preferred.

In this specification, the molecular weight dispersion is a value calculated using the weight-average molecular weight / number-average molecular weight.

Furthermore, when the resin composition includes multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility of at least one polyimide precursor 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 polyimide precursors as a single resin are each within the aforementioned ranges.

Polybenzo[ [Pro-azole]

Regarding the polybenzo[a] used in this invention There are no particular requirements regarding the structure of azole precursors, but it is preferred that they contain repeating units represented by the following formula (3).

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 equation (3), R ¹²³ and R ¹²⁴ have the same meaning as R ¹¹³ in equation (2), and the preferred range is 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. Preferably, the divalent organic group comprises at least one of an aliphatic group and an aromatic group. As an aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably 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 even more preferred.

As a dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferred, and a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups is even more preferred. The number of carbon atoms in the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2-30, more preferably 2-25, further preferably 3-20, even more preferably 4-15, and particularly preferably 5-10. The straight-chain aliphatic group is preferably an alkyl group.

Examples of dicarboxylic acids containing aliphatic groups in a linear chain 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-tetrafluorodicarboxylic acid. Methyl 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, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

(In the formula, Z represents a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

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

[Chemical Formula 12]

In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ -, and * represents the bonding site with other structures independently.

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

In equation (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, it has the same meaning as R ¹¹⁵ in equation (2) above, and the preferred range is also the same.

R ¹²² is preferably a group derived from a diaminophenol derivative. Examples of groups derived from diaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl ion, 4,4'-diamino-3,3'-dihydroxydiphenyl ion, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2,2-bis-(3-amino-4-hydroxyphenyl)propane. Examples of bis(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.

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 to represent the structure described in the above formula. When R ¹²² has the structure represented by the above formula, it is preferable that any two of the four * and # are bonded to nitrogen atoms bound to R ¹²² in formula (3) and the other two are bonded to oxygen atoms bound to R ¹²² in formula (3). It is even better that two * are bonded to oxygen atoms bound to R ¹²² in formula (3) and two # are bonded to nitrogen atoms bound to R ¹²² in formula (3), or two * are bonded to nitrogen atoms bound to R ¹²² in formula (3) and two # are bonded to oxygen atoms bound to 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).

The diaminophenol derivatives represented by formula (A-s) are also preferred.

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

(In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (A-s) above.)

In the above formula (As), it is considered that having a substituent at the position adjacent to the phenolic hydroxyl group, that is, at _R3 , will bring the carbonyl carbon of the amide bond closer to the hydroxyl group, which is particularly good in terms of further improving the effect of achieving a high cyclization rate when 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 high transparency to i-rays and achieve a high cyclization rate when hardened at low temperatures, 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 _R1 include linear or branched alkyl groups having 1 to 8 carbon atoms, in which polystyrene exhibits an excellent balance between maintaining high transparency to X-rays and high cyclization rate during low-temperature curing, while also achieving sufficient solubility in solvents. Regarding azole precursors, _-CH2- , -CH( _CH3 )-, and -C( _CH3 ) _2- are preferred.

For a method of manufacturing the diaminophenol derivative represented by the above formula (A-s), please refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, and such contents are incorporated herein by reference.

Specific examples of the structures of diaminophenol derivatives represented by the above formula (A-s) can be found in paragraphs 0070-0080 of Japanese Patent Application Publication No. 2013-256506, and such contents are incorporated herein by reference. However, it is self-evident that these are not the only possible examples.

Polybenzo[ In addition to the repeated units of formula (3) above, azole precursors may also contain other types of repeated units.

In terms of suppressing warping caused by ring closure, polyphenylene oxide (PPO) It is preferable that the azole precursor contains a diamine residue represented by the following formula (SL) as a repeating unit of other types.

[Chemical Formula 16]

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 can be preferably represented by ^R5s and ^R6s in the b structure being phenyl. Furthermore, the molecular weight of the structure shown in formula (SL) is preferably 400-4,000, and more preferably 500-3,000. By setting the molecular weight within the above range, the polyphenylene oxide content can be reduced more effectively. The elastic modulus of the azole precursor after dehydration and ring closure can achieve both the effect of inhibiting warpage and improving solvent solubility.

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

Polybenzo[ The weight-average molecular weight (Mw) of the azole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. 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 above polybenzo[a] A molecular weight dispersion of 1.4 or higher for the azole precursor is preferred, 1.5 or higher is even better, and 1.6 or higher is further preferred. (Polybenzoxylene) There is no specific upper limit for the molecular weight dispersity of azole precursors. For example, 2.6 or less is preferred, 2.5 or less is better, 2.4 or less is even better, 2.3 or less is even better, and 2.2 or less is even better.

Furthermore, the resin composition contains multiple types of polystyrene. In the case of azole precursors as specific resins, at least one polybenzo[a]azole precursor is present. The weight-average molecular weight, number-average molecular weight, and dispersibility of the azole precursor are preferably within the above-mentioned ranges. Furthermore, the above-mentioned plurality of polybenzo[…] The weight-average molecular weight, number-average molecular weight, and dispersibility of the azole precursor as a resin are also better if they are within the above-mentioned ranges.

[Polyamide imide precursor]

Polyamide imide precursors preferably contain repeating units represented by the following formula (PAI-2).

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 be exemplified as 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 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 combining two or more of these groups with a single bond or by a linking group. It is even more preferred to have an aromatic group with 6 to 20 carbons, or an aromatic group obtained by combining two or more of these groups with a single bond or by a linking group.

As the linking group mentioned above, a linking group formed by -O-, -S-, -C(=O)-, -S(=O) _2- , alkylene, halogenated alkylene, arylene, or two or more of the above bonds is preferred, and a linking group formed by -O-, -S-, alkylene, halogenated alkylene, arylene, or two or more of the above bonds is even more preferred.

Of the aforementioned alkyl groups, those having 1 to 20 carbon atoms are preferred, those having 1 to 10 carbon atoms are more preferred, and those having 1 to 4 carbon atoms are even more preferred.

Of the aforementioned halogenated alkyl groups, those with 1 to 20 carbon atoms are preferred, those with 1 to 10 carbon atoms are more preferred, and those with 1 to 4 carbon atoms are 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.

Of the aforementioned aryl group, phenyl or naphthyl group is preferred, phenyl group is more preferred, and 1,3-phenyl or 1,4-phenyl group is 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 described above.

In this invention, compounds having three carboxyl groups are referred to as tricarboxylic acid compounds.

Two of the three carboxyl groups in the above tricarboxylic acid compound can be anhydride-substituted.

As halogenable tricarboxylic acid compounds used in the manufacture of polyamide imine precursors, examples include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

One or more of these tricarboxylic acid compounds 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 formed 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 formed 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 anhydride-substituted (e.g., trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride acetochlor).

In formula (PAI-2), ^R111 , ^A2 , and ^R113 have the same meaning as ^R111 , ^A2 , and ^R113 in formula (2) above, and the better state is also the same.

Polyamide imide precursors can further include other repeating units.

Other examples of repeating units include the repeating unit represented by equation (2) above, and the repeating unit represented by equation (PAI-1) below.

[Chemical Formula 18]

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 be an example of 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 an aromatic group obtained by combining two or more of these groups with a single bond or by linking groups.

As the linking group mentioned above, a linking group formed by -O-, -S-, -C(=O)-, -S(=O) _2- , alkylene, halogenated alkylene, arylene, or two or more of the above bonds is preferred, and a linking group formed by -O-, -S-, alkylene, halogenated alkylene, arylene, or two or more of the above bonds is even more preferred.

Of the aforementioned alkyl groups, those having 1 to 20 carbon atoms are preferred, those having 1 to 10 carbon atoms are more preferred, and those having 1 to 4 carbon atoms are even more preferred.

Of the aforementioned halogenated alkyl groups, those with 1 to 20 carbon atoms are preferred, those with 1 to 10 carbon atoms are more preferred, and those with 1 to 4 carbon atoms are 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.

Of the aforementioned aryl group, phenyl or naphthyl group is preferred, phenyl group is more preferred, and 1,3-phenyl or 1,4-phenyl group is even more preferred.

Furthermore, it is preferable that R ¹¹⁶ is derived from dicarboxylic acid compounds or dicarboxylic acid dihalides.

In this invention, compounds having two carboxyl groups are referred to as dicarboxylic acid compounds, and compounds having two halogenated carboxyl groups are referred to as dicarboxylic acid dihalides.

In dicarboxylic acid dihalides, the carboxyl group only needs to be halogenated; for example, chlorination is preferred. That is, dicarboxylic acid dihalides are preferably dicarboxylic acid dichloride compounds.

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.

One or more of these dicarboxylic acid compounds or dicarboxylic acid dihalides may be used.

Specifically, as a dicarboxylic acid compound or dicarboxylic acid dihalogenate, it is preferable that the compound or dicarboxylic acid dihalogenate comprises 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 preferable that the compound or dicarboxylic acid dihalogenate comprises 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.

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 hexafluoro... Sebacatedioic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, dohenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4’-biphenylcarboxylic acid, 4,4’-biphenylcarboxylic acid, 4,4’-dicarboxyl diphenyl ether, benzophenone-4,4’-dicarboxylic acid, etc.

As a specific example of a dicarboxylic acid dihalide, a compound with a structure formed by halogenating two carboxyl groups in the aforementioned dicarboxylic acid compounds can be cited.

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

Furthermore, it is preferable that the polyamide-imide precursor contains fluorine atoms in its structure. A fluorine atom content of 10% by mass or more, and less than 20% by mass, is preferred in the polyamide-imide precursor.

Furthermore, to improve adhesion to the substrate, the polyamide imine precursor can be copolymerized with aliphatic groups having a siloxane 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 upper limit to 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 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 upper limit to 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) or formula (PAI-1).

The weight-average molecular weight (Mw) of the polyamide amide 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 particular upper limit specified for the molecular weight dispersion of the polyamide-imide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is even more preferred. Furthermore, when the resin composition includes multiple polyamide-imide precursors 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 precursor are within the above-mentioned ranges. Furthermore, it is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when treating the aforementioned multiple polyamide imide precursors as a single resin are all within the ranges described above.

[Manufacturing methods for polyimide precursors, etc.]

Polyimide precursors 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 alkylating agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, and then reacting it in the presence of diamine and a condensing agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting it with diamine, etc. Among the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting it with diamine is preferred.

Examples of such condensing agents include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

Examples of the aforementioned 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 such halogenating agents include thiocyanate, glyphosate, and phosphorus oxychloride.

In the manufacturing process of polyimide precursors, 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 set according to the raw materials, but 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 process of polyimide precursors, 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 set according to the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

-Pre-constriction agent-

In the manufacturing process of polyimide precursors, etc., it is preferable to seal the carboxylic anhydride, anhydride derivative, or amine group remaining at the ends of the resin, etc., in order to further improve storage stability. When sealing the carboxylic anhydride and anhydride derivative remaining at the ends of the resin, monohydric alcohols, phenols, thiols, benzenethiophenols, monoamines, etc., can be used as end-capping agents. From the viewpoint of reactivity and film stability, monohydric alcohols, 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 tert-butanol, adamantanol, etc. Preferred compounds for phenols include phenols, methoxyphenol, methylphenol, 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, and 1-carboxy-5-aminonaphthalene. Examples of amino acids include 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, and 4-aminobenzenethiophenol. Two or more of these can be used, and by reacting a plurality of end-capping agents, a plurality of different terminal groups can be introduced.

Furthermore, when sealing the amine groups at the ends of the resin, compounds with functional groups capable of reacting with the amine groups can be used for sealing. Preferred sealants 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-norcamphene-2,3-dicarboxylic anhydride. Furthermore, preferred compounds for carboxylic acid chlorides include acetyl chloride, acrylamide chloride, propionyl chloride, methacrylamide chloride, trimethylacetyl chloride, cyclohexanemethyl chloride, 2-ethylhexyl chloride, cinnamic acid chloride, 1-draconanemethyl chloride, heptafluorobutyric acid chloride, stearic acid chloride, and benzoyl chloride.

-Solid precipitation-

In the manufacture of polyimide precursors, a solid precipitation step may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer components are added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, causing the polymer components to precipitate as a solid and then dried, thereby obtaining the polyimide precursor. To improve purity, the processes of re-dissolving, re-precipitating, and drying the polyimide precursor can be repeated. Furthermore, a step of using an ion exchange resin to remove ionic impurities may be included.

[Content]

The content of a specific resin in the resin composition of the present invention, relative to the total solid content of the resin composition, 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. Furthermore, the content of the resin in the resin composition of the present invention, relative to the total solid content of the resin composition, 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.

The resin composition of this invention may contain only one specific resin, or it may contain two or more. When two or more resins are contained, the total amount within the above-mentioned range is preferred.

Furthermore, it is preferable that the resin composition of this invention contains at least two resins.

Specifically, the resin composition of the present invention may collectively comprise two or more specific resins and other resins described below, or may comprise two or more specific resins, but comprising two or more specific resins is preferred.

In the case where the resin composition of the present invention contains two or more specific resins, it is preferable to contain two or more polyimide precursors that are polyimide precursors and are derived from dianhydrides (R ¹¹⁵ as described in formula (2) above) with different structures.

