TWI912328B - Curable resin compositions, cured films, laminates, methods for manufacturing cured films, semiconductor devices, and thermosetting resins. - Google Patents

Abstract

The invention comprises a thermosetting resin having a polymerizable group and an isoimidin structure and a curing resin composition having a radiosensitive polymerization initiator, a curing film formed by curing the aforementioned curing resin composition, a laminate comprising the aforementioned curing film, a method for manufacturing the aforementioned curing film, a semiconductor device comprising the aforementioned curing film or the aforementioned laminate, and a thermosetting resin having a specific structure.

Description

Curable resin compositions, cured films, laminates, methods for manufacturing cured films, semiconductor devices, and thermosetting resins.

This invention relates to a curable resin composition, a curable film, a laminate, a method for manufacturing a curable film, a semiconductor device, and a thermosetting resin.

Previously, the following steps were performed: a curable resin composition containing a thermosetting resin was applied to a substrate, for example, by coating, to form a photosensitive film. Then, exposure, development, and heating were performed as needed to form a cured material (e.g., a cured film) on the substrate. This type of curable resin composition can be applied using known coating methods, thus offering excellent manufacturing adaptability. For example, it allows for a high degree of freedom in designing the shape, size, and application location of the curable resin composition. Considering this excellent manufacturing adaptability, there is increasing anticipation for the industrial application development of the aforementioned curable resin composition.

For example, resins such as polyimide are used in the form of curable resin compositions containing a polyimide precursor as a thermosetting resin. The aforementioned polyimide precursor is, for example, cyclized by heating, and becomes polyimide in the cured material. Polyimide, for example, possesses excellent heat resistance and insulation properties, and is therefore suitable for various applications. While there are no particular limitations on these applications, its use as an insulating film, sealing material, or protective film can be cited as an example of its practical application in mounting semiconductor devices. Furthermore, it can also be used as a base film or cover film for flexible substrates.

For example, Patent Document 1 describes a radiosensitive composition characterized by comprising: (i) 100 parts by weight of a polyisoimide obtained by reacting at least one of the aromatic tetracarboxylic acid dianhydrides selected from pyromellitic dianhydrides and 3,3',4,4'-biphenyltetracarboxylic acid dianhydrides with (b) a mixture of three aromatic diamines, namely diaminodiphenyl ether, diaminodiphenyl ether, and p-phenylenediamine, in a molar ratio of 10-90:10-90:0-35; and (ii) a monomer shown in Formula RZH [where R is an organic group having an ethylene unsaturated group capable of addition polymerization, and Z is -O-, -S-, or ^-NR1- (where ^R1 represents hydrogen or an alkyl group having 1 to 4 carbon atoms). (iii) 10-500 parts by weight, (iv) 0-20 parts by weight of a radiosensitive polymerization initiator or radiosensitive sensitizer, and (v) 0.1-50 parts by weight of a diazide compound. For example, Patent 2 describes a polyimide resin composition containing polyimide, characterized in that it contains a polyimide having a solubility of 0.01-10% by weight relative to dichloromethane (100% by weight) or 1,3-dioxolane (100% by weight) at 25°C and having an aromatic portion, and a compound A having a partial structure with a NICS value in the range of -15.0 to -7.0 and a molecular weight in the range of 250 to 10000.

[Patent Document 1] Japanese Patent Application Publication No. Hei 08-048733 [Patent Document 2] Japanese Patent Application Publication No. 2018-053156

Considering the heat resistance of the various materials contained in the component, it is necessary to cure the curing resin composition containing thermosetting resin at low temperatures. In the cured film obtained from the curing resin composition containing thermosetting resin, it is required to improve the mechanical strength of the cured film when cured at low temperatures.

The purpose of this invention is to provide a curable resin composition that yields a curable film with excellent mechanical strength even when cured at low temperatures, a curable film formed by curing the aforementioned curable resin composition, a laminate containing the aforementioned curable film, a method for manufacturing the aforementioned curable film, and a semiconductor device containing the aforementioned curable film or the aforementioned laminate. Furthermore, the purpose of this invention is to provide a novel thermosetting resin.

Examples of representative embodiments of the present invention are shown below. <1> A curable resin composition comprising a thermosetting resin having a polymerizable group and an isoimidine structure, and a radiosensitive polymerization initiator. <2> A curable resin composition as described in <1>, wherein the thermosetting resin is a polyimide precursor. <3> A curable resin composition as described in <1> or <2>, wherein the thermosetting resin comprises a polyamide structure or a polyamide ester structure. <4> A curable resin composition as described in any one of <1> to <3>, wherein the content of the isoimidine structure contained in the thermosetting resin is 0.001 to 0.3 mmol/g. <5> A heat-curing resin composition as described in any one of <1> to <4>, wherein the aforementioned heat-curing resin has a repeating unit represented by formula (2) or formula (3); [Chemical Formula 1] In formula (2), ^A1 and ^A2 independently represent oxygen atoms or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 independently represent hydrogen atoms or monovalent organic groups; In formula (3), ^R117 represents a trivalent organic group, ^R111 represents a divalent organic group, ^A2 represents an oxygen atom or -NH-, and ^R113 represents a hydrogen atom or monovalent organic group. <6> The curable resin composition as described in <5>, wherein at least one of ^R113 and ^R114 in the above formula (2) contains a polymerizable group. <7> A curable resin composition as described in <5> or <6>, wherein at least one of R ¹¹³ and R ¹¹⁴ in formula (2) above comprises a free radical polymerizable group. <8> A curable resin composition as described in any one of <1> to <7>, used to form an interlayer insulating film for a rewiring layer. <9> A curable film formed by curing any one of the curable resin compositions described in <1> to <8>. <10> A laminate comprising two or more curable films as described in <9>, and comprising a metal layer between at least one of the curable films. <11> A method for manufacturing a curing film, comprising a film forming step of adapting the curable resin composition described in any one of <1> to <8> onto a substrate to form a film. <12> The method for manufacturing a curing film as described in <11> further comprises a heating step of heating the film at a temperature of 80 to 450°C. <13> The method for manufacturing a curing film as described in <11> or <12> further comprises an exposure step of exposing the film and a developing step of developing the film. <14> A semiconductor device comprising the curing film described in <9> or the laminate described in <10>. <15> A thermosetting resin comprising at least one repeating unit selected from a group consisting of repeating units represented by formula (4) and formula (5) below, and at least one repeating unit selected from a group consisting of repeating units represented by any one of formulas (2-1) to (2-3) below; [Chemical Formula 2] In formula (4), ^A1 and ^A2 independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and ^R114 independently represent a hydrogen atom or a monovalent organic group, and at least one of ^R113 and ^R114 contains the group represented by formula (III) below; In formula (5), ^R117 represents a trivalent organic group, ^R111 represents a divalent organic group containing a polymerizable group, ^A2 represents an oxygen atom or -NH-, and ^R113 represents a hydrogen atom or a monovalent organic group. [Chemical Formula 3] In formulas (2-1) to (2-3), ^A1 represents an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R114 represents a hydrogen atom or a monovalent organic group, and ^R117 represents a trivalent organic group; [Chemical Formula 4] In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, R ²⁰¹ represents an hydrocarbon group or a group represented by a bond between a hydrocarbon and at least one structure selected from the group consisting of -O-, -CO-, -S-, _-SO₂- , or ^-NRN- , * indicates a bond site with other structures, and ^RN represents a hydrogen atom or a hydrocarbon group. [Invention Effects]

According to the present invention, a curable resin composition that yields a curable film with excellent mechanical strength even when cured at low temperatures is provided; a curable film formed by curing the aforementioned curable resin composition; a laminate containing the aforementioned curable film; a method for manufacturing the aforementioned curable film; and a semiconductor device containing the aforementioned curable film or the aforementioned laminate. Furthermore, according to the present invention, a novel thermosetting resin is provided.

The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments shown. In this specification, the numerical range indicated by the symbol “~” represents the range including the lower and upper limits of the numerical values recorded before and after the “~”, respectively. In this specification, the term “step” not only refers to an independent step, but also includes steps that cannot be clearly distinguished from other steps, as long as the expected effect of the step can be achieved. Regarding the marking of group (atomic group) in this specification, the markings without substitution and without substitution include both unsubstituent group (atomic group) and substituent group (atomic group). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise stated, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include brightline spectra from mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation. In this specification, "(meth)acrylate" means either or both "acrylate" and "methacrylate," "(meth)acrylic acid" means either or both "acrylic acid" and "methacrylic acid," and "(meth)acrylyl" means either or both "acrylyl" and "methacrylyl." In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl in the structural formula. In this specification, total solids content refers to the total mass of all components of the composition, excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalents according to gel osmosis chromatography (GPC). 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 protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as the holding column. Unless otherwise specified, these molecular weights are determined using THF (tetrahydrofuran) as the washing solution. Furthermore, unless otherwise specified, the detection in GPC measurements 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 third 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 the layers are gradually stacked on the substrate is referred to as "upper," or, in the case of a photosensitive film, the direction from the substrate toward the photosensitive film 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 samples, the "up" direction in this instruction manual may differ from the plumb line pointing upwards. In this instruction manual, unless otherwise stated, each component in the composition may contain two or more compounds corresponding to that component. Also, unless otherwise stated, the content of each component in the composition represents the total content of all compounds corresponding to that component. In this instruction manual, unless otherwise stated, the temperature is 23°C, the pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH. In this instruction manual, the preferred sample combination is considered a better sample.

(Cureable Resin Composition) The cureable resin composition of the present invention comprises a thermosetting resin having a polymerizable group and an isoimidin structure, and a radiation-sensitive polymerization initiator.

The curable 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 curable resin composition of this invention is preferably used to form a photosensitive film for negative development. In this invention, negative development refers to the development of non-exposed areas by means of development during exposure and development, while positive development refers to the development of exposed areas by means of development. As for the above-described exposure method, the above-described developing solution, and the above-described developing method, for example, the exposure method described in the exposure step of the explanation of the method for manufacturing the curable film described later, and the developing solution and developing method described in the developing step are used.

The curable resin composition of this invention can achieve a cured film with excellent mechanical strength even when cured at low temperatures. The mechanism by which the above effect is obtained is not yet clear, but it is speculated to be as follows.

The thermosetting resin used in this invention has an isoimidin structure. The inventors have discovered that by using this thermosetting resin, a cured film with excellent mechanical strength can be obtained even when curing at low temperatures. While the reason for this effect is not yet clear, it is presumed that the alkalinity of the isoimidin structure promotes the curing of the thermosetting resin. For example, it is hypothesized that when the thermosetting resin is a resin containing a polyamide structure or a polyamide ester structure, under relatively low temperature conditions (e.g., 180°C), the alkalinity of the isoimidide structure promotes the amide formation of the polyamide or polyamide ester structure. Therefore, even when curing is performed at low temperatures, a cured film with excellent mechanical strength can be obtained. Furthermore, it is hypothesized that the isoimidide structure itself also transitions to a amide structure with high mechanical strength at relatively low temperatures (e.g., 175°C). Therefore, even when curing is performed at low temperatures, a cured film with excellent mechanical strength can be obtained. Furthermore, the thermosetting resin used in this invention has polymerizable groups, and the curing resin composition of this invention contains a radiosensitive polymerization initiator. Therefore, it is hypothesized that polymerization occurs during exposure or heating, and a cured film with excellent mechanical strength can be obtained even when curing is performed at low temperatures. Furthermore, in the case of prior exposure and development of a previously used curing resin composition containing a thermosetting resin with polymerizable groups and a radiosensitive polymerization initiator, thermosetting occurs while the resins polymerize with each other or with other polymerizable compounds through exposure. In this polymerization state, thermosetting is sometimes difficult due to restrictions on the movement and structural changes of the thermosetting resin. Based on this invention, it is hypothesized that, due to the promotion of thermosetting based on the aforementioned isoimidine structure and the transfer of the isoimidine structure to the imidine structure, a cured film with excellent mechanical strength can be obtained even when curing is carried out at low temperatures during this polymerization process. However, neither Patent 1 nor Patent 2 describes a thermosetting resin composition containing a polymerizable group and an isoimidine structure, nor a curing resin composition containing a radiation-sensitive polymerization initiator.

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

<Specific Resin> The curing resin composition of the present invention comprises a thermosetting resin (hereinafter also referred to as "specific resin") having a polymeric group and an isoimidin structure.

[Polymerizable Group] As a polymerizable group contained in a particular resin, a group capable of undergoing a polymerization reaction by heat, free radicals, etc., is preferred. Examples include free radical polymerizable groups, epoxy groups, oxocyclobutyl groups, hydroxymethyl groups, alkoxymethyl groups, alkoxysilyl groups, benzoxazolyl groups, block isocyanate groups, etc. Among these, free radical polymerizable groups or epoxy groups are preferred as polymerizable groups, with free radical polymerizable groups being more preferred. As a free radical polymerizable group, a group having an ethylene-unsaturated bond is preferred. As a group having an ethylene-unsaturated bond, vinyl, (meth)allyl, vinylphenyl, (meth)acryloxy, (meth)acrylamine, etc., are preferred, with (meth)acryloxy being more preferred. The molar amount of polymeric groups contained in 1g of a specific resin is preferably 0.5–4.0 mmol/g, and more preferably 1.0–3.0 mmol/g. A specific resin may contain only one type of polymeric group, or it may contain two or more types. When it contains two or more types, the total amount within the above range is preferred.

[Isoimimine Structure] Cyclic isoimimine structures are preferred as isoimimine structures contained in a particular resin. A cyclic isoimimine structure refers to a ring structure containing an isoimimine structure, and a 5-membered ring structure containing an isoimimine structure is preferred. Furthermore, a particular resin may have isoimimine structures on its side chains, but it is preferable to have isoimimine structures on its main chain. In this specification, the main chain of the resin refers to the relatively longest molecular chain in the molecule.

Furthermore, the structure represented by formula (1-1) below is preferred as an isoimidin structure. [Chemical Formula 5] In equation (1-1), * denotes a bonding site with other structures, and Cy denotes a ring structure. The ring members contained in Cy can have bonding sites with other structures. As for the ring structure represented by Cy, a 5-membered ring is preferred. Furthermore, it is preferred that the ring members contained in the ring structure represented by Cy, other than N, O, and C (=O) recorded in equation (1-1), are carbon atoms. The ring structure represented by Cy can be a saturated ring structure or an unsaturated ring structure. In the case where the isoimidide structure is as represented by formula (1-1), * is the bonding site with the main chain of a specific resin, and it is preferable that at least one of the ring members contained in the ring structure represented by Cy contains a bonding site with the main chain.

Furthermore, it is preferable that a particular resin contains the structure represented by the following formula (1-2) as a structure comprising an isoimidin structure. [Chemical Formula 6] In equations (1-2), Cy-2 represents a ring structure, n represents an integer greater than 1, and * represents the bonding sites with other structures independently. Cy-2 can be a saturated ring structure or an unsaturated ring structure, but an aromatic ring structure is preferred. Furthermore, Cy-2 can be a hydrocarbon ring structure or a heterocyclic structure, but a hydrocarbon ring structure is preferred. Examples of heteroatoms in the aforementioned heterocyclic structures include nitrogen atoms, oxygen atoms, and sulfur atoms. Moreover, Cy-2 can be a monocyclic structure or a multicyclic structure such as a condensed ring structure, a cross-linked ring structure, or a spirocyclic structure, but a monocyclic structure is preferred. Furthermore, the Cy-2 monocyclic structure refers to a condensed ring structure formed by Cy-2 as a monocyclic structure and the ring structure containing the amide structure described in formula (1-2). It is preferred that each ring structure contained in the above monocyclic or polycyclic structure has 5 or 6 members. n represents an integer greater than or equal to 1, with integers from 1 to 6 being preferred, 1 or 2 being more preferred, and 1 being especially preferred.

Furthermore, it is preferable that a particular resin contains the structure represented by the following formulas (1-3) as a structure comprising an isoimidin structure. [Chemical Formula 7] In equation (1-3), n represents an integer from 1 to 4, and * represents the connection points with other structures independently. In equation (1-3), n of 1 or 2 is preferred, and 1 is even better.

The content of isoimidin structures in a specific resin is preferably 0.001–0.3 mmol/g, more preferably 0.006–0.3 mmol/g, and even more preferably 0.024–0.3 mmol/g. It is hypothesized that as long as the content of isoimidin structures in a specific resin is above 0.001 mmol/g, a cured film with excellent mechanical strength can be obtained even when cured at low temperatures. Furthermore, it is hypothesized that as long as the content of isoimidin structures in a specific resin is 0.3 mmol/g or less, the storage stability of the cured resin composition is excellent because it inhibits the curing of the specific resin when stored, and the filtration is excellent because the solubility of the specific resin itself is increased. The content of the aforementioned isoimidin structures can be determined by nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), and ultraviolet-visible absorption spectroscopy (UV-vis). For example, infrared spectroscopy can be used, and the content can be calculated based on the peak area at 1800 ^cm⁻¹ .

[Polyimide Precursors] There are no particular limitations on the specific resin, as long as it is a thermosetting resin, but polyimide precursors are preferred. As a polyimide precursor, any compound that forms a polyimide ring structure through heating to become a polyimide is acceptable, but inclusion of polyamide or polyamide ester structures is preferred, with inclusion of polyamide ester structures being even more preferred.

[Repeating unit represented by formula (2)] Among these, it is preferable that a particular resin has a repeating unit represented by formula (2) or formula (3) described below, and it is even more preferable that it has a repeating unit represented by formula (2). [Chemical Formula 8] 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 independently represent an oxygen atom or -NH-, with an oxygen atom being preferred. In formula (2), ^R111 represents a divalent organic group. Examples of divalent organic groups include aliphatic groups, cyclic aliphatic groups, and aromatic groups containing straight or branched chains, preferably aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 6 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or combinations thereof, with groups containing aromatic groups with 6 to 20 carbon atoms being more preferred. As a particularly preferred embodiment of the present invention, the group represented by -Ar-L-Ar- can be used as an example. In this group, Ar is an aromatic group, and L is a group comprising an aliphatic hydrocarbon 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 types may be used. Specifically, diamines comprising aliphatic groups (2-20 carbon atoms), cyclic aliphatic groups (6-20 carbon atoms), aromatic groups (6-20 carbon atoms), or combinations thereof are preferred, and diamines comprising aromatic groups (6-20 carbon atoms) are even more preferred. Examples of aromatic groups include the following.

【Chemical Formula 9】 In the formula, A is preferably a single-bonded or fluorine-substituted aliphatic hydrocarbon group of 1 to 10 carbon atoms, -O-, -C(=O)-, -S-, _-SO2- , _-NHCO- , or a combination thereof. It is more preferably a single-bonded or fluorine-substituted alkyl group of 1 to ₃ carbon atoms, -O-, -C(=O)-, -S-, or -SO2- _{. -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2- are even more preferred} . * indicates a bonding site with other structures.

As a diamine, specifically, examples include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, and 4,4'-diamino-3,3 '-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-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] arsenide, bis[4-(3-aminophenoxy)phenyl] arsenide, bis[4-(2-aminophenoxy)phenyl] arsenide, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl arsenide, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4 '-Diaminodiphenylmethane, 4,4'-Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)furan, 4,4'-dimethyl-3,3'-diaminodiphenyl 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, 2,7-diaminophen, 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)hexafluoropropane, 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-trifluoromethylphenoxy)benzene The diamine selected from at least one of the following: 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfonium, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfonium, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

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

In addition, the following diamine can also be used preferentially. [Chemical Formula 10]

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

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

Furthermore, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by formula (51) or formula (61). In particular, from the viewpoints of i-ray transmittance and availability, the divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 11] In formula (51), ^R50 to ^R57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of ^R50 to ^R57 is a fluorine atom, a methyl group, or a trifluoromethyl group. Examples of monovalent organic groups among ^R50 to ^R57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [Chemical Formula 12] In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group. Examples of diamine compounds 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 compounds may be used.

Furthermore, R ¹¹¹ can be a structure containing a polymerizable group. For example, R ¹¹¹ can also be a structure derived from a diamine compound having a polymerizable group. There is no particular limitation on the diamine compound having a polymerizable group, but compounds containing an aromatic ring structure are preferred, and compounds having a structure containing an amino group and a polymerizable group directly linked to an aromatic ring structure are even more preferred. As a polymerizable group, groups including vinyl unsaturated groups, cyclic ether groups, hydroxymethyl groups, or alkoxymethyl groups are preferred; vinyl, (meth)allyl, (meth)acrylamide, (meth)acryloxy, cis-butenediimido, vinylphenyl, epoxy, oxocyclobutyl, hydroxymethyl, or alkoxymethyl groups are more preferred; and (meth)acryloxy, (meth)acrylamide, epoxy, hydroxymethyl, or alkoxymethyl groups are even more preferred. Furthermore, R ¹¹¹ can be formed by reacting a group (epoxy, isocyanate, etc.) that is reactive with the aforementioned reactive groups, a compound having a polymerizable group, and a diamine compound having reactive groups such as carboxyl or hydroxyl groups.