<Other Resins>

The resin composition of this invention may include the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins").

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, resin compositions with excellent paintability can be obtained, and patterns (cured products) with excellent solvent resistance can also be obtained.

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, in the resin composition of the present invention, the content of other resins relative to the total solid content of the resin composition is preferably 80% by weight or less, more preferably 75% by weight or less, further preferably 70% by weight or less, even more preferably 60% by weight or less, and even more preferably 50% by weight 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; it is acceptable as long as it is 0% by mass or more.

The resin composition of this invention may contain only one other resin, or it may contain two or more. When two or more resins are contained, the aggregate amount is preferably within the above-mentioned range.

<Compound B>

The resin composition of this invention includes compound B, which produces a base through the action of a base.

Compound B can be exemplified by compounds having a base group protected by a base-decomposing group.

The base group protected by the base-decomposing group is not particularly limited. For example, it can be a protected group of a known amine that can be deprotected using a alkali. Groups with an aminocarbamate structure are preferred, such as 9-fluorenylmethylaminocarbamate, 1,1-dimethyl-2-cyanomethylaminocarbamate, p-nitrobenzylaminocarbamate, and 2,4-dichlorobenzylaminocarbamate.

Furthermore, it is preferable that compound B contains an amino ester bond. Preferably, the amino ester bond is contained within a base protected by a base-decomposing group, and it is even more preferable that the amino ester bond decomposes to produce an amine through the action of a base.

The alkali produced from compound B by the action of a base is preferably an amine, and secondary or tertiary amines are even better.

Furthermore, for the condylar acid of the base produced from compound B by the action of the base, a pKa of 0 or higher is preferred, 3 or higher is even more preferred, and 6 or higher is still preferred. There is no particular limitation on the lower limit of the pKa of the aforementioned condylar acids, but 30 or lower is preferred.

pKa is the negative common logarithm of the equilibrium constant Ka, representing the dissociation reaction that releases hydrogen ions from an acid. In this specification, unless otherwise stated, pKa is assumed to be a calculation based on ACD/ChemSketch (registered trademark).

In the presence of multiple pKa values of the aforementioned conjugated acids, it is preferable that at least one pKa falls within the aforementioned range.

The base produced from compound B by the action of a base can be a base with only one base group, or it can be a base with two or more base groups.

Furthermore, the alkali produced from compound B through the action of the alkali can be one molecule or more than two molecules.

The molecular weight of the alkali produced from compound B by the action of the alkali is preferably 50-300, and even more preferably 80-250.

There are no particular limitations on the specific examples of the alkali produced, but examples include piperidine, 4-hydroxyethylpiperidine, 4-(3-phenylpropylpiperidine), cyclohexylamine, diisopropylamine, dicyclohexylamine, dimethylpiperidine, 1,3-di-4-piperidinylpropane, 2,6-dimethylpiperidine, methylcyclohexylamine, 4-hydroxymethylpiperidine, diisobutylamine, isopropylcyclohexylamine, and ditert-isobutylamine.

Compound B is preferably represented by formula (1-1), formula (1-2), or formula (1-3), with the compound represented by formula (1-1) being more preferred.

In formula (1-1), ^R1 represents a hydrogen atom or a substituted hydrocarbon, ^R2 represents a substituted hydrocarbon, and ^R1 and ^R2 can bond to form a ring structure; In formula (1-2), ^R1 represents a hydrogen atom or a substituted hydrocarbon, ^R2 represents a substituted hydrocarbon, ^R1 and ^R2 can bond to form a ring structure, ^R3 independently represents a hydrogen atom or a substituted hydrocarbon, ^R4 represents a cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) _2R , fluorinated alkyl or halogen atom, and R represents a substituted hydrocarbon; In formula (1-3), ^R1 represents a hydrogen atom or a substituted hydrocarbon, R ² represents a substitutable hydrocarbon. ^R1 and ^R2 can bond to form a ring structure. ^R3 represents a hydrogen atom or a substitutable hydrocarbon independently. Ar represents an aromatic group substituted with at least one group selected from cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) _2R , fluorinated alkyl, and halogen atom. R represents a substitutable hydrocarbon.

In equation (1-1), ^R1 represents a hydrogen atom or a substitutable group, with a substitutable group being preferred.

Of the aforementioned hydrocarbon groups, alkyl, alkenyl, alkynyl, or aryl are preferred, with alkyl or aryl being even more preferred.

Of the aforementioned alkyl groups, those having 1 to 10 carbon atoms are preferred, and those having 2 to 10 carbon atoms are even more preferred. The aforementioned alkyl groups can be any of straight-chain, branched-chain, or cyclic, or can be groups represented by combinations thereof.

Of the alkenyl groups described above, those having 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are even more preferred. The alkenyl group can be any of linear, branched, or cyclic forms, or can be a group represented by a combination of these.

Of the aforementioned alkynyl groups, those with 2 to 10 carbon atoms are preferred, and those with 2 to 6 carbon atoms are even more preferred. The aforementioned alkynyl group can be any of linear, branched, or cyclic, or can be a group represented by a combination of these.

Of the aforementioned aryl groups, those with 1 to 20 carbon atoms are preferred, those with 6 to 10 carbon atoms are more preferred, and phenyl groups are even more preferred. Furthermore, it is preferable that the aforementioned aryl group is an aromatic hydrocarbon.

As substituents in the aforementioned hydrocarbon groups, known substituents can be used within the scope that achieves the effects of the present invention; examples include hydroxyl groups.

In equation (1-1), ^R2 represents a substitutable hydrocarbon. The preferred state of ^R2 is the same as that of ^R1 in equation (1-1) above.

In equation (1-1), ^R1 and ^R2 can be bonded to form a ring structure. A 5-membered or 6-membered ring structure is preferred, with a 6-membered ring being more desirable. Furthermore, the aforementioned ring structure can be an aliphatic ring structure or an aromatic ring structure, but an aliphatic ring structure is preferred.

Specifically, as a ring structure formed by the ^R1 and ^R2 bonds, piperidine rings that can have substituents can be cited as an example.

Examples of substituents mentioned above include alkyl, hydroxyalkyl, and aralkyl groups.

In equation (1-2), the better states of ^R1 and ^R2 are the same as those of ^R1 and ^R2 in equation (1-1).

In formulas (1-2), ^R3 independently represents a hydrogen atom or a substituted hydrocarbon. Alkyl, alkenyl, alkynyl or aryl are preferred as the above hydrocarbons, alkyl or aryl are more preferred, and alkyl is even more preferred.

Of the aforementioned alkyl groups, those having 1 to 10 carbon atoms are preferred, those having 1 to 4 carbon atoms are more preferred, and methyl groups are even more preferred. The aforementioned alkyl groups can be any of straight-chain, branched-chain, or cyclic, or can be groups represented by combinations thereof.

Of the alkenyl groups described above, those having 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are even more preferred. The alkenyl group can be any of linear, branched, or cyclic forms, or can be a group represented by a combination of these.

Of the aforementioned alkynyl groups, those with 2 to 10 carbon atoms are preferred, and those with 2 to 6 carbon atoms are even more preferred. The aforementioned alkynyl group can be any of linear, branched, or cyclic, or can be a group represented by a combination of these.

Of the aforementioned aryl groups, those with 1 to 10 carbon atoms are preferred, those with 6 to 10 carbon atoms are more preferred, and phenyl groups are even more preferred. Furthermore, it is preferable that the aforementioned aryl group is an aromatic hydrocarbon.

As substituents in the aforementioned hydrocarbon groups, known substituents can be used within the scope that achieves the effects of the present invention; examples include hydroxyl groups.

In formula (1-2), ^R4 represents a cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) _2R , fluorinated alkyl, or halogen atom. From the viewpoint of alkali production efficiency, cyano is preferred. R represents a substitutable hydrocarbon group, preferably alkyl, alkenyl, alkynyl, aromatic hydrocarbon, or a combination thereof. Alkyl, aromatic hydrocarbon, or a combination thereof is more preferred, and alkyl, phenyl, naphthyl, or a combination thereof with 1 to 10 carbon atoms is even more preferred. Examples of substituents in R include halogen atoms, hydroxyl groups, and alkoxy groups.

In equation (1-3), the better states of ^R1 and ^R2 are the same as those of ^R1 and ^R2 in equation (1-1).

In equation (1-3), the best state of ^R3 is the same as that of ^R3 in equation (1-2).

In formula (1-3), Ar represents an aromatic group substituted with at least one group selected from cyano, nitro, -C(=O)OR, -OC(=O)R, -C(=O)R, -S(=O) _2R , fluorinated alkyl, halogen atom.

The optimal state of R is the same as that of R in equation (1-2) above.

Of the aforementioned aromatic groups, those with 1 to 20 carbon atoms are preferred, those with 6 to 10 carbon atoms are even more preferred, and phenyl groups are further preferred. These aromatic groups can be aromatic hydrocarbons or aromatic heterocyclic groups, but aromatic hydrocarbons are preferred.

Furthermore, using a compound without an acid group as compound B is also preferable. Based on the above, it is believed that the migration of metals such as copper is also easily suppressed, resulting in a hardened film with excellent adhesion.

The molecular weight of compound B is preferably 100-700, preferably 100-500, and even more preferably 150-400.

As specific examples of compound B, the following compounds can be cited.

[Chemical Formula 20]

[Chemical Formula 21]

The content of compound B relative to the total mass of the resin composition of the present invention is preferably 0.1~20.0% by mass, more preferably 0.1~10.0% by mass, and even more preferably 0.5~5.0% by mass.

<Organometallic complexes>

From the perspective of drug resistance, it is preferable that the resin composition of this invention contains organometallic complexes.

Organometallic complexes only need to be organic complexes containing metal atoms, but complexes containing both metal atoms and organic groups are preferred. Compounds in which the organic groups coordinate to the metal atoms are even better, and metallocene compounds are even more preferred.

In this invention, metallocene compounds refer to organometallic complexes having two cyclopentadienyl anionic derivatives, which can have substituents, as n5-ligands.

There are no particular limitations on the aforementioned organic groups, but hydrocarbon groups or groups formed by combinations of hydrocarbon groups and heteroatoms are preferred. Oxygen, sulfur, and nitrogen atoms are preferred as heteroatoms.

In this invention, it is preferred that at least one of the organic groups is a cyclic group, and even more preferred that at least two are cyclic groups.

The cyclic bases mentioned above are preferably selected from 5-membered and 6-membered cyclic bases, with 5-membered cyclic bases being even more preferred.

The aforementioned cyclic group can be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferred.

As a 5-membered cyclic group, cyclopentadienyl is preferred.

Furthermore, it is preferable that the organometallic complex used in this invention contains 2 to 4 cyclic groups per molecule.

The metals included in the organometallic complex are not particularly limited, but metals corresponding to Group 4 elements are preferred. It is even more preferred to select at least one metal from the group consisting of titanium, zirconium, and ruthenium, and it is further preferred to select at least one metal from the group consisting of titanium and zirconium. Titanium is particularly preferred.

Organometallic complexes can contain two or more metal atoms, or they can contain only one metal atom, but containing only one metal atom is preferred. When an organometallic complex contains two or more metal atoms, it can contain only one type of metal atom, or it can contain two or more types of metal atoms.

The organometallic complex is preferably a ferrocene compound, a titanium diacene compound, a zirconia diacene compound, or a hafnocene compound; more preferably a titanium diacene compound, a zirconia diacene compound, or a hafnocene compound; even more preferably a titanium diacene compound or a zirconia diacene compound; and most preferably a titanium diacene compound.

The organometallic complex with a photoradical polymerization initiation energy is also one of the preferred states of this invention.

In this invention, the concept of a photoradical polymerization initiation energy indicates the ability to generate free radicals capable of initiating free radical polymerization upon light irradiation. For example, when a composition containing a radical crosslinker and an organometallic complex is irradiated with light in a wavelength range where the organometallic complex absorbs light but the radical crosslinker does not, the presence or absence of a photoradical polymerization initiation energy can be determined by confirming whether the radical crosslinker disappears. When confirming the presence or absence of disappearance, an appropriate method can be selected based on the type of radical crosslinker; for example, confirmation can be made simply by IR determination (infrared spectroscopy) or HPLC determination (high-performance liquid chromatography).

When the organometallic complex possesses a photoradical polymerization initiation energy, metallocene compounds are preferred, with titanium diacene, zirconium diacene, or titanium diacene being even more preferred, titanium diacene or zirconium diacene being further preferred, and titanium diacene being particularly preferred.

When the organometallic complex does not possess a photoradical polymerization initiation energy, it is preferable that the organometallic complex is selected from at least one compound chosen from the group consisting of titanium diacene compounds, tetraalkoxy titanium compounds, nitrified titanium compounds, titanium chelates, zirconium diacene compounds, and titanium diacene compounds; more preferably, it is selected from at least one compound chosen from the group consisting of titanium diacene compounds, zirconium diacene compounds, and titanium diacene compounds; even more preferably, it is selected from at least one compound chosen from the group consisting of titanium diacene compounds and zirconium diacene compounds; and titanium diacene compounds are particularly preferred.

The molecular weight of organometallic complexes is preferably 50–2,000, and even more preferably 100–1,000.