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 groups represented by formulas (52) or (62) below are even more preferred. In formulas (52) or (62), * independently represents the bonding site with other structures. [Chemical Formula 13] In formula (52), R ¹¹² is preferably a group selected from a single bond or a group of 1 to 10 carbon atoms that can be substituted by a fluorine atom, including aliphatic hydrocarbons, -O-, -CO-, -S-, -SO _2- and -NHCO-, and combinations thereof. It is even more preferable to select a group selected from a single bond, a group of 1 to 3 carbon atoms that can be substituted by a fluorine atom, including alkyl groups, -O-, -CO-, -S- and -SO _2- . It is even more preferable to select a divalent group from the group including -CH _2- , -C(CF ₃ ) _2- , -C(CH ₃ ) _2- , -O-, -CO-, -S- and -SO _2- .

Regarding R ¹¹⁵ , examples include the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more may be used. It is preferable that the tetracarboxylic dianhydride is represented by the following formula (O). [Chemical Formula 14] 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-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane. Alkane dianhydrides, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydrides, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydrides, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydrides, 1,4,5,6-naphthalenetetracarboxylic acid dianhydrides, 2,2',3,3'-diphenyltetracarboxylic acid dianhydrides, 3,4,9,10-perylenetetracarboxylic acid dianhydrides, 1,2,4,5-naphthalenetetracarboxylic acid dianhydrides, 1,4,5,8-naphthalenetetracarboxylic acid dianhydrides, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydrides, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydrides, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydrides, 1,2,3,4-benzenetetracarboxylic acid dianhydrides, and such alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

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

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, as R ¹¹¹ , the residual group of a diaminophenol derivative can be cited.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and even more preferably both contain a polymerizable group. The polymerizable group is a group capable of undergoing a polymerization reaction by heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having ethylene unsaturated bonds, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxocyclobutyl, benzoxazolyl, block isocyanate, hydroxymethyl, and amino groups. As a free radical polymerizable group in polyimide precursors, a group having ethylene unsaturated bonds is preferred. Examples of groups having ethylene-like unsaturated bonds include vinyl, (methyl)allyl, and groups represented by formula (III) below, with groups represented by formula (III) below being preferred.

【Chemical Formula 15】

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In formula (III), * indicates a bonding site with other structures. In formula (III), R ²⁰¹ represents an hydrocarbon group or a group represented by a bond between an hydrocarbon group and at least one structure selected from the group consisting of -O-, -CO-, -S-, _-SO2- or ^-NRN- , preferably an alkyl group having 2 to 12 carbon atoms, _-CH2CH (OH) _CH2- , or a polyalkylene group. Preferred examples of R ²⁰¹ include ethyl, propyl, trimethylene, tetramethylene, 1,2-butadiene, 1,3-butadiene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH _2- , polyalkylene, ethyl, propyl, trimethylene, -CH ₂ CH(OH)CH _2- , polyalkylene, and polyalkylene, with polyalkylene being even more preferred. Furthermore, R ²⁰¹ is preferably a group containing a urea bond, a ethyl carbamate bond, or an ester bond. Examples of such groups include, for instance, groups represented by *-L ^U1 -X ^U1 -L ^U2 -#. L ^U1 represents an hydrocarbon group or a group represented by a hydrocarbon group and a bond selected from at least one structure of the group consisting of -O-, -CO-, -S-, _-SO2- , or ^-NRN- , preferably an alkyl group having 2 to 12 carbon atoms, _-CH2CH (OH) _CH2- , or a polyalkylene group. X ^U1 represents a urea bond, a ethyl carbamate bond, or an ester bond. L ^U2 represents an hydrocarbon group or a group represented by a hydrocarbon group and a bond selected from at least one structure of the group consisting of -O-, -CO-, -S-, _-SO2- , or ^-NRN- , preferably an alkyl group having 2 to 12 carbon atoms, _-CH2CH (OH) _CH2- , or a polyalkylene group. * has the same meaning as * in formula (III), and # indicates a bond site with an oxygen atom in formula (III). In this invention, a polyalkylene group refers to a group obtained by directly bonding two or more alkylene groups. The alkylene groups in the plurality of alkylene groups contained in the polyalkylene group may be the same or different. When the polyalkylene group contains a plurality of alkylene groups with different alkylene groups, the arrangement of the alkylene groups in the polyalkylene group may be random, block-shaped, or alternating. It is preferred that the number of carbon atoms in the alkylene group (the number of carbon atoms including the substituents when the alkylene group has substituents) is 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have substituents. Examples of 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 alkoxy groups are preferred, with polyvinyloxy or polypropyleneoxy being more preferred, and polyvinyloxy being even more preferred. In the groups obtained by bonding a plurality of ethyleneoxy groups with a plurality of alkoxy groups, the ethyleneoxy and alkoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred states of the repetition number of ethyleneoxy groups in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organogroup. Examples of monovalent organogroups include aromatic groups and aralkyl groups bonded to one, two, or three carbon atoms constituting the aryl group, preferably one. Specifically, examples include aromatic groups with 6 to 20 carbon atoms having an acid group, and aralkyl groups with 7 to 25 carbon atoms having an acid group. More specifically, examples include phenyl groups and benzyl groups having an acid group. An OH group is preferred. It is also more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, or 4-hydroxybenzyl.

From the perspective of solubility in organic solvents, it is preferable that R ¹¹³ or R ¹¹⁴ is a monovalent organic group. As a monovalent organic group, it is preferable to include straight-chain or branched alkyl groups, cyclic alkyl groups, or aromatic groups, with aromatic-substituted alkyl groups being even more preferred. It is preferable that the alkyl group has 1 to 30 carbon atoms. The alkyl group can be any of straight-chain, branched, or cyclic. Examples of alkyl groups that can be straight-chain or branched include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, dibutyl, tributyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy). Cyclic alkyl groups can be monocyclic or polycyclic. Examples of monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alkyl groups include adamantyl, norcamphenyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphenyl, dicyclohexyl, and pinenyl. Among these, cyclohexyl is the most suitable from the perspective of balancing high sensitivity. Furthermore, as aromatic-substituted alkyl groups, linear alkyl groups substituted with aromatic groups (described later) are preferred. As an aromatic group, specifically, it refers to substituted or unsubstituted benzene rings, naphthalene rings, cyclopentadiene rings, indene rings, azulene rings, heptaene rings, indene rings, perylene rings, fused pentaphenyl rings, acenaphthene rings, phenanthrene rings, anthracene rings, fused benzene rings, cyclopentadiene rings, triphenylene rings, fumonisin rings, biphenyl rings, pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, thiazole rings, pyridine rings, and pyridine rings. The following rings are available: pyrimidine ring, pyridinium ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, pyridinium ring, pyridinium ring, pyridinium ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, caffeine ring, acridine ring, caffeine ring, thiophene ring, chromene ring, pyridoxazoline ring, caffeinethiazoline ring, or caffeine ring. Benzene rings are preferred.

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.

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 decomposes under the action of acid to produce an alkaline-soluble group such as a phenolic hydroxyl group or a carboxyl group, but acetal, ketal, silyl group, silyl ether group, and tertiary alkyl ester group are preferred. From the viewpoint of exposure sensitivity, acetal is more preferred. Specific examples of acid-degradable groups include tributoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tributoxycarbonylmethyl, and trimethylsilyl ether group. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl are preferred.

Furthermore, it is preferable that the polyimide precursor contains fluorine atoms in its structural units. It is preferable that the fluorine atom content in the polyimide precursor is 10% by mass or more, and 20% by mass or less.

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

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

^A1 , ^A2 , ^R111 , ^R113 , and ^R114 are each independently equivalent to ^A1 , ^A2 , ^R111 , ^R113 , and ^R114 in equation (2), and their preferred ranges are also the same. ^R112 is equivalent to ^R112 in equation (52), and its preferred range is also the same.

Polyimide precursors may contain one or more repeating structural 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 structural units besides the repeating units of formula (2) mentioned above.

Polyimide precursors containing repeating units as represented by formula (3) are also preferred. [Formula 17] In formula (3), 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 (3), 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 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, -O-, -S-, -C(=O)-, -S(=O) _2- , alkylene, halogenated alkylene, arylene, or a linking group formed by two or more of these bonds is preferred; -O-, -S-, alkylene, halogenated alkylene, arylene, or a linking group formed by two or more of these bonds is even more preferred. As the alkylene group mentioned above, alkylene having 1 to 20 carbon atoms is preferred, alkylene having 1 to 10 carbon atoms is more preferred, and alkylene having 1 to 4 carbon atoms is even more preferred. As the halogenated alkylene group mentioned above, halogenated alkylene having 1 to 20 carbon atoms is preferred, halogenated alkylene having 1 to 10 carbon atoms is even more preferred, and halogenated alkylene having 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the aforementioned halogenated alkyl groups include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. The aforementioned halogenated alkyl groups may contain hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms, but substitution with halogen atoms is preferred. Examples of preferred halogenated alkyl groups include (di-trifluoromethyl)methylene. As for the aforementioned aryl groups, phenyl or naphthyl groups are preferred, with phenyl groups being more preferred, and 1,3-phenyl or 1,4-phenyl groups being even more preferred.

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

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

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

In equation (3), ^R111 , ^A2 , and ^R113 have the same meaning as ^R111 , ^A2 , and ^R113 in equation (2) above, and the better state is also the same.

The polyimide precursor preferably comprises at least one repeating unit selected from the group consisting of repeating units represented by any one of the following formulas (2-1) to (2-3) as a repeating unit having an isoimidin structure. [Chemical Formula 18] In equations (2-1) to (2-2), ^R111 , ^R114 , ^R115 , and ^A1 have the same meanings as ^R111 , ^R114 , ^R115 , and ^A1 in equation (2) above, and the preferred states are also the same. In equation (2-3), ^R111 and ^R117 have the same meanings as ^R111 and ^R117 in equation (3) above, and the preferred states are also the same.

The total content of any of the repeating units represented by equations (2-1) to (2-3) can be set as the amount of isoimidin structure in a particular resin within the above range.

As an embodiment of the polyimide precursor of the present invention, an example is provided where the total content of the repeating unit represented by formula (2), the repeating unit represented by formula (3), and any repeating unit represented by formulas (2-1) to (2-3) is 50 mol% or more of all repeating units. It is more preferable for the total content to be 70 mol% or more, further preferable for 90 mol% or more, and especially preferable for more than 90 mol%. There is no particular limitation on the upper limit of the total content. All repeating units in the polyimide precursor except for the terminal can be any one of the repeating units represented by formula (2), the repeating unit represented by formula (3), and any repeating unit represented by formulas (2-1) to (2-3).

The weight-average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. Furthermore, the number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The molecular weight dispersion of the above-mentioned polyimide precursor is preferably 2.5 or higher, more preferably 2.7 or higher, and even more preferably 2.8 or higher. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor. For example, 4.5 or below is preferred, 4.0 or below is better, 3.8 or below is further preferred, 3.2 or below is even better, 3.1 or below is still better, 3.0 or below is even better, and 2.95 or below is particularly preferred. In this specification, the molecular weight dispersion is a value calculated using weight average molecular weight / number average molecular weight.

Polyimide precursors may also contain other repeating units. Examples of such repeating units include those represented by the formula (PAI-1) below. [Formula 19]

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

Furthermore, R ¹¹⁶ is preferably derived from dicarboxylic acid compounds or dicarboxylic acid dihalides. In this invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide. The carboxyl groups in a dicarboxylic acid dihalide only need to be halogenated; for example, chlorination is preferred. That is, a dicarboxylic acid dihalide is preferably a dicarboxylic acid dichloride compound. Examples of halogenable dicarboxylic acid compounds or dicarboxylic acid dihalides that can be used in the manufacture of polyamide-imide precursors include linear or branched aliphatic, cyclic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides. Only 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 preferred that the dicarboxylic acid compound or dicarboxylic acid dihalogenate contains a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more of these groups via a linker. It is even more preferred that the dicarboxylic acid compound or dicarboxylic acid dihalogenate contains an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more of the aromatic groups having 6 to 20 carbon atoms via a linker.

Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, octanoic acid, dodecafluorooctanoic acid, azelaic acid, sebacic acid, and 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 above-mentioned dicarboxylic acid compounds can be given.

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.

[Method for Manufacturing a Specific Resin] A specific resin can be synthesized, for example, by the method shown in Route 1 or Route 2 below. However, the method for synthesizing the specific resin of the present invention is not limited to these methods.

-Route 1- In the step of obtaining a half-ester by adding an alcohol to a tetracarboxylic acid dianhydride, followed by adding a diamine to obtain a resin containing a polyamide structure, the diamine is made to function in a state where the anhydride remains in the system by adjusting the stoichiometry of the alcohol or by subsequently adding the amount of tetracarboxylic acid, thereby obtaining a polyamide-amide copolymer. Then, by using a suitable condensing agent to close the amide ring, a resin having an isoamide structure can be obtained. A summary of the synthetic scheme in Route 1 above is shown below. [Chemical Formula 20]

The manufacture of the aforementioned resins containing polyamide structures is preferably carried out in a solvent. Examples of solvents include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, and tetrahydroxyfuran. The temperature and reaction time in the manufacturing of the above-mentioned resin containing polyamide structure can be set appropriately according to known conditions, but for example, it can be set to 40-200°C and 10 minutes to 20 hours.

In the step of obtaining the resin containing the polyamide structure described above, a halogenating agent can be used to halogenate the half-ester. Examples of halogenating agents include _SOCl2 and phosphochloride. Alternatively, it is preferable to use a non-halogen catalyst without using the aforementioned halogenating agent. As a non-halogen catalyst, known amide catalysts that do not contain halogen atoms can be used without particular limitation, such as boroxine trimers, N-hydroxyl compounds, tertiary amines, phosphate esters, amine salts, urea compounds, and carbodiimide compounds. Examples of the aforementioned carbodiimide compounds include N,N'-diisopropylcarbodiimide and N,N'-dicyclohexylcarbodiimide.

Examples of condensing agents used for ring-closing of the aforementioned acetic acid moiety include acetic anhydride-pyridine reagents, acetic anhydride-triethylamine reagents, trifluoroacetic anhydride, and carbodiimide condensing agents such as dicyclohexylcarbodiimide. The temperature and reaction time in the aforementioned ring closure can be appropriately set according to known conditions, but for example, they can be set to 40–200°C and 10 minutes–20 hours.

-Route 2- In the step of adding a diamine to a tetracarboxylic dianhydride and assuming it to be a resin containing a polyamide structure, obtaining a polyisoimide by ring closure using a suitable condensing agent, and then reacting an alcohol with the aforementioned polyisoimide to obtain a resin containing a polyamide structure, the amount of alcohol added is adjusted to retain the isoimide structure, thereby obtaining a resin having an isoimide structure. A summary of the synthetic scheme in Route 2 above is shown below. [Chemical Formula 21]

The manufacture of the aforementioned resin containing a polyamide structure is preferably carried out in a solvent. As a solvent, the same solvents mentioned in route 1 above can be used. The temperature and reaction time in the manufacture of the aforementioned resin containing a polyamide structure can be appropriately set according to known conditions, but for example, they can be set to 40–200°C for 10 minutes to 20 hours.

Examples of the aforementioned condensing agents include, for instance, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-dicyclohexylcarbodiimide, and N,N'-diisopropylcarbodiimide as carbodiimide-based condensing agents; N,N'-carbonyldiimidazole and 1,1'-carbonyldi(1,2,4-triazole) as imidazole-based condensing agents; and 4-(4,6-dimethoxy-1,3,5-trimethoxy-2-yl)-4-methylmorpholine hydrochloride hydrate and trifluoromethanesulfonic acid (4,6-dimethoxy- 1,3,5-Triazol-2-yl)-(2-octyloxy-2-oxoethyl)dimethylammonium; as phosphonium-based condensing agents, 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytripyrrolidone phosphonium hexafluorophosphate, (7-azabenzotriazol-1-yloxy)tripyrrolidone phosphonium hexafluorophosphate, chlorotripyrrolidone phosphonium hexafluorophosphate, bromotris(dimethylamino)phosphonium hexafluorophosphate, 3-(diethoxyphosphatoxy)-1,2,3-benzotriazol-4(3H)-one; as urea-based condensing agents, O-(benzotriazol-1-yl)-N,N,N ',N'-Tetramethylurea hexafluorophosphate, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethylurea hexafluorophosphate, O-(N-succinimidyl)-N,N,N',N'-tetramethylurea tetrafluoroborate, O-(N-succinimidyl)-N,N,N',N'-tetramethylurea hexafluorophosphate, O-(3,4-dihydro-4-oxo-1,2,3-benzotriazol-3-yl)-N,N,N',N'-tetramethylurea tetrafluoroborate, S-(1-oxide-2-pyridyl)-N,N,N',N'-tetramethylthiourea tetrafluoroborate, O-[2 [-oxo-1(2H)-pyridyl]-N,N,N’,N’-tetramethylurea tetrafluoroborate, {{[(1-cyano-2-ethoxy-2-oxoylethylene)amino]oxy}-4-morpholinomethylene} dimethylammonium hexafluorophosphate; as a fluoroalkyl condensing agent, 2-chloro-1,3-dimethylimidazoline hexafluorophosphate, 1-(chloro-1-pyrrolidinylmethylene)pyrrolidone hexafluorophosphate, 2-fluoro-1,3-dimethylimidazoline hexafluorophosphate, fluoro-N,N,N’,N’-tetramethylformamidine hexafluorophosphate, acetic anhydride-pyridine reagents, acetic anhydride-triethylamine reagents, trifluoroacetic anhydride, etc. Furthermore, additives can be used simultaneously with condensing agents. Examples of additives include 1-hydroxybenzotriazole, 1-hydroxy-7-azabenzotriazole, N-hydroxysuccinimide, and N,N'-disuccinimide carbonate. Among these, stable and isoimidide polymers that can be isolated can be obtained, thus carbodiimide-based condensing agents are preferred, especially 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride).

Before adding the aforementioned condensing agent, the ends of the resin containing the polyamide structure can be sealed using an end-sealing component. Examples of end-sealing components include monoamines, monoisocyanates, and monocarboxylic acid actives (e.g., compounds having an anhydride, chlorohydrin, or thionylchlorohydrin structures). The reaction conditions when using the aforementioned end-sealing components are not particularly limited, and can be appropriately set according to the type of end-sealing component. However, for example, a temperature of 10–200°C and a reaction time of 10 minutes to 20 hours are possible.

In either of the above pathways 1 and 2, the polymerizable group contained in a particular resin can be introduced by using an alcohol having a polymerizable group (e.g., hydroxyethyl methacrylate, etc.) as the alcohol, using a diamine having a polymerizable group as the diamine, or by pre-introducing a reactive group (e.g., carboxyl group, hydroxyl group, etc.) into the resin having an isoimidine structure, and by reacting a reactive group (e.g., epoxy group, isocyanate group, etc.) that can react with the above reactive group and a compound having a polymerizable group with the resin.

In either of the above-described pathways 1 and 2, a step of precipitating a solid and then redissolving it may be included. Specifically, this can be achieved by precipitating the polyimide precursor in the reaction solution in a solvent such as water or alcohol, and then redissolving the polyimide precursor, such as tetrahydrofuran, in a soluble solvent. Furthermore, a step of drying the polyimide precursor may also be included. This drying step yields a powdered polyimide precursor.

[Content] The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total solid content of the composition. Furthermore, the content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solid content of the composition. The composition of the present 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.

<Radiation-Induced Polymerization Initiator> The composition of this invention includes a radiation-induced polymerization initiator. The radiation-induced polymerization initiator is any compound that reacts with radiation to produce a polymerization initiator, but a photopolymerization initiator is preferred. Furthermore, radiation refers to electron beams, ultraviolet radiation, X-rays, alpha rays, beta rays, gamma rays, etc., with ultraviolet radiation being preferred.

[Photopolymerization Initiator] The composition of this invention preferably includes a photopolymerization initiator as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitizing to light in the ultraviolet to visible region is preferred. Alternatively, it can be an active agent that generates active free radicals by interacting with a photoexcitation sensitizer. Furthermore, the oxime compound described later is preferred as the above-mentioned photoradical polymerization initiator.

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 range of about 300–800 nm (preferably 330–500 nm). The molar absorptivity of the compound can be determined using known methods. For example, it is preferable to determine it using a UV-Vis spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) with ethyl acetate solvent at a concentration of 0.01 g/L.

As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (such as compounds with a trihalomethane skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethane skeleton, etc.), 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, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron-aromatic hydrocarbon complexes. For details regarding these contents, 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 into this specification.

As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611 can be cited, and that content is incorporated into this specification. KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferred in commercially available products.

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

As a hydroxyacetophenone initiator, it can use IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF).

As an aminoacetophenone-based initiator, it can be used with commercially available products such as IRGACURE 907, IRGACURE 369 and IRGACURE 379 (all products manufactured by BASF).

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.

Examples of phosphine-based initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Additionally, commercially available products such as IRGACURE-819 or IRGACURE-TPO (both manufactured by BASF) can be used.

Examples of metallocene compounds include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).

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 (residual exposure) and also act as photocuring accelerators.