As organometallic complexes, compounds represented by the following formula (P) are preferred examples.

In formula (P), M represents a metal atom, and R are each an independent substituent.

Preferably, R is selected independently from aromatic groups, alkyl groups, halogen atoms, and alkyl sulfonyloxy groups.

In formula (P), iron, titanium, zirconium, or ruthenium atoms are preferred as the metal atom represented by M; titanium, zirconium, or ruthenium atoms are even more preferred; titanium or zirconium atoms are further preferred; and titanium atoms are particularly preferred.

As for the aromatic group in R of formula (P), examples of aromatic groups with 6 to 20 carbon atoms are preferred, such as phenyl, 1-naphthyl, or 2-naphthyl.

As for the alkyl group in R of formula (P), alkyl groups with 1 to 20 carbon atoms are preferred, and alkyl groups with 1 to 10 carbon atoms are even more preferred. Examples include methyl, ethyl, propyl, octyl, isopropyl, tributyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl.

Examples of halogen atoms in the aforementioned R group include F, Cl, Br, and I.

As the alkyl group constituting the alkyl sulfonyloxy group in R above, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is even more preferred. Examples include methyl, ethyl, propyl, octyl, isopropyl, tributyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl.

The R group mentioned above can also have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acetyl, alkoxycarbonyl, aryloxycarbonyl, acetyloxy, monoalkylamine, dialkylamine, monoarylamine, and diarylamine.

Specific examples of organometallic complexes are not particularly limited, but examples include tetraisopropoxytitanium, tetra(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetate)titanium, diisopropoxybis(acetate acetone)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium, pentamethylcyclopentadienyltrimethyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds.

In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 may be used, but are not limited thereto.

The content of organometallic compounds relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass. A lower limit of 1.0% by mass or more is more preferred, 1.5% by mass or more is further preferred, and 3.0% by mass or more is particularly preferred. An upper limit of 25% by mass or less is more preferred.

One or more organometallic complexes may be used. When using two or more, it is preferable that the total amount be within the range mentioned above.

Solvents

The resin composition of this invention preferably includes a solvent.

Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfides, 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, methyl 3-ethoxypropionic acid)). Ethyl esters, etc.), 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.

Examples of preferred ethers 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 ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydroglucanone are considered superior examples.

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

As an ion, dimethyl ion is a preferred 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-methoxymorpholine, and N-acetylmorpholine are considered preferred.

Among ureas, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinedione are considered superior 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 monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

Regarding solvents, from the perspective of improving coating properties, mixing two or more forms is preferable.

In this invention, a solvent selected from 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, or a mixture of two or more solvents, is preferred. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone, or the simultaneous 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 this 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 coating thickness and coating method.

The resin composition of this invention may contain only one solvent or two or more solvents. When containing two or more solvents, it is preferable that the total amount falls within the above-mentioned range.

[Aggregation Initiator]

The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to include a photopolymerization initiator.

Photopolymerization initiators are preferably photoradical polymerization initiators. There are no particular limitations on the photoradical polymerization initiator; it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are photosensitizing to light in the ultraviolet to visible regions are preferred. Alternatively, an active agent that interacts with a photosensitive agent to generate active free radicals can 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 (Varian Medical Systems, Inc., Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g/L.

As a photoradical polymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (e.g., those with trihalomethanes) can be cited. Compounds with skeletons, possessing Compounds with a diazole skeleton, compounds containing trihalomyl groups, etc., acetyphosphine compounds such as acetyphosphine oxide, hexaaryl diimidazole, 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, iron-aromatic complexes, etc. For details regarding these, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and these contents are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, the compound 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 peracid-based initiators described in Japanese Patent Application Publication No. 2019-167313 are also incorporated herein by reference.

As a ketone compound, examples include those described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, and this content is incorporated herein by reference. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used 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, and this content is incorporated herein by reference.

As α-hydroxyketone initiators, the following can be used: 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).

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 amide-based phosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine 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 (residue) 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 compounds described in International Publication No. 20 The compounds described in Japanese Patent Application Publication No. 15/152153, Japanese Patent Application Publication No. 2017/051680, Japanese Unexamined Patent Application No. 2017-198865, compounds described in paragraphs 0025 to 0038 of Japanese Patent Application Publication No. 2017/164127, and compounds described in Japanese Patent Application Publication No. 2013/167515, etc., 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 possess an intramolecular linker with a >C=N-O-C(=O)- group.

Among commercially available products, IRGACURE OXE 01, IR GACURE 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 ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-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 structures can be used.

Oxime compounds with dicyclic rings can also be used as photoradical polymerization initiators. Specific examples of dicyclic oxime compounds include the compounds described in Japanese Patent Application Publication No. 2014-137466 and 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 a carbazole ring forming a naphthalene ring skeleton can also be used. Specific examples of such oxime compounds include those described in International Publication No. 2013/083505, the contents of which are 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, and these contents are incorporated herein by reference.

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

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

As a photoradical polymerization initiator, oxime compounds with hydroxyl substituents bonded to the carbazole skeleton can also be used. Compounds described in International Publication No. 2019/088055 can be cited as such photopolymerization initiators, and this information is incorporated herein by reference.

As a photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an electron-withdrawing group on the aromatic ring Ar ^OX1 can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cycloalgyl Ar ^OX1 include vinyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfinyl, arylsulfinyl, and cyano. Vinyl and nitro are preferred, but vinyl is more preferred due to its ease of forming films with excellent lightfastness, and benzoyl is even more 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 compound represented by formula (OX1) and formula (OX2), with the compound represented by formula (OX2) being more preferred.

In the formula, ^RX1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetyl, acetoxy, amino, phosphine, aminomethyl, or aminosulfonyl; ^RX2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetoxy, or amino; and ^RX3 to ^RX14 each independently represent a hydrogen atom or a substituent.

Among them, 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 specific examples of oxime compounds (OX), the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 are cited, and this content is incorporated into this specification.

Examples of optimal oxime compounds include those with specific substituents as described in Japanese Patent Application Publication No. 2007-269779 and those with thioaryl groups as described in Japanese Patent Application Publication No. 2009-191061, and these are incorporated herein by reference.

From the perspective of exposure sensitivity, photoradical polymerization initiators are selected from sources including trihalomethanes. Compounds, benzyl dimethyl ketone compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetophosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halogenated compounds Compounds from the group consisting of diazole compounds and 3-aryl-substituted coumarin compounds are preferred.

A further preferred photoradical polymerization initiator is trihalomethane trihalomethane. Compounds, α-aminoketone compounds, acetylsphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, selected from compounds including trihalomethanes. It is further preferred to use at least one compound from the group consisting of compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds, and it is even more preferred to use metallocene compounds or oxime compounds.

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-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-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. Compounds represented by formula (I) below can also be used.

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 or 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 a group identical to ^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 28]

In the formula, R ^I05 ~ R ^I07 are the same as R ^I02 ~ R ^I04 in the above formula (I).

Furthermore, the photoradical polymerization initiators may also include compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469, and this content is incorporated into this specification.

As a photoradical polymerization initiator, a photoradical polymerization initiator with two or more functionalities can be used. By using such a photoradical polymerization initiator, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Furthermore, when using compounds with asymmetrical structures, the crystallinity decreases while the solubility in solvents increases, making it difficult to precipitate 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 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017/033680; and compounds (E) and (G) described in Japanese Patent Application Publication No. 2013-522445. The photoinitiators described in this specification include Cmpd1-7 as disclosed in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiator (A) described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669.

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, further preferably 0.5-15% by mass, and even more preferably 1.0-10% by mass. The photopolymerization initiator may be contained in only one type or in two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

Furthermore, photopolymerization initiators sometimes also function as thermal polymerization initiators; therefore, heating with an oven or heating plate can sometimes further facilitate crosslinking based on the photopolymerization initiator.

[Sensitizer]

Resin components may include sensitizers. Sensitizers absorb specific active radiation to become electronically excited. These electronically excited sensitizers then come into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., thereby generating electron transfer, energy transfer, and heating. As a result, 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, benzophenone-based, milchnerone-based, coumarin-based, pyrazole azo, aniline azo, triphenylmethane-based, anthraquinone-based, anthracene-based, anthraquinone-based, benzylene-based, oxocyanine-based, pyrazolotriazole azo, pyridone azo, anthocyanin-based, and phenanthrene-based sensitizers are all suitable. Series, pyrrolopyrazole azomethine series, Compounds such as phthalocyanine, benzopyran, and indigo series.

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-dimethylaminophenylenepropyl dihydroindone, p-dimethylaminobenzyl dihydroindone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2- (p-Dimethylaminophenylethylene)benzothiazole, 2-(p-Dimethylaminophenylethylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated-7-dimethylaminocoumarin, 3-ethoxycarbonyl-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-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-phenylbenzimidazole, 1-phenyl-5-phenyltetrazole, 2-phenylbenzothiazole, 2-(p-dimethylaminostyryl)benzo[[...]] Zyrazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoaniline, N-methylacetamide, 3',4'-dimethylacetamide, etc.

Alternatively, other sensitizing pigments can be used.

For detailed information regarding the sensitized pigments, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, and this information is incorporated into this specification.

When the resin composition contains a sensitizer, the sensitizer content relative to the total solids 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 can be used, or two or more sensitizers can be used simultaneously.

[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-, _-SO₂ , -S-, -NO-, SH, PH, SiH, and GeH within the molecule, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having a thiocarbonyl sulfide group for 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 may also use the compounds described in paragraphs 0152-0153 of International Publication No. 2015/199219, and that content is incorporated into 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 further 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.

A photoacid generator is a compound that produces at least one of Brinzyl acid and Lewis acid upon irradiation with light in the range of 200 nm to 900 nm. Preferably, the irradiated light has a wavelength of 300 nm to 450 nm, and more preferably 330 nm to 420 nm. When used alone or in conjunction with a sensitizer, a photoacid generator capable of producing acid through photosensitivity is preferred.

Examples of 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 sulfonamides.

Examples of photoacid generators used in the resin composition of this invention include, for instance, quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonic acid compounds, and onmium salt compounds.

From the perspectives of sensitivity and preservation stability, organohalogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred; from the perspective 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 diazonium compound, it is possible to obtain a resin composition that is photosensitive to the i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) of a conventional ultraviolet mercury lamp.

As hydroxyl compounds, specific examples include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tributanol, 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, 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 manufactured by ASAHI YUKIZAI CORPORATION 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. (The following are product names: 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-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl ether, but it is not limited to these.

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

Among these, compounds containing phenolic compounds and esters with a 4-naphthoquinone diazidesulfonate group are preferred as quinone diazide compounds. This allows for higher sensitivity and higher resolution to 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, and more preferably 10 to 40 parts by weight, relative to 100 parts by weight of the resin. 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 in the oxime sulfonate compound; however, oxime sulfonate compounds represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) are preferred.

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. Preferably, the alkyl group in ^X3 is a straight-chain or branched alkyl group having 1 to 4 carbon atoms. Preferably, the alkoxy group in ^X3 is a straight-chain or branched alkoxy group having 1 to 4 carbon atoms. Preferably, the halogen atom in ^X3 is a chlorine or fluorine atom.

In equation (OS-1), m3 represents an integer from 0 to 3, with 0 or 1 being preferred. When m3 is 2 or 3, the complex numbers ^X3 can 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.

Specific examples of oxime sulfonate compounds represented by formula (OS-1) include 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, and these contents are incorporated herein by reference.

In formulas (OS-103) to (OS-105), ^Rs1 represents alkyl, aryl, or heteroaryl; sometimes there are multiple ^Rs2 that independently represent hydrogen, alkyl, aryl, or halogen atoms; sometimes there are multiple ^Rs6 that independently represent halogen, alkyl, alkoxy, sulfonic acid, aminosulfonyl, or alkoxysulfonyl; 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 group (preferably with 1 to 30 carbons), aryl group (preferably with 6 to 30 carbons), or heteroaryl group (preferably with 4 to 30 carbons) represented by R s1 may have known substituents within the range that can achieve the effects of the present invention.

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 formulas (OS-103) to (OS-105), a ring containing Xs as a member is a 5-member ring or a 6-member ring.

In equations (OS-103) to (OS-105), ns represents 1 or 2. When Xs is 0, 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 with 1 to 30 carbon atoms) and alkoxy group (preferably with 1 to 30 carbon atoms) represented by R ^s6 may have substituents.

In equations (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 even better, and 0 being exceptionally good.

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).

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

In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, with 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), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, with a hydrogen atom being preferred.

R ^t2 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 either one of them or a mixture thereof.

Specific examples of oxime sulfonate compounds represented by formulas (OS-103) to (OS-105) are 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, and these contents are incorporated herein by reference.

Other preferred embodiments of oxime sulfonate compounds containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In formula (OS-101) or formula (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 formula (OS-102), ^Ru2a represents alkyl or aryl.

In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5- , -CH _2- , -CR ^u6 H- or CR ^u6 R ^u7- , and R ^u5 ~ R ^u7 represent alkyl or aryl groups independently.

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 preferred 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. The above-mentioned substituents may also have substituents.

The compound represented by formula (OS-101) is preferably represented by formula (OS-102).