As specific examples of oxime compounds, compounds disclosed in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, and Japanese Patent Application Publication No. 2006-342166 may be used.

Preferred oxime compounds include, for example, compounds with the following structures: 3-benzoxylinosylbutane-2-one, 3-acetoxylinosylbutane-2-one, 3-propoxylinosylbutane-2-one, 2-acetoxylinosylpentane-3-one, 2-acetoxylinosyl-1-phenylpropane-1-one, 2-benzoxylinosyl-1-phenylpropane-1-one, 3-(4-toluenesulfonoxy)iminobutane-2-one, and 2-ethoxycarbonylosyl-1-phenylpropane-1-one. In the compositions of the present invention, the use of oxime compounds (oxime-based photopolymerization initiators) as photoradical polymerization initiators is particularly preferred. Oxime photopolymerization initiators have a linker group >C=N-O-C(=O)- within the molecule.

【Chemical Formula 22】

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, the photoradical polymerization initiator 2 disclosed in Japanese Patent Application Publication No. 2012-014052) are also suitable. Furthermore, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) are also suitable. Additionally, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) is also suitable. Furthermore, oxime compounds with the following structure can also be used. [Chemical Formula 23]

Oxime compounds with cyclohexane can also be used as photopolymerization initiators. Specific examples of oxime compounds with cyclohexane include the compound described in Japanese Patent Application Publication No. 2014-137466 and the compound described in Japanese Patent No. 06636081.

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

Furthermore, oxime compounds containing fluorine atoms can also be used. Specific examples of such oxime compounds include the compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36 to 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.

As the best oxime compounds, examples include the oxime compounds with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and the oxime compounds with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061.

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

Further preferred photoradical polymerization initiators are trihalomethane trihalomethane compounds, α-aminoketone compounds, acetophosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. It is even more preferred to select at least one compound from the group consisting of trihalomethane trihalomethane compounds, α-aminoketone compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. It is even more preferred to use metallocene compounds or oxime compounds. It is even more preferred to use 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. Additionally, compounds represented by formula (I) below can also be used.

【Chemical Formula 24】

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

【Chemical Formula 25】

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

Furthermore, the photoradical polymerization initiators can also be the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photopolymerization initiator is included, its content relative to the total solid content of the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. The photopolymerization initiator may be one type or may contain two or more types. When two or more photopolymerization initiators are included, the total amount is preferably within the above range.

[Photoacid Generator] Furthermore, it is preferable that the composition of the present invention includes a photoacid generator as a radiosensitive polymerization initiator. By including the photoacid generator and polymerizable compounds (other than free radical polymerizable compounds, as described later) in the composition, it is also possible to achieve a state in which, for example, the acid generated in the exposed area promotes the crosslinking reaction of the aforementioned polymerizable compounds, making the exposed area less susceptible to removal by the developing solution than the non-exposed area. According to this state, a negative pattern can be obtained.

As a photoacid generator, there are no particular limitations as long as it generates acid through exposure. Examples include quinone diazonium compounds, diazonium salts, phosphonium salts, strontium salts, monium salts, styrannium salts, acetylene sulfonates, oxime sulfonates, diazonium, diazonium, and sulfonate compounds such as orthonitrobenzyl sulfonate.

Examples of quinone diazonium compounds include those obtained by bonding a quinone diazonium sulfonate ester to a polyhydroxyl compound, those obtained by bonding a quinone diazonium sulfonic acid sulfonamide to a polyamine compound, and those obtained by bonding a quinone diazonium sulfonic acid to a polyhydroxyl polyamine compound via at least one of an ester bond and a sulfonamide bond. In this invention, for example, it is preferable that at least 50 mol% of the functional groups of such polyhydroxyl or polyamine compounds are substituted with quinone diazonium compounds.

In this invention, at least one of 5-naphthoquinone diazonium sulfonate and 4-naphthoquinone diazonium sulfonate is preferably used as the diazonium sulfonate. The 4-naphthoquinone diazonium sulfonate compound is absorbent in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazonium sulfonate compound extends to the g-ray region of a mercury lamp and is suitable for g-ray exposure. In this invention, it is preferable to select the 4-naphthoquinone diazonium sulfonate compound or the 5-naphthoquinone diazonium sulfonate compound based on the exposure wavelength. Furthermore, the same molecule may contain naphthoquinone disulfonate compounds having 4-naphthoquinone disulfonyl and 5-naphthoquinone disulfonyl groups, or it may contain both 4-naphthoquinone disulfonate compounds and 5-naphthoquinone disulfonate compounds.

The aforementioned naphthoquinone diazonium compounds can be synthesized via esterification of a compound with a phenolic hydroxyl group and a quinone diazonium sulfonate compound, or they can be synthesized using known methods. Using these naphthoquinone diazonium compounds further improves resolution, sensitivity, and film residue. Examples of the aforementioned naphthoquinone diazonium compounds include 1,2-naphthoquinone-2-diazazo-5-sulfonic acid or 1,2-naphthoquinone-2-diazazo-4-sulfonic acid, as well as salts or esters of these compounds.

Examples of compounds that are onium salts or sulfonates include those described in paragraphs 0064 to 0122 of Japanese Patent Application Publication No. 2008-013646.

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

【Chemical Formula 26】

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

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

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

【Chemical Formula 27】

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

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 hydrogen or alkyl being more preferred. In compounds where two or more ^Rs2 are present, it is preferred that one or two are alkyl, aryl, or halogen atoms, more preferred that one is alkyl, aryl, or halogen atom, and especially preferred that one is alkyl and the remainder are hydrogen atoms. The alkyl or aryl group represented by ^Rs2 may have a substituent T. In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, with O being more preferred. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a member is a 5-member ring or a 6-member ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns being 1 is preferred, and when Xs is S, ns being 2 is preferred. In formulas (OS-103) to (OS-105), the alkyl group (preferably with 1 to 30 carbon atoms) and alkoxy group (preferably with 1 to 30 carbon atoms) represented by ^Rs6 may have substituents. In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6. Integers from 0 to 2 are preferred, 0 or 1 are more preferred, and 0 is particularly preferred.

Furthermore, the compound represented by formula (OS-103) is preferably represented by formula (OS-106), formula (OS-110), or formula (OS-111); the compound represented by formula (OS-104) is preferably represented by formula (OS-107); and the compound represented by formula (OS-105) is preferably represented by formula (OS-108) or formula (OS-109). [Chemical Formula 28]

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

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

In formulas (OS-106) to (OS-111), ^Rt9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, with a hydrogen atom being preferred. ^Rt2 represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime can be any one of them or a mixture thereof. Specific examples of the 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.

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

【Chemical Formula 29】

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

In formula (OS-101) or formula (OS-102), ^Ru1 to ^Ru4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amino 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 the compound represented by formula (OS-102). Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring can be either one or a mixture thereof. Specific examples of compounds represented by formula (OS-101) are the compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674, and these contents are incorporated herein by reference. Among the above-mentioned compounds, b-9, b-16, b-31, and b-33 are preferred.

In addition, commercially available products can be used as photosensitive acid generators. Examples of commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250, Omnicat 270 (both manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

Furthermore, the following compound, represented by the structural formula 30, can be cited as a better example.

As a photoacid generator, it is also suitable for organic halogenated compounds. As organic halogenated compounds, specific examples include Wakabayashi et al.'s "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication Nos. 46-4605, 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, and M.P. Hutt's "Jurnal of Heterocyclic Compounds described in Chemistry 1 (No. 3), (1970), etc., especially trihalomyl-substituted oxazole compounds: S-trihalomyl compounds. More preferably, S-trihalomyl derivatives formed by at least one mono-, di-, or trihalomyl-substituted methyl group bonded to an S-trihalomyl ring can be cited, specifically, for example, 2,4,6-tris(monochloromethyl)-S-trihalomyl, 2,4,6-tris(dichloromethyl)-S-trihalomyl, 2,4,6-tris(trichloromethyl)-S-trihalomyl, 2-methyl-4,6-bis(trichloromethyl)-S-trihalomyl, 2-n-propyl-4,6-bis(trichloromethyl)-S -trichlorophenyl, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-phenyl-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl] [2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-tris-tris-phenyl]-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-tris-phenyl, 2-styryl-4,6-bis(trichloromethyl)-s-tris-phenyl, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-tris-phenyl, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris-phenyl, 2-(4-naphthoxy) Naphthyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-phenylthio-4,6-bis(trichloromethyl)-s-tris, 2-benzylthio-4,6-bis(trichloromethyl)-s-tris, 2,4,6-tris(dibromomethyl)-s-tris, 2,4,6-tris(tribromomethyl)-s-tris, 2-methyl-4,6-bis(tribromomethyl)-s-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-tris, etc.

As a photoacid generator, organoborate compounds are also applicable. Specific examples of organoborate compounds include Japanese Patent Application Publication Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9-188710, 2000-131837, 2002-107916, Japanese Patent No. 2764769, and Japanese Patent Application No. 2000-310808, as well as Kunz, Martin, “Rad Tech’98. Proceeding April”. The organoborates recorded in "19-22, 1998, Chicago", etc.; the organoboron-strontium complexes or organoboron-oxystrontium complexes recorded in Japanese Patent Application Publication No. 6-157623, Japanese Patent Application Publication No. 6-175564, Japanese Patent Application Publication No. 6-175561; and the organoboron-strontium oxidized complexes recorded in Japanese Patent Application Publication No. 6-175554 and Japanese Patent Application Publication No. 6-175553. Organoboronium complexes, organoboronium complexes described in Japanese Patent Application Publication No. 9-188710, and organoboronium transition metal coordination complexes described in Japanese Patent Application Publication Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014, etc.

As a photoacid generator, disulfide compounds can also be used. Examples of disulfide compounds include compounds described in Japanese Patent Application Publication No. 61-166544 and Japanese Patent Application No. 2001-132318, as well as diazonium compounds.

Examples of such onium salt compounds include S.I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), and T.S. Bal et al. Diazo salts described in al, Polymer, 21,423 (1980); ammonium salts described in U.S. Patent No. 4,069,055; phosphonium salts described in the specifications of U.S. Patent Nos. 4,069,055 and 4,069,056; phosphonium salts described in the specifications of European Patent Nos. 104,143, 339,049, and 410,201; tin salts described in Japanese Patent Nos. 2-150848 and 2-296514; and European Patent Nos. 370,693 and 390,056. The strontium salts described in the specifications of patents 214, 233,567, 297,443, 297,442, 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, 2,904,626, 3,604,580, and 3,604,581, and J.V. Crivello. Selenium salts described in J.V. Crivello et al., Macromolecules, 10(6), 1307(1977), J.V. Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047(1979), and arsenic salts, pyridinium salts, and other onium salts described in C.S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988).