Furthermore, in the aforementioned oxime sulfonate compounds, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring can be either one of them or a mixture thereof.

Specific examples of compounds represented by formula (OS-101) include those 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, and these contents are incorporated herein by reference.

Of the compounds mentioned above, b-9, b-16, b-31, and b-33 are preferred.

[Chemical Formula 33]

Commercially available examples 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, compounds represented by the following structural formulas can be cited as better examples.

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 MP Hutt's "Jurnal of Heterocyclic Compounds described in Chemistry, No. 1 (1970), etc., are included in this specification. In particular, compounds substituted with trihalomethanes can be cited. Azole compounds: S-triazole Compounds are a better example.

More preferably, at least one mono-, di-, or trihalomethane-substituted methyl group and s-trihalomethane can be cited as examples. S-three formed by ring bonding Derivatives, specifically, for example, 2,4,6-tris(monochloromethyl)-s-tris 2,4,6-Tris(dichloromethyl)-s-tris 2,4,6-Tris(trichloromethyl)-s-tris 2-Methyl-4,6-bis(trichloromethyl)-s-tri 2-n-propyl-4,6-bis(trichloromethyl)-s-tri 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tri 2-Phenyl-4,6-bis(trichloromethyl)-s-tri 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-tri 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tri 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-tri 2-Styryl-4,6-bis(trichloromethyl)-s-tri 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-tri 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-tri 2-(p-Tolyl)-4,6-bis(trichloromethyl)-s-tri 2-(4-naphthoxynaphthyl)-4,6-bis(trichloromethyl)-s-tri 2-Phenylenyl-4,6-bis(trichloromethyl)-s-tri 2-Benzylthio-4,6-bis(trichloromethyl)-s-tri 2,4,6-Tris(dibromomethyl)-s-tris 2,4,6-Tris(tribromomethyl)-s-tris 2-Methyl-4,6-bis(tribromomethyl)-s-tri 2-Methoxy-4,6-bis(tribromomethyl)-s-tri wait.

Examples of organoborate compounds include, for instance, Japanese Patent Application Publication Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9-188710, 2000-131837, 2002-107916, Japanese Patent No. 2764769, 2002-116539, and Kunz, Martin, “Rad Tech’98. Proceedings”. 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 ilmenides disclosed in Japanese Patent Application Publication No. 9-188710, and organoboronium transition metal coordination ilmenides such as those in Japanese Patent Application Publication Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014, the contents of which are incorporated herein by reference.

Examples of disulfide compounds include those 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, are described in the specifications of these 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.

As onium salts, examples can be given by the general formulas (RI-I) to (RI-III).

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 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 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, alkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 2 to 12 carbon atoms, alkylamide groups of alkyl groups with 1 to 12 carbon atoms, or arylamide groups of aryl groups with 6 to 20 carbon atoms, 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 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 each 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 the 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 each independently represent an aryl or alkyl, alkenyl, or alkynyl group with 6 to 20 carbon atoms that can have 1 to 6 substituents. Preferably, aryl is 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 of alkyl groups having 1 to 12 carbon atoms, alkylamide or arylamide groups of alkyl groups having 1 to 12 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 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 37]

[Chemical Formula 38]

[Chemical Formula 39]

The photosensitive acid generator is preferably used at 0.1-20% by weight relative to the total solids content of the resin composition, more preferably at 0.5-18% by weight, further preferably at 0.5-10% by weight, even more preferably at 0.5-3% by weight, and still more preferably at 0.5-1.2% by weight.

Photosensitive acid generators can be used alone or in combination of multiple types. When using multiple types in combination, the total amount is preferably within the range described above.

Furthermore, it is preferable to use it simultaneously with a sensitizer in order to impart photosensitivity to the desired light source.

Alkali-producing agents

The resin composition of the present invention may include a alkali-generating agent. The alkali-generating agent is a compound capable of generating alkali through physical or chemical action. Preferred alkali-generating agents for the resin composition of the present invention include thermal alkali-generating agents and photoalkali-generating agents.

Assume that the alkali-generating agent does not contain compound B.

The resin composition of this invention preferably contains an alkali-generating agent, more preferably a thermal alkali-generating agent or a light alkali-generating agent, and even more preferably a thermal alkali-generating agent. By including a thermal alkali-generating agent in the resin composition, such as one that can promote the cyclization reaction of the precursor by heating, the cured material exhibits good mechanical properties or chemical resistance, for example, its performance as an interlayer insulating film for rewiring layers included in semiconductor packaging becomes better.

As a base-producing agent, it can be either an ionic or nonionic base-producing agent. Examples of bases produced from a base-producing agent include, for example, secondary and tertiary amines.

There are no particular limitations on the alkali-generating agent of this invention, and known alkali-generating agents can be used. Examples of known alkali-generating agents include, for instance, aminomethyloxime compounds, aminomethylhydroxylamine compounds, carbamic acid compounds, methylamine compounds, acetylamine compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonic acid amide compounds, imidazole derivative compounds, aminoimidide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimidide compounds, phthalimide derivative compounds, and acetoimide compounds.

Specific compounds that can be cited as nonionic alkali generators include those represented by formulas (B1), (B2), or (B3).

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 cyclohexane ring or a benzene ring, with a cyclohexane 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.

As for Rb ³ , examples 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 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 groups. ^Rb3 may also have substituents within the scope of the invention's effects.

The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² have the same meaning as Rb ¹ and Rb ² in formula (B1), respectively.

Rb ¹³ can be an alkyl group (preferably with 1-24 carbons, more preferably with 2-18 carbons, and even more preferably with 3-12 carbons), an alkenyl group (preferably with 2-24 carbons, more preferably with 2-18 carbons, and even more preferably with 3-12 carbons), an aryl group (preferably with 6-22 carbons, more preferably with 6-18 carbons, and even more preferably with 6-12 carbons), or an aralkyl group (preferably with 7-23 carbons, more preferably with 7-19 carbons, and even more preferably with 7-12 carbons). Substituents may be present within the scope of achieving the effects of the present invention. Among these, it is preferred that Rb ¹³ be an aralkyl group.

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

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

Furthermore, the compound represented by formula (B1-1) is preferably the same as the compound represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² have the same meaning as Rb ¹¹ and Rb ¹² in formula (B1-1).

Rb ¹⁵ and Rb ¹⁶ are preferably hydrogen atoms, alkyl groups (1-12 carbons are preferred, 1-6 are more preferred, and 1-3 are even more preferred), alkenyl groups (2-12 carbons are preferred, 2-6 are more preferred, and 2-3 are even more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, and 6-10 are even more preferred), aralkyl groups (7-23 carbons are preferred, 7-19 are more preferred, and 7-11 are even more preferred), or preferably hydrogen atoms or methyl groups.

Rb ¹⁷ is an alkyl group (preferably with 1-24 carbons, more preferably with 1-12 carbons, and even more preferably with 3-8 carbons), an alkenyl group (preferably with 2-12 carbons, more preferably with 2-10 carbons, and even more preferably with 3-8 carbons), an aryl group (preferably with 6-22 carbons, more preferably with 6-18 carbons, and even more preferably with 6-12 carbons), or an aralkyl group (preferably with 7-23 carbons, more preferably with 7-19 carbons, and even more preferably with 7-12 carbons), wherein an aryl group is preferred.

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

In this specification, a "linker chain" refers to an atomic chain that connects two atoms or groups of atoms in the shortest possible (minimum 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 linker chain consists of 4 carbon atoms; and the number of atoms in the linker chain path (i.e., the number of atoms constituting the linker chain, hereinafter also referred to as the "linker chain length") is 4.

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, 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 0102-0168 of International Publication No. 2020/066416 and those described in paragraphs 0143-0177 of International Publication No. 2018/038002.

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

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 further preferred. 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 1-24 carbons, more preferably 2-18, and even more preferably 3-12 carbons) and hydrocarbon groups (preferably 1-24 carbons, more preferably 1-12, and even more preferably 1-10 carbons), respectively. Specifically, aliphatic hydrocarbons (preferably 1-24 carbons, more preferably 1-12, and even more preferably 1-10 carbons) or aromatic hydrocarbons (preferably 6-22 carbons, more preferably 6-18, and even more preferably 6-10 carbons) are examples, with aliphatic hydrocarbons being preferred. If aliphatic hydrocarbons are used as ^RN1 and ^RN2 , the resulting base will be highly basic, and therefore preferred. Furthermore, aliphatic and aromatic hydrocarbons can have substituents, and these substituents can be located within an aliphatic hydrocarbon chain or an aromatic ring, with oxygen atoms present in the substituents. In particular, examples of aliphatic hydrocarbons having oxygen atoms within a 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 with 3 to 12 carbon atoms are preferred, with 3 to 6 being even more preferred. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

Groups relating to combinations of alkyl and cycloalkyl groups preferably have 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of groups relating to combinations of alkyl and cycloalkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

The alkyl group containing oxygen atoms in the chain is preferably composed of 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight or branched.

From the perspective of increasing the boiling point of the alkali produced by decomposition (described later), it is preferable that ^RN1 and ^RN2 are alkyl groups with 5 to 12 carbon atoms. In formulations where close adhesion with metals (e.g., copper) is important, it is preferable to have cyclic alkyl groups or alkyl groups with 1 to 8 carbon atoms.

^RN1 and ^RN2 can be linked together to form a ring structure. When forming a ring structure, oxygen atoms, etc., 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 the formed ring structure, a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1) is preferred; examples include pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, pyrazoleidine rings, piperidine rings, and piperidine rings. Cyclic rings, morpholinic rings, etc., can be best exemplified by pyrrolidine rings, pyrrolidine rings, piperidine rings, and piperidine rings. Cyclic, morpholine cyclic.

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

As a protecting group, a protecting group that decomposes under the action of an acid or alkali is preferred; examples of protecting groups that decompose under the action of an acid are readily available.

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). Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, epioxypropyl, oxocyclobutane, tetrahydrofuranyl, and tetrahydropyranyl (THP).

There are no particular restrictions on the type of linker 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 contain atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linker group that can contain an oxygen atom in the chain is preferred; groups relating to divalent aliphatic hydrocarbons, divalent aromatic hydrocarbons, or combinations thereof that can contain an oxygen atom in the chain are even more preferred; and divalent aliphatic hydrocarbons that can contain an oxygen atom in the chain are even more preferred. It is preferable that these groups do not contain 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.

For linear or branched chain alkyl groups, those with 1 to 12 carbon atoms are preferred, 2 to 6 are more preferred, and 2 to 4 are even more preferred.

Cyclic alkyl groups with 3 to 12 carbon atoms are preferred, and those with 3 to 6 carbon atoms are even better.

Groups related to combinations of cyclic and cycloalkyl groups with 4 to 24 carbon atoms are preferred, 4 to 12 are more preferred, and 4 to 6 are even more preferred.

Alkyl groups containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight or branched. Alkyl groups with 1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are even more preferred.

The linear or branched alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched alkenyl group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3.

Cyclic alkenyl groups with 3 to 12 carbon atoms are preferred, and 3 to 6 are even better. The number of C=C bonds in the cyclic alkenyl groups is preferably 1 to 6, even better with 1 to 4, and further preferably 1 to 2.

Aryl groups with 6-22 carbon atoms are preferred, 6-18 are even better, and 6-10 are still preferred.

The arylalkyl group having 7-23 carbon atoms is preferred, 7-19 is even better, and 7-11 is further preferred.

Among them, chain-like alkylene, cyclic alkylene, alkylene having an oxygen atom in the chain, chain-like alkenyl, aryl, aryl, and alkylene are preferred, with 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and oxyethylene (especially 1,2-ethyleneoxy-1,2-ethylene) being even more preferred.

Examples of alkali-producing agents include the following, but this invention is not intended to be limited thereto.

[Chemical Formula 46]

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.

[Chemical Formula 47]

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

When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of the resin in the resin composition of the present invention. A lower limit of 0.3 parts by weight or more is preferred, and 0.5 parts by weight or more is further preferred. An upper limit of 30 parts by weight or less is 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 using two or more, it is preferable that the total amount be within the above-mentioned range.

<Polymerizing compounds>

The resin composition of this invention preferably contains polymeric compounds.

As polymerizable compounds, examples include free radical crosslinkers or other crosslinking agents.

[Free radical crosslinking agent]

The resin composition of this invention preferably contains a free radical crosslinker.

Free radical crosslinkers are compounds possessing free radical polymerizable groups. Preferably, the free radical polymerizable group contains an ethylene-unsaturated bond. Examples of such ethylene-unsaturated groups include vinyl, allyl, vinylphenyl, (meth)acrylyl, cis-butenidimino, and (meth)acrylamide groups.

Among these, (meth)acrylonitrile, (meth)acrylamide, and vinylphenyl are preferred as groups containing vinyl unsaturated bonds, and (meth)acrylonitrile is more preferred from a reactivity point of view.

Free radical crosslinkers are preferably compounds with one or more ethylene unsaturated bonds, but compounds with two or more are even better. Free radical crosslinkers can have three or more ethylene unsaturated bonds.

Of 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 even more preferred, and compounds having 2 to 6 ethylene unsaturated bonds are further preferred.