As onium salts, examples can be given by the general formulas (RI-I) to (RI-III). [Chemical Formula 31] In formula (RI-I), Ar ₁₁ represents an aryl group having 1 to 6 substituents and having 20 or fewer carbon atoms. Examples of preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 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, alkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms, alkylamide or arylamide 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 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 an aryl group with 20 or fewer 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 1 to 12 carbon atoms, alkynyl groups with 1 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, alkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 1 to 12 carbon atoms, alkylamide or arylamide groups with 1 to 12 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 ₂₁ ^- represents a monovalent anion, which is 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 1 to 6 substituents and fewer than 20 carbon atoms. Preferably, considering reactivity and stability, an aryl group is preferred. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 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, alkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms, alkylamide or arylamide 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.

As specific examples, the following can be cited: [Chemical Formula 32] 【Chemical Formula 33】 【Chemical Formula 34】 【Chemical Formula 35】

When the photoacid generator is included, its content relative to the total solid content of the 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 2 to 15% by mass. The photoacid generator may contain only one type or more types. When two or more photoacid generators are contained, their total content is preferably within the above range.

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

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl 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., 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.

As ethers, preferred examples include 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.

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

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

As an ion, dimethyl ion could be cited as a better example.

Among the amides, N-methyl-2-pyrrolidone, N-ethyl-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-acetymorpholine are considered superior.

Among ureas, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone are good examples.

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

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

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

From a coatability perspective, it is preferable to set the solvent content such that the total solids concentration of the curable resin composition of this invention is 5-80% by mass, more preferably 5-75% by mass, further preferably 10-70% by mass, and even more preferably 40-70% by mass. The solvent content can be adjusted according to the desired coating thickness and coating method.

The solvent may contain only one type or more types. When the solvent contains more than one type, it is preferable that the total amount of solvents is within the range described above.

<Onium Salts> The curable resin composition of the present invention may also contain onium salts. In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, the inclusion of onium salts is preferred. The type of onium salt is not particularly limited, and ammonium salts, imine salts, strontium salts, zirconia salts, or phosphonium salts are preferred. Among these, ammonium salts or imine salts are preferred from the viewpoint of high thermal stability, and strontium salts, zirconia salts, or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

Furthermore, onmium salts are salts containing both cations and anions with an onmium structure. These cations and anions can be bonded via covalent bonds or not. That is, onmium salts can be intramolecular salts containing both cation and anion portions within the same molecular structure, or they can be intermolecular salts formed by ionic bonding between cation and anion molecules that are distinct molecules. Intermolecular salts are preferred. Furthermore, in the curable resin composition of the present invention, the aforementioned cation portion or cation molecule can be bonded to the aforementioned anion portion or anion molecule by ionic bonds, and can also be dissociated. As the cation in the onmium salt, ammonium cation, pyridinium cation, strontium cation, monium cation, or phosphonium cation are preferred, and it is even more preferred to select at least one cation from the group consisting of tetraalkylammonium cation, strontium cation, and monium cation.

The onium salt used in this invention can be a thermal alkali generator, as described later. A thermal alkali generator is a compound that produces alkali upon heating; examples include compounds that produce alkali when heated to above 40°C. Examples of onium salts include those described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. Furthermore, onium salts used in the field of polyimide precursors can also be used without particular restriction.

When the curable resin composition of the present invention contains onium salts, the content of onium salts relative to the total solid content of the curable resin composition of the present invention is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, further preferably 20% by mass or less, and even more preferably 10% by mass or less, and can be 5% by mass or less, or even 4% by mass or less. One or more onium salts can be used. When two or more are used, the total amount within the above range is preferred.

<Hot Alkali Generator> The curing resin composition of the present invention may also contain a hot alkali generator. In particular, when the curing resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain a hot alkali generator. The hot alkali generator may be a compound corresponding to the onmium salts described above, or it may be a hot alkali generator other than the onmium salts described above. Examples of hot alkali generators other than the onmium salts described above include nonionic hot alkali generators. Examples of nonionic hot alkali generators include compounds represented by formula (B1) or formula (B2). [Chemical Formula 36]

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.

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

The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below. [Chemical Formula 37]

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

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

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

Furthermore, the compound represented by formula (B1-1) is preferably the same as the compound represented by formula (B1-1a). [Chemical Formula 38]

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 hydrogen atoms, alkyl groups (preferably with 1 to 12 carbons, more preferably with 1 to 6 carbons, and even more preferably with 1 to 3 carbons), alkenyl groups (preferably with 2 to 12 carbons, more preferably with 2 to 6 carbons, and even more preferably with 2 to 3 carbons), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), aralkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), hydrogen atoms, or methyl groups are preferred. Rb ¹⁷ is an alkyl group (preferably with 1 to 24 carbons, more preferably with 1 to 12 carbons, and even more preferably with 3 to 8 carbons), an alkenyl group (preferably with 2 to 12 carbons, more preferably with 2 to 10 carbons, and even more preferably with 3 to 8 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 12 carbons), or an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 12 carbons), wherein an aryl group is preferred.

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.

The following compounds can be cited as specific examples of compounds that act as thermal alkali generators among the aforementioned onium salts, or as specific examples of thermal alkali generators other than the aforementioned onium salts.

【Chemical Formula 39】

【Chemical Formula 40】

【Chemical Formula 41】

The content of the alkali-generating agent relative to the total solid content of the curing resin composition of the present invention is preferably 0.1% to 50% by mass. A lower limit of 0.5% by mass or more is preferred, and 1% by mass or more is further preferred. An upper limit of 30% by mass or less is preferred, and 20% by mass or less is further preferred. One or more alkali-generating agents can be used. When using two or more, the total amount within the above range is preferred.

<Other Resins> The 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"). Examples of other resins include polyamide-imide, polyamide-imide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, and acrylic resins. For example, by further adding acrylic resins, a composition with excellent coatability can be obtained, and an organic film with excellent solvent resistance can be obtained. For example, by replacing or excluding the polymerizable compounds described later, an acrylic resin with a high polymerizable value of less than 20,000 by weight average molecular weight can be added to the composition, thereby improving the coatability of the composition, the solvent resistance of the organic film, etc.

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

[Photoalkali Generator] The curing resin composition of this invention may contain a photoalkali generator as a photosensitizer. By containing a photoalkali generator in the curing resin composition, it is also possible to achieve the following state: for example, by utilizing the alkali generated in the exposed area to promote the cyclization of a specific resin, the exposed area is less susceptible to removal by the developer than the unexposed area. According to this state, negative relief patterns can be obtained. Furthermore, the curing of the specific resin after development can also be promoted by light.

As a photoalkali generator, there are no particular restrictions as long as it produces alkali through exposure; any known method can be used. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and Examples of ionic compounds that can be neutralized by forming salts through alkaline components include transition metal complexes, compounds with structures such as ammonium salts, compounds that are potential salts formed by the formation of salts by the amidoside portion of a carboxylic acid, and nonionic compounds such as carbamate derivatives, oxime derivatives, and acetic acid compounds that potential for alkalinity through ethyl carbamate bonds or oxime bonds. These compounds are described in S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006). In this invention, preferred examples of photoalkali generators include carbamate derivatives, amide derivatives, amide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

There are no particular limitations on the alkaline substance produced from the photoalkali generator, but compounds with amine groups can be cited, especially polyamines such as monoamines or diamines, and amidines. From the perspective of acetylation rate, a higher pKa is preferred for the aforementioned alkaline substance, which is a conjugated acid DMSO (dimethyl sulfoxide). A pKa of 1 or higher is preferred, and 3 or higher is even better. There are no particular upper limits for the aforementioned pKa, but 20 or lower is preferred. Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, and the value can be found in Determination of Organic Structures by Physical Methods (authors: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; ed.: Braude, E.A., Nachod, F.C.; Academic Press, New York, 1955) or Data for Biochemical Research (authors: Dawson, R.M.C. et al.; Oxford, Clarendon Press, 1959). For compounds not described in these references, the pKa will be calculated using ACD/pKa software (made by ACD/Labs) and derived from the structural formula.

From the perspective of the storage stability of curable resin compositions, it is preferable to use a photoalkali generator that does not contain salt in its structure, and preferably one where the nitrogen atom of the alkali portion produced in the photoalkali generator has no charge. It is also preferable to use covalent bonds to latent the produced alkali as a photoalkali generator, and preferably one where the alkali production mechanism involves the breaking of the covalent bond between the nitrogen atom of the produced alkali portion and its neighboring atom. A photoalkali generator that does not contain salt in its structure can be made neutral, thus improving solvent solubility and extending its shelf life. For this reason, it is preferable that the amine produced by the photoalkali generator used in this invention is a primary or secondary amine. Furthermore, from the viewpoint of the resistance of the pattern to chemicals, it is preferable that the photoalkali generator contains a salt in its structure.

Furthermore, for the reasons stated above, as a photoalkali generator, it is preferable to use covalent bonds to potentially generate alkali, and even better to use amide bonds, carbamate bonds, or oxime bonds to potentially generate alkali. Examples of photoalkali generators of the present invention include, for example, those with a cinnamic acid amide structure disclosed in Japanese Patent Application Publication No. 2009-080452 and International Patent Application Publication No. 2009/123122; those with a carbamate structure disclosed in Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008-247747; and those with an oxime structure or an aminoformyl oxime structure disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581. However, the invention is not limited to these examples. In addition, known photoalkali generator structures may also be used.

In addition, as photoalkali generators, examples include compounds described in paragraphs 0185-0188, 0199-0200 and 0202 of Japanese Patent Application Publication No. 2012-093746, compounds described in paragraphs 0022-0069 of Japanese Patent Application Publication No. 2013-194205, compounds described in paragraphs 0026-0074 of Japanese Patent Application Publication No. 2013-204019, and compounds described in paragraph 0052 of International Publication No. 2010/064631.

In addition, commercially available products can be used as photoalkali generators. Examples of commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), A2502, B5085, N0528, N1052, O0396, O0447, and O0448 (manufactured by Tokyo Chemical Industry Co., Ltd.).

When a photoalkali generator is included, its content relative to the total solid content of the curing 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 2 to 15% by mass. The photoalkali generator may contain only one type or more types. When two or more photoalkali generators are contained, their total content is preferably within the above range.

<Thermal Polymerization Initiator> The 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, the polymerization reaction of the resin and polymerizable compound can also proceed in the heating step described later, thus further improving solvent resistance.

As a thermal free radical polymerization initiator, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited as examples.

When a thermal polymerization initiator is included, its content relative to the total solid content of the 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 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 included, the total amount is preferably within the above range.