Furthermore, from the viewpoint of the film strength of the obtained pattern (hardened 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, more preferably below 1,500, and even more preferably below 900. A lower limit for 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 affinity 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 having 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 having 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 replace the aforementioned unsaturated carboxylic acids can also be used, such as unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, and such contents 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 (methyl) addition. Compounds obtained by esterification of acrylate, such as (meth)acrylate amino esters described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, and polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, as well as epoxy acrylates and other multifunctional acrylates or methacrylates as products of the reaction of epoxy resins with (meth)acrylate, 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 possess 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 cycloaliform ring and having two or more ethylene-containing 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 vinyl phosphonic 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 0048-0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087-0131 of International Publication No. 2015/199219 are also preferred, and their contents are incorporated into this specification.

Furthermore, the following compounds, described together with specific examples of formulas (1) and (2) in Japanese Patent Application Publication No. 10-062986, can also be used as free radical crosslinking agents. These compounds are obtained by esterification of (meth)acrylate following 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, and such contents are incorporated into 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 are preferred. These oligomer types can also be used.

Commercially available free radical crosslinking agents include, for example, SR-494 (a tetrafunctional acrylate with four ethynooxy groups) manufactured by Sartomer Company, Inc.; SR-209, 231, and 239 (a difunctional methyl acrylate with four ethoxy groups) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with six pentylooxy groups) manufactured by Nippon Kayaku Co., Ltd.; TPA-330 (a trifunctional acrylate with three isobutylooxy groups); amine ester oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.); NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300; and UA-7200 (Shin-Nakamura Chemical). (Manufactured by Nippon Kayaku 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 (manufactured by NOF CORPORATION), etc.

As free radical crosslinking agents, amine ester 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 amine ester compounds with an ethylene oxide skeleton 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 Nos. 63-277653, 63-260909, and 01-105238, can also be used.

Free radical crosslinkers can be free radical crosslinkers containing acid groups such as carboxyl or phosphate groups. It is preferable that the free radical crosslinker containing acid groups is an ester of an aliphatic polyhydroxyl 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 polyhydroxyl compound. Particularly preferred is that, in the free radical crosslinker containing acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of an aliphatic polyhydroxyl compound, the aliphatic polyhydroxyl compound is a neopentyl tetrol or dinepentyl tetrol. Commercially available examples include, for instance, polybasic acid-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 mgKOH/g, with a particularly preferred value of 1~100 mgKOH/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.

As specific compounds, the following can be used: 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, 1,6-hexanediol diacrylate, etc. Dimethacrylates, dihydroxymethyltricyclodecane dimethacrylates, dihydroxymethyltricyclodecane dimethacrylates, ethylene oxide (EO) adduct dimethacrylates of bisphenol A, EO adduct dimethacrylates of bisphenol A, propylene oxide (PO) adduct dimethacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylates, cyanuric acid (EO) modified diacrylates, cyanuric acid (EO) modified dimethacrylates, difunctional acrylates having other amine ester bonds, and difunctional methacrylates having amine ester 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 (hardener), a monofunctional free radical crosslinker can be used better as the free radical crosslinker. As a monofunctional free radical crosslinking agent, the following are preferred: 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 epoxypropyl 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, can be considered as 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 greater than 0% by mass and less than 60% by mass. A lower limit of 5% by mass or more is more preferred. An upper limit of 50% by mass or less is more preferred, and 30% by mass or less is even more preferred.

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

[Other cross-linking agents]

The resin composition of this invention preferably includes other crosslinking agents that are different from the aforementioned free radical crosslinking agents.

In this invention, "other crosslinking agents" refers 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. More 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.

Preferably, the acid or alkali mentioned above is generated from the photoacid generator or photoalkali generator during the exposure step.

As other crosslinking agents, compounds having at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl, and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl, and alkoxymethyl is directly bonded to a nitrogen atom are even more preferred.

Other crosslinking agents include, for example, compounds that have the structure of replacing the hydrogen atom of the aforementioned amino groups with acetaldehyde, or formaldehyde and an alcohol, in a reaction involving melamine, glycourea, urea, alkyl urea, benzoguanamine, or similar amino-containing compounds, via acetoxymethyl, hydroxymethyl, or alkoxymethyl groups. The method of 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, oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds can also be used.

Crosslinking agents that use melamine as a component of the aforementioned amine-containing compounds are called melamine-based crosslinking agents; crosslinking agents that use urea, urea, or alkylurea are called urea-based crosslinking agents; crosslinking agents that use alkylurea are called alkylurea-based crosslinking agents; and crosslinking agents that use 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 include alkoxymethyl or acetoxymethyl groups directly on the nitrogen atom of an aromatic group or a urea structure described below, or on a tri-atom. Compounds with top substitution are used as structural examples.

The alkoxymethyl or acetomethyl group in the above compounds preferably has 2 to 5 carbon atoms, with 2 or 3 carbon atoms being more preferred, and 2 carbon atoms being even more preferred.

The total number of alkoxymethyl and aceoxymethyl groups in the above compounds is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

The molecular weight of the above-mentioned compounds is preferably below 1500, with 180-1200 being more preferred.

R ₁₀₀ indicates alkyl or acetylated.

_R101 and _R102 represent monovalent organic groups independently and can bond with each other to form a ring.

Compounds in which alkoxymethyl or acetomethyl groups are directly substituted onto an aromatic group include, for example, various compounds of the following general formula.

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl or acetyl group, and R ₁₀₃ represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to produce an alkaline soluble group (e.g., a group that is desorbed under the action of an acid, or a group represented by -C(R ⁴ ) ₂ COOR 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 is desorbed under the action of an acid.)).

R ₁₀₅ independently represents alkyl or alkenyl groups, 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 alkali-soluble groups, groups that are desorbed under the action of acid, ^{and R5} in the group represented by -C( ^R4 ) _2COOR5 , examples include -C( _R36 )( _R37 )( _R3s ), -C( _R36 )( _R37 )( _OR39 ), and -C( _R01 )( _R02 )( _OR39 ).

In the formula, R ₃₆ to R ₃₉ independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups. R ₃₆ and R ₃₇ can bond together to form a ring.

Of the aforementioned alkyl groups, those having 1 to 10 carbon atoms are preferred, and those having 1 to 5 carbon atoms are even more preferred.

The alkyl group mentioned above can be either linear or branched.

Of the aforementioned cycloalkyl groups, those with 3 to 12 carbon atoms are preferred, and those with 3 to 8 carbon atoms are even more preferred.

The aforementioned cycloalkyl groups can be monocyclic or polycyclic structures, such as condensed rings.

The aryl group is preferably an aromatic hydrocarbon with 6 to 30 carbon atoms, and phenyl is even more preferred.

Of the aforementioned aralkyl groups, those with 7 to 20 carbon atoms are preferred, and those with 7 to 16 carbon atoms are even more preferred.

The aforementioned aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred states of these alkyl and aryl groups are the same as those of the aforementioned alkyl and aryl groups.

The alkenyl group described above is preferably an alkenyl group with 3 to 20 carbon atoms, and even more preferably an alkenyl group with 3 to 16 carbon atoms.

Furthermore, these groups may also have known substituents to the extent that the effects of this invention can be achieved.

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

The group that decomposes to produce an alkaline-soluble group by the action of acid, or that is desorbed by the action of acid, is preferably a trialkyl ester group, an acetal group, a cumyl ester group, or an enol ester group. More preferably, it is a trialkyl ester group or an acetal group.

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

[Chemical Formula 51]

[Chemical Formula 52]

For compounds containing at least one of alkoxymethyl and aceoxymethyl groups, commercially available compounds or those synthesized by known methods may be used.

From a heat resistance perspective, alkoxymethyl or acetomethyl groups are directly bonded to the aromatic ring or tricyclic ring. Compounds with ring substitution are preferred.

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

Specific examples of urea crosslinkers 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, and monopropoxymethylated glycourea. Glycourea crosslinking agents including hydroxylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea; Urea crosslinking agents including dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea; Monohydroxymethylated ethoxyurea or dihydroxymethylated ethoxyurea. Ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea, etc., are ethylene urea-based crosslinking agents; monohexyl methylated ethoxypropionate urea, dihydroxymethylated ethoxypropionate urea, monomethoxymethylated ethoxypropionate urea, dimethoxymethylated ethoxypropionate urea, monoethoxymethylated ethoxypropionate urea, dipropoxymethylated ethoxypropionate urea, monobutoxymethylated ethoxypropionate urea, or dibutoxymethylated ethoxypropionate urea, etc., are ethoxypropionate urea-based crosslinking agents; 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, 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)diphenylbenzene. Methyl ketone, methoxymethylbenzoate, 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, the resin composition of this invention comprises compounds selected from epoxides, cyclobutane compounds, and benzo[a]benzene. At least one compound from the group of compounds is preferred as an alternative crosslinking agent.

-Epoxy compounds (compounds containing epoxy groups)-

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

Epoxy compounds containing polyethylene oxide are preferred. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide indicates that the number of repeating units of ethylene oxide is 2 or more, 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, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by 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 can also be used more effectively.

[Chemical Formula 53]

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 improved elongation, a value of n = 1-2 and m = 3-7 is preferable.

-Oxycyclobutane compounds (compounds containing oxycyclobutane groups)-

Examples of oxocyclobutane compounds include compounds having two or more oxocyclobutane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-oxocyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxocyclobutane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxocyclobutyl)methyl] ester. As specific examples, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., ITD. is preferred; two or more of these can be used alone or in combination.

-Benzo Compounds (compounds containing benzoxazole groups) -

Due to the crosslinking reaction caused by the ring-opening addition reaction, benzo[a] The compound does not produce degassing during hardening, thereby further reducing thermal shrinkage and inhibiting warping, which is therefore preferable.

As benzo[a] A better example of a compound could be a Pd-type benzo[a] , Fa type benzo (The above are product names, manufactured by Shikoku Chemicals Corporation), benzo[a]benzene of polyhydroxystyrene resin Addition compounds, phenolic varnish type dihydrobenzo[2] 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 weight, more preferably 0.1-20% by weight, further preferably 0.5-15% by weight, and particularly preferably 1.0-10% by weight. The other crosslinking agents may be present in only one type or in two or more types. When two or more other crosslinking agents are present, it is preferable that their total content falls within the above range.

Metal adhesion modifiers

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 agent]

Examples of silane coupling agents include, for instance, 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 the compounds described in 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 included in this specification. 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 54]

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-isocyanate propyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination with two or more.

[Aluminum-based adjuvants]

Examples of aluminum-based additives include aluminum tri(ethyl acetate)aluminum, aluminum tri(acetoacetone)aluminum, and aluminum diisopropanol of 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 such contents are incorporated into 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 in the range of 0.1 to 10 parts by weight, and even more preferably in the range of 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 can 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 inhibitors

It is preferable that the resin composition of this invention further includes a migration inhibitor. By including the migration inhibitor, the transfer of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively inhibited.

There are no particular limitations as a migration inhibitor, but examples can be given of those with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, etc.). Azole ring, thiazolyl ring, pyrazole ring, isocyanate Azole ring, isothiazol ring, tetrazol ring, pyridine ring, tadalafil Cyclic rings, pyrimidine rings, pyridine rings Cyclic, piperidine cyclohexane, piperidine cyclohexane Cyclic rings, morpholinic rings, 2H-pyranic rings and 6H-pyranic rings, tricyclic rings Compounds containing cyclohexane, compounds with thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivatives, and acehydrazine derivatives are preferred. 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 are preferred.

Alternatively, ion-capturing 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 0073-0076 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 into this specification.

Specific examples of migration inhibitors include the following compounds.

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 0.01~5.0% by mass, more preferably 0.05~2.0% by mass, and even more preferably 0.1~1.0% by mass.

The migration inhibitor may be a single agent or two or more. When there are two or more migration inhibitors, it is preferable that their total number falls within the range described above.

<Polymerization Inhibitors>

The resin composition of this invention preferably contains 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-tert-butyl-p-cresol, gallnutol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine monocyanate, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, and ethylenylene. Diaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)- ...2,6-dimethylbenzyl)-2,6-dimethylbenzyl)-2,6-dimethylbenzyl)-2,6-dimethylbenzyl)-2,6-dimethylbenzyl)-2,6- -2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxo radical, 2,2,6,6-tetramethylpiperidine 1-oxo radical, phenthia ,coffee 1,1-Diphenyl-2-pyrrolidinehydrazine, dibutyldithiocopper(II) carbonate, 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 such contents are incorporated into this specification.

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 0.01~20% by weight, more preferably 0.02~15% by weight, and even more preferably 0.05~10% by weight.

The polymerization inhibitor may be a single agent or two or more. When there are two or more polymerization inhibitors, it is preferable that their total amount falls within the range described above.

<Acid trap>

To minimize 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 is 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, preferably include compounds having imidazole, diazabicyclic, onium, trialkylamine, aniline, or pyridine structures; alkylamine derivatives having hydroxyl and/or ether bonds; and aniline derivatives having 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 bellium structure include tetrabutylammonium hydroxide, triarylstromium hydroxide, benzylmethylstromium hydroxide, strom hydroxides with a 2-oxoalkyl group, specifically triphenylstromium hydroxide, tri(tert-butylphenyl)stromium hydroxide, bis(tert-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 (diazabicycloundecyl), and DABCO (1,4-di... Nitrogen-containing bicyclic [2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, 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, aminomorphine, aminoalkyl Phosphorus, etc.