<Thermal Acid Generator> The composition of this invention may include a thermal acid generator. The thermal acid generator has the effect of promoting cross-linking reactions of at least one compound selected from compounds having hydroxymethyl, alkoxymethyl, or acetomethyl groups, epoxides, cyclobutanes, and benzoxazines by generating acid through heating.

The thermal decomposition onset temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. Furthermore, if a thermal acid generator is selected that does not generate acid during drying (pre-baking: approximately 70–140°C) after the composition is applied to the substrate, but generates acid during the final heating (curing: approximately 100–400°C) after patterning in subsequent exposure and development, the decrease in sensitivity during development can be suppressed, which is therefore preferable. Regarding the thermal decomposition onset temperature, it is determined by heating the thermal acid generator in a pressure-resistant capsule at 5°C/min to 500°C, taking the lowest heating peak temperature as the result. As equipment used to measure the temperature at which thermal decomposition begins, examples include the Q2000 (manufactured by TA Instruments).

It is preferable that the acid produced from the hot acid generator is a strong acid, such as p-toluenesulfonic acid, benzenesulfonic acid and other aromatic sulfonic acids, methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid and other alkylsulfonic acids, or trifluoromethanesulfonic acid and other halogen sulfonic acids. As an example of such a hot acid generator, the one described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935 can be cited.

Among these, considering the minimal residue in organic membranes and the minimal reduction in the physical properties of the organic membranes, those producing alkylsulfonic acids or halogen sulfonic acids with 1 to 4 carbon atoms are preferred. As hot acid generators, the following are preferred: (4-hydroxyphenyl)dimethyl strontium methanesulfonic acid, (4-((methoxycarbonyl)oxy)phenyl)dimethyl strontium methanesulfonic acid, benzyl(4-hydroxyphenyl)methyl strontium methanesulfonic acid, benzyl(4-((methoxycarbonyl)oxy)phenyl)methyl strontium methanesulfonic acid, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)strontium methanesulfonic acid, and trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)strontium methanesulfonic acid). Phenyl)dimethyl strontium salt, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethyl strontium salt, benzyl(4-hydroxyphenyl)methyl strontium salt, benzyl(4-((methoxycarbonyl)oxy)phenyl)methyl strontium salt, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl) strontium salt, 3-(5-(((propanesulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(ortho-tolyl)propionitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred.

Furthermore, the compound described in paragraph 0059 of Japanese Patent Application Publication No. 2013-167742 is also preferred as a thermal acid generator.

The content of the hot acid generator is preferably 0.01 parts by weight or more relative to 100 parts by weight of a specific resin, and more preferably 0.1 parts by weight or more. By containing more than 0.01 parts by weight, the cross-linking reaction is promoted, thereby further improving the mechanical properties and solvent resistance of the organic membrane. Furthermore, from the viewpoint of the electrical insulation of the organic membrane, 20 parts by weight or less is preferred, 15 parts by weight or less is even better, and 10 parts by weight or less is even more preferred.

<Polymerizable Compound> Preferably, the curable resin composition of the present invention contains a polymerizable compound. Examples of polymerizable compounds include free radical polymerizable compounds or other polymerizable compounds. Among these, it is preferable that the curable resin composition of the present invention contains a photoradioactive polymerization initiator as a radiosensitive polymerization initiator and a free radical polymerizable compound as a polymerizable compound; it is even more preferable that it contains a free radical polymerizable group as a polymerizable group in a specific resin, contains a photoradioactive polymerization initiator as a radiosensitive polymerization initiator, and contains a free radical polymerizable compound as a polymerizable compound.

<Free Radical Polymerizing Compound> The curable resin composition of the present invention preferably also contains a free radical polymerizing compound. A free radical polymerizing compound is a compound having a free radical polymerizing group. As a free radical polymerizing group, it is preferable to have a group containing an ethylene unsaturated bond. Examples of such groups containing ethylene unsaturated bonds include vinyl, allyl, vinylphenyl, and (meth)acrylonitrile groups. Among these, (meth)acrylonitrile is preferred as the group containing an ethylene unsaturated bond, and from a reactivity point of view, (meth)acrylonitrileoxy is more preferred.

The free radical polymerizable compound is any compound having one or more ethylene unsaturated bonds, and compounds having two or more are preferred. A compound having two ethylene unsaturated bonds is preferably a compound having two of the aforementioned groups containing ethylene unsaturated bonds. Furthermore, from the viewpoint of the film strength of the obtained pattern, the curable resin composition of the present invention preferably contains compounds having three or more ethylene unsaturated bonds as free radical polymerizable compounds. Among the compounds having three or more ethylene unsaturated bonds, compounds having 3 to 15 ethylene unsaturated bonds are preferred, compounds having 3 to 10 ethylene unsaturated bonds are more preferred, and compounds having 3 to 6 ethylene unsaturated bonds are even more preferred. Furthermore, it is preferable that the compounds having three or more ethylene unsaturated bonds are compounds having three or more of the aforementioned groups containing ethylene unsaturated bonds; more preferably, compounds having 3 to 15 groups; even more preferably, compounds having 3 to 10 groups; and especially preferably, compounds having 3 to 6 groups. Furthermore, from the viewpoint of the film strength of the obtained pattern, it is also preferable that the curable resin composition of the present invention comprises compounds having two ethylene unsaturated bonds and compounds having three or more ethylene unsaturated bonds.

The molecular weight of the free radical polymerizable compound is preferably below 2,000, more preferably below 1,500, and even more preferably below 900. The lower limit of the molecular weight of the free radical polymerizable compound is preferably above 100.

Specific examples of free radical polymerizable compounds 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 polyols, and amides of unsaturated carboxylic acids and polyamines. 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. Additionally, as another example, compounds that replace the aforementioned unsaturated carboxylic acids can 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, compounds with a boiling point above 100°C at normal pressure are preferred for free radical polymerization. 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, hexanediol (meth)acrylate, trihydroxymethyl propane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanate, glycerol, or trihydroxymethyl ethane, which are added to polyfunctional alcohols with ethylene oxide or propylene oxide followed by (meth)acrylate polymerization. Compounds obtained by esterification, such as ethyl aminocarbamates of (meth)acrylate described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, epoxy acrylates as reaction products of epoxy resins and (meth)acrylic acid, and other multifunctional acrylates or methacrylates and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting compounds such as glycidyl (meth)acrylate, which have cyclic ether groups and vinyl unsaturated bonds, with polyfunctional carboxylic acids.

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

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

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be used, and such contents are incorporated into this specification.

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

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

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

Commercially available free radical polymerizable compounds include, for example, SR-494 (a tetrafunctional acrylate with four ethynooxy chains) manufactured by Sartomer Company, Inc.; SR-209, 231, and 239 (difunctional methyl acrylate with four ethoxy chains) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with six pentylooxy chains) manufactured by Nippon Kayaku Co., Ltd.; TPA-330 (a trifunctional acrylate with three isobutylooxy chains); ethyl carbamate oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.); NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300; and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.). (Manufactured by 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 polymerizable compounds, ethyl carbamate acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and ethyl carbamate compounds with an ethylene oxide backbone 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 polymerizable compound, compounds having an amino group structure or a sulfide structure within the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

Free radical polymerizable compounds can be free radical polymerizable compounds containing acid groups such as carboxyl groups and phosphate groups. It is preferable that the free radical polymerizable compound 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 polymerizable compound containing acid groups is formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of an aliphatic polyhydroxyl compound. Particularly preferred are free radical polymerizable compounds containing acid groups formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of an aliphatic polyhydroxyl compound, in which 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 polymerizable compounds containing acid groups is 0.1–40 mg KOH/g, and particularly preferably 5–30 mg KOH/g. As long as the acid value of the free radical polymerizable compound is within the above range, the manufacturing process is excellent, resulting in excellent developing properties. Furthermore, polymerizability is good. On the other hand, from the viewpoint of developing speed in alkaline developing, the preferred acid value for free radical crosslinkers containing acid groups is 0.1–300 mg KOH/g, and particularly preferably 1–100 mg KOH/g. The above acid values are determined according to JIS K 0070:1992.

From the perspectives of pattern resolution and film stretchability, it is preferable to use difunctional methacrylates or acrylates in the curing resin composition of this invention. Specific compounds that can be used include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol diacrylate. Dimethacrylates, including dihydroxymethyltricyclodecane diacrylate, dihydroxymethyltricyclodecane dimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylate, EO-modified diacrylate of isocyanuric acid, EO-modified dimethacrylate of isocyanuric acid, difunctional acrylates having other ethyl carbamate bonds, and difunctional methacrylates having ethyl carbamate bonds. Two or more of these can be mixed as needed. Furthermore, from the perspective of suppressing warping by controlling the elastic modulus of the accompanying pattern, monofunctional radical polymerizable compounds can be used more effectively as radical polymerizable compounds. As a monofunctional free radical polymerizable compound, the following are preferred: n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, butoxyethyl methacrylate, carbitol methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, N-hydroxymethyl methacrylamide, glycidyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, and other methacrylate derivatives; N-vinylpyrrolidone, N-vinylcaprolactone and other N-vinyl compounds; alkenyl epoxypropyl ether, diallyl phthalate, trimellitic acid triallyl and other alkenyl compounds. As monofunctional free radical polymerizable compounds, compounds with a boiling point above 100°C at normal pressure are preferred in order to suppress volatilization before exposure.

In the case of free radical polymerizable compounds, it is preferable that their content relative to the total solid content of the curable resin composition of the present invention is more than 0% by mass and less than 60% by mass. A lower limit of 5% by mass or more is more 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 polymerizable compounds can be used alone or in combination of two or more. When using two or more compounds simultaneously, it is preferable that their total amount be within the range mentioned above.

<Other Polymerizing Compounds> Preferably, the curable resin composition of this invention includes other polymerizing compounds different from the aforementioned free radical polymerizing compounds. In this invention, other polymerizing compounds refer to polymerizing compounds other than the aforementioned free radical polymerizing compounds. Preferably, these compounds have a plurality of groups within their molecules that, through photosensitization by the aforementioned photosensitizer, promote the formation of covalent bonds between themselves and other compounds in the composition or their reaction products. Preferably, these compounds have a plurality of groups within their molecules that, through the action of an acid or alkali, promote the formation of covalent bonds between themselves and other compounds in the composition or their reaction products. Preferably, the aforementioned acid or alkali is an acid or alkali generated during the exposure step from a photoacid generator or photoalkali generator acting as a photosensitizer. As other polymerizable compounds, compounds having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups are preferred, and compounds having a structure in which at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups is directly bonded to a nitrogen atom are even more preferred. As other polymerizable compounds, examples include compounds having a structure in which the hydrogen atom of the amine group is replaced by hydroxymethyl or alkoxymethyl groups through a reaction of formaldehyde or formaldehyde and an alcohol with melamine, glycourea, urea, alkyl urea, benzoguanamine, or other amine-containing compounds. The method 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 are also acceptable. As for the aforementioned compounds containing amine groups, polymeric compounds using melamine are referred to as melamine-based polymeric compounds, polymeric compounds using urea, urea, or alkylurea are referred to as urea-based polymeric compounds, polymeric compounds using alkylurea are referred to as alkylurea-based polymeric compounds, and polymeric compounds using benzoguanidine are referred to as benzoguanidine-based polymeric compounds. Among these, it is preferable that the curable resin composition of the present invention includes at least one compound selected from the group consisting of urea-based polymeric compounds and melamine-based polymeric compounds, and it is even more preferable that it includes at least one compound selected from the group consisting of urea-based polymeric compounds and melamine-based polymeric compounds described below.