These acid-capturing agents can be used alone or in combination of two or more.

The composition of this invention may or may not contain an acid scavenging agent. However, if 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 in U.S. Patent Application Publication No. 2013/0034812) and paragraphs 0101-0104, 0107-0109, etc., in Japanese Patent Application Publication No. 2008-250074, and such contents 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. These 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 form a film with a uniform thickness and minimal thickness unevenness.

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 SC1-068, 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, and these contents are incorporated into this specification. Block polymers may also be used as fluorinated surfactants; for example, compounds described in Japanese Patent Application Publication No. 2011-89090 may be cited, and these contents are incorporated into this specification.

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 propyleneoxy groups). Examples of fluorinated surfactants used in this invention include the following compounds.

The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.

Fluorinated surfactants can also utilize fluoropolymers with vinyl unsaturated groups on their side chains. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 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 preferably contain 3-40% by mass, more preferably 5-30% by mass, and most preferably 7-25% by mass. Fluorinated surfactants within this fluorine content range are effective in terms of coating thickness uniformity 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 Coming 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 FUJIFILM Wako Pure Chemical Corporation), 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 Shih-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 WO04, WO05, WO17 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

Surfactants can be used alone or in combination of two or more.

The surfactant content relative to the total solids content 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 inhibition caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoylamine can be added to the resin composition of this invention, thereby causing it to exist unevenly on the surface of the resin composition of this 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, and that content is incorporated into this specification.

When the resin composition of the present invention contains higher fatty acid derivatives, the content of the 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 higher fatty acid derivatives, it is preferable that their total content is within the above range.

[Thermal polymerization initiator]

The resin composition of this invention may include a thermal polymerization initiator, and more 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, polymerization reactions of resins and polymerizable compounds can also occur, thus further improving solvent resistance. Furthermore, sometimes the aforementioned photopolymerization initiators also have the function of initiating polymerization through heat, and can sometimes be added as thermal polymerization initiators.

Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which serve as initiators for thermal free radical polymerization, are included in this specification.

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 be one type or may contain two or more types. When two or more thermal polymerization initiators are contained, the total amount within the above range is preferred.

[Inorganic particles]

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

For the average particle size of the aforementioned inorganic particles, 0.01–2.0 μm is preferred, 0.02–1.5 μm is more preferred, 0.03–1.0 μm is further preferred, and 0.04–0.5 μm is especially preferred.

The aforementioned average particle size of the inorganic particles is 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 measurements are difficult to perform, measurements can also be made using centrifugal sedimentation transmission, X-ray transmission, and laser diffraction/scattering methods.

[Ultraviolet absorber]

The composition of this invention may include a UV absorber. As a UV absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triglyceride-based UV absorbers can be used. It is a UV absorber.

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 ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate are cited. Furthermore, as a tri- Examples of ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethylolpropane. 2-[4-[(2-hydroxy-3-tetrazoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethylphenyl 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethylphenyl Mono(hydroxyphenyl)tri Compound; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trimethylphenyl 2,4-Bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-trimethylphenyl 2,4-Bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trimethylphenyl Isobis(hydroxyphenyl)tri Compound; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(hydroxyphenyl) 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(hydroxyphenyl) 2,4,6-Tris[2-Hydroxy-4-(3-Butoxy-2-Hydroxypropoxy)phenyl]-1,3,5 ... Tris(hydroxyphenyl)tri Compounds, etc.

In this invention, the aforementioned ultraviolet absorbers can be used individually or in combination of two or more.

The composition of the present invention may or may not contain an ultraviolet absorber, but when it does contain an ultraviolet absorber, the content of the ultraviolet absorber relative to the total solid content of the composition of the present 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, it is possible to form a resin layer with excellent chemical resistance even when cured at low temperatures.

As usable organic titanium compounds, examples include those in which the organic groups are bonded to titanium atoms via covalent or ionic bonds.

Specific examples of organic titanium compounds are shown in I) to VII) below:

I) Titanium chelates: Among these, titanium chelates with two or more alkoxy groups are preferred due to their excellent resin stability and ability to produce 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.

II) Tetraalkoxytitanium compounds: Examples include tetra(n-butanol)titanium, tetraethanoltitanium, tetra(2-ethylhexanol)titanium, tetraisobutanoltitanium, tetraisopropanoltitanium, tetramethanoltitanium, tetramethoxypropanoltitanium, tetramethylphenyloxytitanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyltitanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc.

III) Titanium-ceramsite compounds: Examples include pentamethylcyclopentadienyltrimethyltitanium, 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, etc.

IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecanephenyl sulfonate) isopropoxide, etc.

V) Titanium oxide compounds: Examples include titanium bis(pentanedione), titanium bis(tetramethylheptanedione), and titanium phthalocyanine oxide.

VI) Tetraacetone titanium compounds: such as tetraacetone titanium, etc.

VII) Titanium ester coupling agents: for example, isopropyltris(2-dodecylbenzenesulfonate) titanium salt, etc.

Among these, from the viewpoint of exhibiting better drug resistance, at least one compound selected from the group consisting of I) titanium chelates, II) tetraalkoxytitanium compounds and III) dicrocene titanium compounds is preferred as an organic titanium compound. 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, more preferably 0.1 to 2 parts by weight. When the amount is 0.05 parts by weight or more, the resulting curing pattern exhibits better heat resistance and chemical resistance; conversely, when the amount is 10 parts by weight or less, the composition exhibits superior storage stability.

[Antioxidants]

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 can be used. Compounds having a substituent at the site (orthoside) adjacent to the phenolic hydroxyl group are preferred. As the above-mentioned 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 are also preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxane-phosphine-heptacyclohepta-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxane-phosphine-heptacyclohepta-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-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 use compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, and this content is incorporated into this specification. 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, and their contents are incorporated herein by reference. Commercially available products that are potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

Examples of better antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

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 present in the resin. Furthermore, it can inhibit metal oxidation by preventing rust formation in metallic 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 it may also have substituents. Among these, alkyl ethers and -NH- are preferred from the viewpoint of solubility in the developing solution and metal adhesion; -NH- is preferred from the viewpoint of interaction with resins and metal adhesion during metal complex formation.

Examples of compounds represented by general formula (3) are given below, but are not limited to the following structures.

[Chemical Formula 58]

[Chemical Formula 59]

[Chemical Formula 60]

[Chemical Formula 61]

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 adding an amount of 0.1 parts by weight or more, it is easier to obtain improved elongation properties or adhesion to metal materials, even under high temperature and humidity environments. Conversely, by adding an amount of 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.

[Anticoagulant]

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 others.

The composition of the present invention may or may not contain an anti-coagulant, but when it does contain an anti-coagulant, the content of the anti-coagulant relative to the total solid content of the composition of the present 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 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 polymers]

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

In this invention, other polymeric compounds can be used alone or in combination of two or more.

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 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, relative to the total solid content of the composition of this invention.

<Properties of 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 3,000 ^mm² /s to 8,000 ^mm² /s is even more preferred. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. When it is below 1,000 ^mm² /s, it is difficult to coat with the film thickness required for a reinforcing insulation film, for example, and when it is above 12,000 ^mm² /s, the coating surface morphology may deteriorate.

The amount of acid groups contained in the composition (also known as the "anti-corrosion acid value") is preferably below 6.0 mg KOH/g per 1g of the resin composition of the present invention, and even more preferably below 5.0 mg KOH/g.

There is no particular limit to the amount of the aforementioned acid groups; it can be 0 mg KOH/g.

Examples of acid groups mentioned above include those with a pKa of 15 or less, such as carboxyl groups and phenolic hydroxyl groups.

The acid value of the aforementioned corrosion inhibitor was determined, for example, by titration using potassium hydroxide.

The resin composition of this invention contains compound B, which exhibits excellent stability; therefore, even with a reduction in the amount of acid groups, excellent storage stability is maintained. In other words, it is not necessary to adjust the composition to an acidic state to improve its storage stability.

<Restrictions on the substances contained in resin components>

The resin composition of this invention preferably has a moisture content of 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 exceeding 2.0% may impair the storage stability of the resin composition.

Methods for maintaining moisture content include adjusting the humidity of the storage conditions and reducing the porosity of the storage container.

From an insulation perspective, 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 unintended metallic impurities in the resin composition of the present invention, the following methods can be employed: selecting raw materials with low metal content as the 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 apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible.

Considering the use 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 preferred, less than 300 ppm by mass is more preferred, and less than 200 ppm by mass is even more preferred. Of these, a halogen ion content of less than 5 ppm by mass is preferred, less than 1 ppm by mass is more preferred, and less than 0.5 ppm by mass is even more preferred. Chlorine and bromine atoms can be cited as examples of halogen atoms. It is preferred that the total number of chlorine and bromine atoms, or the total number of chloride and bromine ions, falls within the above-mentioned ranges.

One good example of a method for regulating the content of halogen atoms is ion exchange treatment.

As a container for the resin composition of the present invention, conventionally known containers can be used. Furthermore, as a container, to prevent impurities from contaminating 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 formed from the six resins. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

<Curing of resin components>

By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

The cured material of this invention is a cured material formed by curing the resin composition of this invention.

Curing of the resin composition is preferably carried out by heating, with a heating temperature in the range of 120°C to 400°C being more preferred, in the range of 140°C to 380°C being even more preferred, and in the range of 170°C to 350°C being particularly preferred. The morphology of the cured resin composition is not particularly limited, and it can be in the form of a film, rod, sphere, or granules, depending on the application. In this invention, a film-like form of the cured composition is preferred. Furthermore, by pattern processing of the resin composition, the shape of the cured composition can be selected according to applications such as forming a protective film on the wall surface, forming beer halls for conduction, adjusting impedance or electrostatic capacitance or internal stress, and imparting heat dissipation. The thickness of the cured material (the film formed by the cured material) 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

<Properties of hardened resin compounds>

The amide reaction rate of the cured resin composition of this invention is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. When it is less than 70%, the mechanical properties of the cured product may be poor.

The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

The glass transition temperature (Tg) of the cured resin composition of this invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

<Preparation of Resin Components>

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 achieved using methods such as mixing based on agitator blades, mixing based on a ball mill, and mixing by rotating the container itself.

The optimal temperature for mixing is 10–30°C, with 15–25°C being even better.

Furthermore, to remove foreign matter such as dust or particulate matter from the resin composition of this invention, filtration using a filter is preferable. Regarding the filter pore size, for example, pores of 5 μm or less are preferred, 1 μm or less is preferred, 0.5 μm or less is even better, and 0.1 μm or less is further preferred. 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 combined. For example, a connection could be made by connecting a 1μm pore size HDPE filter as the first stage and a 0.2μm pore size HDPE filter as the second stage in series. Furthermore, various materials can be filtered multiple times. Multiple filtrations constitute circulating filtration. Alternatively, filtration can be performed after pressurization. When pressurizing and filtering, the pressure applied 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, even better 0.05 MPa or higher and 0.7 MPa or lower, and further 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. As the adsorption material, known adsorption materials can be used. Examples include inorganic adsorption materials such as silicone and zeolite, and organic adsorption materials such as activated carbon.

Furthermore, after filtration using a filter, the resin composition filled in the bottle can be placed under reduced pressure and degassed.

(Method for manufacturing hardened materials)

The method for manufacturing the cured material of this invention preferably includes a film-forming step of applying a resin composition to a substrate to form a film.

Furthermore, the method for manufacturing the cured material of this invention includes, more preferably, the above-described film formation step, the selective exposure step of the film formed by the film formation step, and the development step of developing the film exposed by the exposure step with a developing solution to form a pattern.

The method for manufacturing the cured material of this invention preferably includes at least one of the above-described film formation step, the above-described exposure step, the above-described development step, a heating step for heating the pattern obtained by the development step, and a post-development exposure step for exposing the pattern obtained by the development step.

Furthermore, the manufacturing method of this invention, including the above-described film formation step and the step of heating the above-described film, is also preferable.

The following provides a detailed explanation of each step.

<Membrane Formation Steps>

The resin composition of this invention can be used in the film formation process for forming films on a substrate.

The method for manufacturing the cured material of this invention preferably includes a film-forming step of applying a resin composition 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 disposed on the surface of such 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, as a substrate, a plate-shaped, preferably panel-shaped, substrate (base plate) can be used.

Furthermore, when a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer formed from a hardened material) 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.

Furthermore, it is also applicable to the method of transferring a coating, formed by pre-applying it to a pseudo-support using the aforementioned application method, onto a 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 can be performed to remove excess film from the ends of the substrate. Examples of such steps include edge bead rinsing (EBR) and back rinse.

Alternatively, a pre-wetting step can be used, in which various solvents are applied to the substrate to improve its wettability before the resin composition is applied.

<Drying Steps>

The aforementioned membrane, after the membrane formation step (layer formation step), can be used in the drying step (drying step) to remove the solvent.

That is, the method for manufacturing the hardened material of this invention may include a drying step, which dries the film formed by the film forming step.

Furthermore, it is preferable to perform the drying step described above after the film formation step and before the exposure step.

The optimal drying temperature for the membrane during the drying process is 50-150°C, with 70-130°C being even better, and 90-110°C being even more desirable. Alternatively, drying can be achieved by reducing pressure. For drying time, examples include 30 seconds to 20 minutes, 1 minute to 10 minutes, and 2 minutes to 7 minutes, all of which are preferable.

<Exposure Steps>

The aforementioned film can be used in the exposure step of selectively exposing films.

That is, the method for manufacturing the cured material of this invention may include an exposure step that selectively exposes the film formed by the film formation step.

Selective exposure means exposing only a portion of the film. Furthermore, through selective exposure, exposed areas (exposed areas) and unexposed areas (non-exposed areas) are formed on the film.

Regarding the exposure amount, there are no special requirements as long as it can harden the resin composition of this invention. For example, it is preferable to use an exposure energy of 50~10,000mJ/ ^cm2 at a wavelength of 365nm, and even better to use 200~8,000mJ/ ^cm2 .

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

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 (three 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, and exposure to i-rays is particularly 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 formed by the resin composition of this invention. However, examples include exposure using a photomask and exposure based on direct laser imaging.

<Heating steps after exposure>

The aforementioned film can be used in the post-exposure heating step (post-exposure heating step).

That is, the method for manufacturing the cured material of this 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 development step.

The optimal heating temperature during the post-exposure heating step is 50℃~140℃, with 60℃~120℃ being even better.

The optimal heating time after exposure is 30 seconds to 300 minutes, with 1 to 10 minutes being even better.

Regarding the heating rate during the post-exposure heating process, a rate of 1-12°C/min from the initial heating temperature to the maximum heating temperature is preferred, 2-10°C/min is even better, and 3-10°C/min is still preferable.

Furthermore, the heating rate can be appropriately adjusted during the heating process.

There are no particular limitations on the heating mechanism used in the post-exposure heating step; commonly known heating plates, ovens, infrared heaters, etc., can be used.

Furthermore, it is also preferable to conduct the experiment in a low-oxygen environment by allowing inert gases such as nitrogen, helium, and argon to flow through during heating.

<Development Steps>

The exposed film can then be used in the developing process to create patterns using a developing solution.

That is, the method for manufacturing the cured material of this invention may include a developing step, in which a developing solution is used to develop a film exposed by an exposure step to form a pattern. Development removes either the exposed or unexposed portions of the film, thus forming the pattern.

The process of developing a film to remove the unexposed portions of the film is called negative development, while the process of developing a film to remove the exposed portions of the film is called positive development.

[Developer]

As examples of developing solutions used in the developing process, alkaline aqueous solutions or developing solutions containing organic solvents can be cited.

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, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. 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 are preferred, and TMAH is even more preferred. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01~10% by mass, more preferably 0.1~5% by mass, and even more preferably 0.3~3% by mass.

When the developing solution contains organic solvents, esters are preferably exemplified as follows: 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-valerate, 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- Methyl alkoxypropionate, 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 as... Ketones, preferably including methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, preferably including aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; ionoids, preferably including dimethyl ionoid; and alcohols, preferably including methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc.; and amides, preferably including N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

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

The developing solution can further contain other ingredients.

Other components include, for example, well-known surfactants and well-known defoamers.

[Developer supply method]

Regarding the method of supplying the developer, 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 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.

Considering the penetrability of the developer, the removal of non-image areas, and manufacturing efficiency, a method of supplying the developer using a straight nozzle or a continuous supply method using a spray nozzle is preferable. From the perspective of the developer's penetration into the image area, a spray nozzle method is even better.

Alternatively, after continuously supplying developer using a vertical nozzle, the substrate can be rotated to remove the developer. After drying by rotation, the substrate can be continuously supplied again using the vertical nozzle, and the substrate can be rotated to remove the developer again. 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.

For development time, 10 seconds to 10 minutes is preferred, and 20 seconds to 5 minutes is even better. There are no specific temperature requirements for the developing solution, but it is best performed between 10 and 45°C, and even better between 18 and 30°C.

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

[Rinse Solution]

When the developing solution is an alkaline aqueous solution, water can be used as the rinsing solution. When the developing solution contains an organic solvent, a solvent different from the solvent contained in the developing solution can be used as the rinsing solution (e.g., water, or an organic solvent different from the organic solvent contained in the developing solution).

When the rinsing solution contains organic solvents, the organic solvents that are esters include, for example, 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., methyl 2-methoxy-2-methylpropionate, etc.) 2-Ethoxy-2-methylpropionate ethyl ester, 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 as ketones Examples of preferred cyclic hydrocarbons include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; cyclic hydrocarbons include toluene, xylene, and anisole; cyclic terpenes include limonene; ionoids include dimethyl ionoid; alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and amides include 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.

Rinse solutions may further include other ingredients.

Other components include, for example, well-known surfactants and well-known defoamers.

[Method for supplying the rinsing solution]

Regarding the method of supplying the rinsing solution, there are no particular restrictions 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 by 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 to supply the rinsing solution to the exposed film using a straight nozzle or in a continuous manner, and even better to supply the rinsing solution using a spray nozzle.

Furthermore, as a method for supplying the rinsing solution in the rinsing step, methods include continuously supplying the rinsing solution to the substrate, maintaining the rinsing solution in a substantially static state on the substrate, vibrating the rinsing solution on the substrate using ultrasound or the like, and combinations of these methods.

The ideal rinsing time is 10 seconds to 10 minutes, with 20 seconds to 5 minutes being even better. There are no specific temperature requirements for the rinsing solution, but it is best performed between 10 and 45°C, and even better between 18 and 30°C.

<Heating Steps>

The pattern obtained through the developing step (or, in the case of a rinsing step, the rinsed pattern) can be used in the heating step that heats the pattern obtained through the aforementioned developing process.

That is, the method for manufacturing the hardened material of this invention may include a heating step, which heats the pattern obtained by the developing step.

Furthermore, the method for manufacturing the cured material of this invention may include a heating step, which heats a pattern obtained by other methods without a developing step or a film obtained by a film forming step.

During the heating step, resins such as polyimide precursors are cyclized to form polyimide resins.

Furthermore, cross-linking of unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins is also performed.

The optimal heating temperature (maximum heating temperature) in the heating process is 50-450℃, better is 150-350℃, further better is 150-250℃, even better is 160-250℃, and exceptionally good is 160-230℃.

The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the above-described pattern by heating and utilizing the action of alkali produced from the aforementioned alkali generator, alkali produced from the aforementioned compound B, etc.

Regarding the heating process, it is preferable to increase the temperature at a rate of 1-12°C/min from the initial temperature to the maximum heating temperature. A heating rate of 2-10°C/min is more preferable, and 3-10°C/min is even better. Setting the heating rate to 1°C/min or higher ensures productivity while preventing 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, a heating rate of 1-8°C/second from the initial temperature to the maximum heating temperature is preferable, 2-7°C/second is even better, and 3-6°C/second is even more preferable.

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 process 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 at a temperature 20°C to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

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

The upper limit of the heating temperature mentioned above is preferably below 350℃, even better below 250℃, and further preferably below 240℃.

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 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; a cooling rate of 1-5°C/minute is preferable in this case.

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 through the heating step and under reduced pressure. An oxygen concentration of 50 ppm (by volume) or lower is preferred, and 20 ppm (by volume) or lower is even better.

There are no particular limitations on the heating mechanism used in the heating process; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

<Post-exposure steps>

The pattern obtained by the developing step (or, in the case of a washing step), either in lieu of or excluding the heating step described above, can also be used in the post-exposure step of the pattern after the exposure developing 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, it can, for example, promote cyclization reactions of polyimide precursors by exposure to photoalkali generators, or desorption reactions of acid-degrading groups by exposure to photoacid generators.

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 50~20,000mJ/ ^cm2 , and even better if the exposure energy at the wavelength where the photosensitive compound is sensitive is converted to 100~15,000mJ/ ^cm2 .

The post-development exposure step can be performed using the same light source as described in the exposure steps above; broadband light is preferred.

<Metal Layer Formation Steps>

The pattern obtained by the developing step (preferably a pattern used in at least one of the heating step and the post-exposure developing step) can be used in the metal layer formation step where a metal layer is formed on the pattern.

That is, the method for manufacturing the hardened material of the present invention preferably includes a metal layer formation step, which forms a metal layer on a pattern obtained by a developing step (preferably a pattern for at least one of a heating step and a post-developing 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. Copper and aluminum are preferred, with 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 combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electroplating. As a preferred example of electroplating, electroplating using copper sulfate or copper cyanide plating solutions can be cited.

Regarding the thickness of the metal layer, a thickness of 0.01~50 μm for the thickest portion is preferred, and 1~10 μm is even better.

<Uses>

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 electronic components, interlayer insulating films for redistribution layers, and stress-relief films. Other examples 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 Polyimide,” April 2008; Masaaki Kakimoto, supervisor; 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 this invention, or the cured material itself, 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.

(Laminates and methods for manufacturing laminates)

The laminate of this invention refers to a structure having multiple layers formed by the hardening agent of this invention.

The laminate of this invention comprises two or more layers formed of a hardened material, and may also be a laminate consisting of three or more layers.

At least one of the two or more layers formed by the aforementioned hardened material in the aforementioned laminate is a layer formed by the hardened material of the present invention. From the viewpoint of suppressing shrinkage of the hardened material or deformation of the hardened material accompanying such shrinkage, it is also preferable that all the layers formed by hardened materials in the aforementioned laminate are layers formed by the hardened material of the present invention.

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

The laminate of this invention comprises two or more layers formed of a hardened material, and it is preferable that a metal layer is included between any of the layers formed of the hardened material. Preferably, the metal layer is formed by the aforementioned metal layer formation step.

That is, the method for manufacturing the laminate of the present invention, between the multiple steps of manufacturing the hardened material, preferably includes a metal layer formation step of forming a metal layer on the layer formed by the hardened material. The preferred form of the metal layer formation step is as described above.

As an example of the aforementioned laminate, a preferred example is a laminate consisting of at least three layers sequentially stacked: a first layer formed of a hardener, a metal layer, and a second layer formed of a hardener.

Preferably, both the first and second layers formed by the cured material are layers formed by the cured material of the present invention. The resin composition of the present invention used to form the first layer and the resin composition of the present invention used to form the second layer can be of the same composition or different compositions. The metal layers in the laminate of the present invention are preferably used as metal wiring such as rewiring layers.

<Layering Steps>

The method for manufacturing the laminate of this invention preferably includes a lamination step.

The lamination step includes a series of steps that sequentially perform 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 on the surface of the pattern (resin layer) or metal layer. Alternatively, it may be a repetition of at least one of (a) the film formation step and (d) the heating step and the post-development exposure step. Furthermore, after at least one of (d) the heating step and the post-development exposure step, (e) the metal layer formation step may be included. It is self-evident that the lamination step may further appropriately include the aforementioned drying step, etc.

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

Performing the above layering steps 2-20 times is preferable, and 2-9 times is even better.

For example, in a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer configuration, it is preferable to have 2 or more but less than 20 resin layers, and it is even more preferable to have 2 or more but less than 9 resin layers.

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 deposition steps of the resin composition layer (resin layer) and the metal layer formation step of the present invention, the resin composition layer (resin layer) and the metal layer of the present invention can be deposited alternately.

(Surface activation treatment steps)

The method for manufacturing the laminate of the present invention preferably includes a surface-activating 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. However, it can also be performed after the above-mentioned development step, specifically after the surface-activation treatment of 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. Thus, 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 perform surface-activation treatment on part or all of the exposed resin composition layer (resin layer). This surface-activation treatment of the resin composition layer improves adhesion to the metal layer and resin layer disposed on the surface-activated surface. 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 facilitating improved 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 a 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, 1000~100,000 J/ ^m² is even better, and 10,000~50,000 J/ ^m² is optimal.

(Manufacturing method of semiconductor devices)

Furthermore, this invention also discloses semiconductor devices comprising the cured material or the laminate of this invention.

Furthermore, this invention also discloses a method for manufacturing a semiconductor device, including a method for manufacturing a cured material of this invention or a method for manufacturing a 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, reference can be made to paragraphs 0213-0218 of Japanese Patent Application Publication No. 2016-027357 and the description in Figure 1, and these contents are incorporated herein by reference.

[Implementation Example]

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 varied, provided 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 based on quality.

<Method for manufacturing precursors of cyclic resins>

[Synthetic Example 1: Synthesis of precursor A-1 (polymer A-1) of cyclic resin]

A diester of 4,4'-oxophthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diethylene glycol dimethyl ether (or diethylene glycol dimethyl ether) were synthesized by mixing at 60 °C for 4 hours. The mixture was then stirred at 60 °C for 4 hours. Next, the reaction mixture was cooled to -10 °C, and 17.0 g of thiocyanate was added over 60 minutes while maintaining the temperature at -10 ± 5 °C. After dilution with 50 mL of N-methylpyrrolidone, a solution obtained by dissolving 12.6 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10±5 °C, and the mixture was stirred at room temperature for 2 hours.

Next, 6000g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was collected by filtration and dissolved in 500g of tetrahydrofuran. 6000g of water (a poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered again and dried under reduced pressure at 45°C for 3 days.

46.6 g of dried powder was dissolved in 419.6 g of tetrahydrofuran, followed by the addition of 2.3 g of triethylamine, and stirred at room temperature for 35 minutes. The solution was then added to 3000 g of ethanol, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by Ambertec Ltd.) were added, and the mixture was stirred for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain the precipitate. The precipitate was collected by filtration and dried at 45°C for 24 hours under reduced pressure to obtain 45.1 g of polymer A-1.

The molecular weight of polymer A-1 was determined by gel osmosis chromatography (standard polystyrene conversion), and the weight-average molecular weight (Mw) was 20,000. The structure of polymer A-1 is presumed to be represented by the following formula (A-1).

[Synthetic Example 2: Synthesis of precursor A-2 (polymer A-2) of cyclic resin]

23.48 g of 4,4'-oxophthalic dianhydride (ODPA) and 22.27 g of bis(phthalic dianhydride) (BPDA) were added to a separable flask, along with 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of tetrahydrofuran. The mixture was stirred at room temperature (25°C), and 24.66 g of pyridine was added while stirring to obtain the reaction mixture. After the reaction reached thermal equilibrium, it was cooled to room temperature and allowed to stand for 16 hours.

Next, while cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes with stirring. Then, 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of tetrahydrofuran was added over 60 minutes with stirring. After stirring at room temperature for 2 hours, 7.17 g of ethanol was added and stirred for 1 hour, followed by the addition of 136.83 g of tetrahydrofuran. The precipitate formed in the reaction mixture was removed by filtration, thus obtaining the reaction solution.

The obtained reaction solution was added to 716.21 g of ethanol, thereby generating a precipitate of crude polymer. The crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran, thus obtaining a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer. After filtering off the precipitate, it was vacuum dried to obtain 80.3 g of powdered polymer A-2. The molecular weight of polymer A-2 was determined by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000. The structure of polymer A-2 is presumed to be represented by the following formula (A-2).

[Synthetic Examples 3-7: Synthesis of precursors A-3-A-7 (polymers A-3-A-7) of cyclic resins]

By appropriately modifying the compounds used, polymers A-3 to A-7 with structures represented by any one of formulas (A-3) to (A-7) were synthesized using the same method as in Synthesis Example 1.

The Mw of polymer A-3 is 20,500, the Mw of polymer A-4 is 20,000, the Mw of polymer A-5 is 21,000, the Mw of polymer A-6 is 19,000, and the Mw of polymer A-7 is 22,000.

[Chemical Formula 62]

<Implementation Examples and Comparative Examples>

In each embodiment, the components listed in the table below were mixed to obtain each resin composition. Furthermore, in each comparative example, the components listed in the table below were mixed to obtain each comparative composition.

Specifically, the content of each component recorded in the table is set to the amount (parts by mass) recorded within the parentheses in each column of the table.

The obtained resin composition and the comparative composition were pressure filtered using 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 ingredient.

Furthermore, the "Anticorrosion Acid Value" column in the table indicates the amount of acid groups contained in 1g of the composition, in mgKOH/g.

The detailed information for each component listed in the table is as follows.

[Precursors to cyclic resins]

A-1 to A-7: Polymers A-1 to A-7 obtained by the above synthesis example.

[Photosensitizer (photopolymerization initiator)]

B-1~B-3: Compounds with the following structures

[Organometallic complex]

X-1: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium

X-2: Pentamethylcyclopentadienyltrimethyltitanium

X-3: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium

X-4: Tetraisopropoxytitanium (manufactured by Matsumoto Fine Chemical Co., Ltd.)

X-5: Diisopropoxybis(acetyl acetone)titanium (manufactured by Matsumoto Fine Chemical Co., Ltd.)

X-6~X-8: Compounds with the following structures.

[Chemical Formula 65]

X-1 and X-3 mentioned above are compounds with photoradical polymerization initiation energies.

[Polymerizable compounds (free radical crosslinkers)]

C-1~C-2: Compounds with the following structures

[Polymerization inhibitors/migration inhibitors]

D-1~D-5: Compounds with the following structures

[Additives]

E-2~E-3: Compounds with the following structures

I-1~I-2: Compounds with the following structures

[Chemical Formula 68]

[Metal adhesion modifier]

F-1~F-2: Compounds with the following structures

In the above structural formula, Et represents the ethyl group.

[Other alkali-producing agents]

G-1~G-2: Compounds with the following structures

H-11: Compounds with the following structure

[Chemical Formula 70]

[Compound B]

H-1~H-10, H-12~H-26: Compounds with the following structures

[Soluble]

NMP: N-methyl-2-pyrrolidone

EL: Ethyl lactate

DMSO: Dimethyl sulfoxide

GBL: γ-Butyrolactone

<Evaluation>

[Evaluation of stability retention]

The viscosities (0 days) of the resin compositions prepared in each embodiment and comparative example, as well as the comparative composition, were measured using an E-type viscometer. After standing at 25°C for 14 days in a light-proof, sealed container, the viscosity was measured again using an E-type viscometer (14 days). The viscosity change rate (%) was calculated according to the following formula. Based on the obtained viscosity change rate (%), the following evaluation criteria were used to evaluate the composition, and the evaluation results were recorded in the "Storage Stability" column of the table below. A lower viscosity change rate indicates higher storage stability.

Viscosity change rate (%) = |100×{1-(viscosity (14 days)/viscosity (0 days))}|

Viscosity was measured at 25°C, and other measurements were performed according to JIS Z 8803:2011.

-Evaluation Criteria- Evaluation Criteria-

A: Viscosity variation rate is below 5%.

B: Viscosity variation rate exceeding 5% but below 10%.

C: Viscosity variation rate exceeding 10% but below 15%.

D: Viscosity variation rate exceeding 15% but below 20%.

E: The viscosity variation rate exceeds 20%.

[Evaluation of elongation at break]

The resin compositions or comparative compositions prepared in each embodiment and comparative example were applied to a silicon wafer by spin coating, thereby forming a resin layer.

The silicon wafer with the obtained resin layer was dried at 100°C for 5 minutes on a heated plate, thereby obtaining a resin composition layer with a uniform thickness of approximately 15 μm on the silicon wafer.

In the examples where the developing condition column in the table below is marked "negative," the entire surface of the resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ/ ^cm² . The exposure wavelength is recorded in the "Exposure Wavelength (nm)" column of the table. In the examples where the developing condition column in the table is marked "positive," no exposure was performed.

In the example where the exposure condition is marked "M", a stepper motor was used as the light source for the exposure.

In the example where the exposure condition is marked "D", a direct exposure apparatus (ADTECDE-6UH III) was used as the light source for the exposure.

In the example designated as "A" in the "Curing Method" column, a heating plate was used to heat the exposed resin composition layer under a nitrogen atmosphere at a rate of 10°C/min. After reaching the temperature recorded in the "Curing Temperature (°C)" column of the table, this temperature was maintained for 3 hours.

In the example designated as "B" under "Curing Method," an infrared lamp heating device (ADVANCE RIKO, Inc., RTP-6) was used to heat the resin films obtained in each embodiment at a rate of 10°C/min under a nitrogen atmosphere. After reaching the temperature specified in "Curing Temperature (°C)," this temperature was maintained for 3 hours.

The hardened resin composition layer (hardened material) was immersed in a 4.9% (w/w) hydrofluoric acid aqueous solution and then peeled off from the silicon wafer. The peeled-off hardened material was punched using a punching machine to produce test pieces with a sample width of 3 mm and a sample length of 30 mm. The elongation along the long side of the obtained test pieces was measured using a tensile testing machine (Tensilon) at a crosshead speed of 300 mm/min at 25°C and 65% RH (relative humidity) according to JIS-K6251. Five measurements were performed, and the arithmetic mean of the elongation at break (elongation at break) from the five measurements was used as the index value.

The evaluation was conducted according to the following criteria, and the results are recorded in the "Elongation at Break" column of the table. Generally speaking, the higher the value, the better the film strength of the cured material.

-Evaluation Criteria- Evaluation Criteria-

A: The above indicator value is above 65%.

B: The above indicator value is above 60% and below 65%.

C: The above indicator value is above 55% and below 60%.

D: The above indicator value is above 50% and below 55%.

E: The above indicator value is less than 50%.

[Evaluation of close contact]

The resin composition or comparative composition prepared in each embodiment and comparative example was applied in layers onto a copper substrate by spin coating, thereby forming a resin composition layer or a comparative composition layer. The copper substrate with the obtained resin composition layer or comparative composition layer was dried on a heating plate at 100°C for 5 minutes, thereby forming a uniform resin composition layer or comparative composition layer with a thickness of 20 μm on the copper substrate. In the example where "development condition" is marked as "negative" in the table, a photomask with a square non-masking portion of 100 μm was used. In the example where "development condition" is marked as "positive" in the table, a photomask with a square masking portion of 100 μm was used. The resin composition layer or comparison composition layer on the copper substrate was exposed to light with an exposure wavelength (nm) recorded in the table's "exposure wavelength (nm)" column at an exposure energy of 500 mJ/ ^cm² .

In the example where the exposure condition is marked "M", a stepper motor was used as the light source for the exposure.

In the example marked "D" in the exposure conditions column, direct laser imaging exposure was performed within a 100μm square area using a direct exposure apparatus (ADTECDE-6UH III) as the light source without a photomask.

Then, the resin layer was developed with cyclopentanone for 60 seconds, resulting in a square resin layer of 100 μm.

In the example designated as "A" in the "Curing Method" column, a heating plate was used to heat the exposed resin composition layer under a nitrogen atmosphere at a rate of 10°C/min. After reaching the temperature recorded in the "Curing Temperature (°C)" column of the table, this temperature was maintained for 3 hours.

In the example designated as "B" under "Curing Method," an infrared lamp heating device (ADVANCE RIKO, Inc., RTP-6) was used to heat the resin films obtained in each embodiment at a rate of 10°C/min under a nitrogen atmosphere. After reaching the temperature specified in "Curing Temperature (°C)," this temperature was maintained for 3 hours.

The shear force of a 100 μm square resin layer on a copper substrate was measured using an adhesive strength tester (XYZ TEC, CondorSigma) at 25°C and 65% relative humidity (RH), and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Adhesion" column of the table. Generally speaking, a higher shear force indicates better metal adhesion (copper adhesion) of the hardened film.

-Evaluation Criteria- Evaluation Criteria-

A: The shear force exceeded 30gf.

B: Shear force exceeding 25gf but below 30gf.

C: Shear force exceeding 20gf but below 25gf.

D: Shear force is below 20gf.

Also, 1 gf is 0.00980665 N.

The results above demonstrate that by using the resin composition of this invention, a resin composition with excellent preservation stability and superior elongation at break of the cured product can be obtained.

The comparative composition in Comparative Example 1 does not contain compound B but contains a large amount of "H-11" as another alkali generator. In this state, it is evident that the composition exhibits poor storage stability.

Comparative Example 2 uses a composition that does not contain compound B but contains a small amount of "H-11" as another alkali-generating agent. In this state, the difference in elongation at break of the obtained hardened product is evident.

<Implementation 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 with 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 (Nikon Co., Ltd., NSR1505 i6). Exposure was performed using a mask (a binary mask with a 1:1 line-to-space pattern and a linewidth of 10 μm) at a wavelength of 365 nm. 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 the 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 interlayer insulating films for these redistribution layers, and normal operation was confirmed.

Claims (14)

A resin composition comprising: selected from polyimide precursors, polyphenylene oxides, etc. At least one resin from the group consisting of azole precursors and polyamide-imide precursors; and compound B, which generates a base by the action of a base, wherein compound B is a compound represented by the following formula (1-1): In equation (1-1), ^R1 represents a substitutable hydrocarbon, ^R2 represents a substitutable hydrocarbon, and ^R1 and ^R2 can bond together to form a ring structure. The resin composition as described in claim 1, wherein the alkali produced from compound B is an amine. The resin composition as described in claim 1 or claim 2, wherein compound B has an amino ester bond. The resin composition as described in claim 1 or claim 2 further comprises a thermo-alkali generator or a photoalkali generator. The resin composition as described in claim 1 or claim 2 further comprises a calorific value-generating agent. The resin composition as described in claim 1 or claim 2 further comprises a photopolymerization initiator. The resin composition as described in claim 1 or claim 2 further comprises a polymeric compound. The resin composition as described in claim 1 or claim 2, wherein compound B is selected from at least one of the following compounds: A hardened material formed by hardening any of the resin compositions described in claims 1 to 8. A laminate comprising two or more layers formed of the hardened material described in claim 9, and including a metal layer between any of the layers formed of the aforementioned hardened material. A method for manufacturing a hardened material, comprising a film formation step of adapting a resin composition described in any one of claims 1 to 8 onto a substrate to form a film. The method for manufacturing a hardened material as described in claim 11 includes an exposure step of selectively exposing the aforementioned film and a development step of developing the aforementioned film using a developing solution to form a pattern. The method for manufacturing the hardened material as described in claim 11 includes a heating step of heating the aforementioned film at a temperature of 50-450°C. A semiconductor device comprising the cured material described in claim 9.