Specific examples of melamine-based polymeric compounds include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

Specific examples of urea-based polymerizable compounds include monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetramethoxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea; dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, dibutoxymethylurea, etc., urea-based polymerizable compounds; monohydroxymethylated ethylurea or dihydroxymethylated glycourea... Polymers of the ethoxyurea family, including monomethoxymethylated ethoxyurea, dimethoxymethylated ethoxyurea, monoethoxymethylated ethoxyurea, diethoxymethylated ethoxyurea, monopropoxymethylated ethoxyurea, dipropoxymethylated ethoxyurea, monobutoxymethylated ethoxyurea, or dibutoxymethylated ethoxyurea; Polymers of the ethoxyurea family, including monohydroxymethylated ethoxyurea, dihydroxymethylated ethoxyurea, monomethoxymethylated ethoxyurea, dimethoxymethylated ethoxyurea, monoethoxymethylated ethoxyurea, dipropoxymethylated ethoxyurea, monobutoxymethylated ethoxyurea, or dibutoxymethylated ethoxyurea; Polymers of the ethoxyurea family, including 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidineone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone, etc.

Specific examples of benzoguanidine polymeric compounds include monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated 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 benzenediethanol, 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, methoxymethylbenzoic acid methoxymethylphenyl ester, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4’,4’’-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5’-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3’,5,5’-tetra(methoxymethyl)-1,1’-biphenyl-4,4’-diol, etc.

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

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

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

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

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trihydroxymethylpropane 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) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, and EPICL. ON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (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, Rika Resin (registered trademark) BEO-20E (the above are product names, manufactured by DIC CORPORATION), 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, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (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.

[Oxycyclobutane compounds (compounds containing oxycyclobutyl groups)] Examples of oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl] ester, etc. As a specific example, the ARON OXETANE series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO.,LTD. can be used better, and two or more of them can be used alone or in combination.

[Benzoxazol compounds (compounds containing benzoxazole groups)] Because crosslinking is caused by ring-opening addition, benzoxazol compounds do not produce degassing during hardening, thereby further reducing thermal shrinkage and inhibiting warping, and are therefore preferred.

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

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

<Compounds having a sulfonamide structure, compounds having a thiourea structure> From the viewpoint of improving the adhesion of the obtained pattern to the substrate, the curable resin composition of the present invention preferably also includes at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure.

[Compounds possessing a sulfonylurea structure] The sulfonylurea structure is represented by the following formula (S-1). [Chemical Formula 42] In formula (S-1), R represents a hydrogen atom or an organic group. R can bond with other structures to form a ring structure, and * represents the bonding site with other structures independently. It is preferable that R is the same group as ^R2 in formula (S-2) below. Compounds having a sulfonamide structure can be compounds having two or more sulfonamide structures, but compounds having one sulfonamide structure are preferred.

Compounds with a sulfonamide structure, preferably those represented by the formula (S-2) below, are preferred. [Chemical Formula 43] In formula (S-2), ^R1 , ^R2 , and ^R3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of ^R1 , ^R2 , and ^R3 can bond together to form a ring structure. It is preferable that ^R1 , ^R2 , and ^R3 each independently represent a monovalent organic group. Examples of ^R1 , ^R2 , and ^R3 include hydrogen atoms or groups obtained by combining two or more of the following: alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, or combinations thereof. Among the aforementioned alkyl groups, those with 1 to 10 carbon atoms are preferred, and those with 1 to 6 carbon atoms are even more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Examples of cycloalkyl groups are cycloalkyl groups with 5 to 10 carbon atoms, and more preferably cycloalkyl groups with 6 to 10 carbon atoms. Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of alkoxy groups are alkoxy groups with 1 to 10 carbon atoms, and more preferably alkoxy groups with 1 to 5 carbon atoms. Examples of alkoxy groups are methoxy, ethoxy, propoxy, butoxy, and pentoxy. Examples of alkoxysilyl groups are alkoxysilyl groups with 1 to 10 carbon atoms, and more preferably alkoxysilyl groups with 1 to 4 carbon atoms. Examples of alkoxysilyl groups include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Among the aryl groups, those with 6 to 20 carbon atoms are preferred, and those with 6 to 12 carbon atoms are even more preferred. The aryl groups may have substituents such as alkyl groups. Examples of aryl groups include phenyl, tolyl, xylyl, and naphthyl. Examples of heterocyclic groups mentioned above include those obtained by removing a hydrogen atom from heterocyclic structures such as triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridyl ring, pyridine ring, piperidine ring, piperidine ring, morpholinium ring, dihydropiperanium ring, tetrahydropyranyl, and trihydropyranyl ring.

Among these, compounds in which ^R1 is aryl and ^R2 and ^R3 are each independently hydrogen atoms or alkyl groups are preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[Compounds with a thiourea structure] The thiourea structure is represented by the following formula (T-1). [Chemical Formula 44] In equation (T-1), ^R4 and ^R5 independently represent hydrogen atoms or monovalent organic groups, respectively. ^R4 and ^R5 can bond to form a ring structure. ^R4 can bond with other structures bonded to it to form a ring structure. ^R5 can bond with other structures bonded to it to form a ring structure. * independently represent the bonding sites with other structures.

It is preferable that ^R4 and ^R5 are each an independent hydrogen atom. Examples of ^R4 and ^R5 include hydrogen atoms or groups obtained by combining two or more of the following: alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, or alkyl groups. Among the alkyl groups, those with 1 to 10 carbon atoms are preferred, and those with 1 to 6 carbon atoms are even more preferred. Examples of the alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Among the cycloalkyl groups, those with 5 to 10 carbon atoms are preferred, and those with 6 to 10 carbon atoms are even more preferred. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of alkoxy groups include those with 1 to 10 carbon atoms, and those with 1 to 5 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy. Examples of alkoxysilyl groups include those with 1 to 10 carbon atoms, and those with 1 to 4 carbon atoms. Examples of alkoxysilyl groups include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of aryl groups include those with 6 to 20 carbon atoms, and those with 6 to 12 carbon atoms. The aforementioned aryl groups may have substituents such as alkyl groups. Examples of aryl groups include phenyl, tolyl, xylyl, and naphthyl. Examples of heterocyclic groups include groups obtained by removing a hydrogen atom from heterocyclic structures such as triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridyl ring, pyridine ring, piperidine ring, piperidine ring, morpholinium ring, dihydropiperanium ring, tetrahydropyranyl, and trihydropyranyl ring. Compounds having a thiourea structure can be compounds having two or more thiourea structures, but compounds having one thiourea structure are preferred.

Compounds with a thiourea structure, preferably those represented by formula (T-2), are preferred. [Chemical Formula 45] In equation (T-2), ^R4 to ^R7 represent hydrogen atoms or monovalent organic groups, and at least two of ^R4 to ^R7 can bond with each other to form a ring structure.

In formula (T-2), ^R4 and ^R5 have the same meaning as ^R4 and ^R5 in formula (T-1), and the preferred states are also the same. In formula (T-2), it is preferred that ^R6 and ^R7 are each independently monovalent organic groups. In formula (T-2), the preferred states of the monovalent organic groups in ^R6 and ^R7 are the same as the preferred states of the monovalent organic groups in ^R4 and ^R5 in formula (T-1).

Examples of compounds with a thiourea structure include N-acetylacetonate, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-dalcanyl thiourea, N-benzoyl thiourea, N,N'-diphenyl thiourea, 1-benzyl-phenyl thiourea, 1,3-dibutyl thiourea, 1,3-diisopropyl thiourea, 1,3-dicyclohexyl thiourea, 1-(3-(trimethoxysilyl)propyl)-3-methyl thiourea, trimethyl thiourea, tetramethyl thiourea, N,N-diphenyl thiourea, ethylene thiourea (2-imidazoline thione), carbimazole, and 1,3-dimethyl-2-thioethindrone.

[Content] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the curing resin composition of the present invention is preferably 0.05-10% by mass, more preferably 0.1-5% by mass, and even more preferably 0.2-3% by mass. The curing resin composition of the present invention may contain only one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure, or it may contain two or more compounds. When only one compound is contained, the content of that compound is within the above range, and when two or more compounds are contained, the total amount is preferably within the above range.

<Migration Inhibitor> The curing resin composition of the present invention preferably also contains a migration inhibitor. By including the migration inhibitor, the transfer of metal ions originating from the metal layer (metal wiring) into the photosensitive film can be effectively inhibited.

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

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

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

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

【Chemical Formula 46】

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

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

<Polymerization Inhibitor> It is preferable that the curing resin composition of the present invention contains a polymerization inhibitor.

As polymerization inhibitors, preferred examples include hydroquinone, teremethoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallnutol, p-tert-butylhydroquinone (tert-butylhydroquinone), 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Phenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenanthrene, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylene ethyl 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-nitrosophenylhydroxylamine monocyanate, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-tert-butylhydroxytoluene, 1,4-naphthoquinone, 1,3,5-tris(4-tert-butyl-3-hydroxyl)- 2,6-Dimethylbenzyl)-1,3,5-tris(2,4,6)-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, phenthiazolinone, 1,1-diphenyl-2-pyrrolidine, dibutyldithiocopper(II), nitrobenzene, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitroso-N-phenylhydroxyamine ammonium salt, etc. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

Furthermore, the following compounds can be used.

【Chemical Formula 47】

In the case where the curing resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the curing resin composition of the present invention is preferably 0.01 to 20.0% by mass, preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass.

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

<Metal Adhesion Modifier> The curable 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, aluminum-based adhesives, titanium-based adhesives, compounds with sulfonylurea structures and compounds with thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, as described in paragraphs 0050 to 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 formula, Et represents ethyl.

【Chemical Formula 48】 Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-piperylpropylmethyldimethoxysilane, 3-piperylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination with two or more.

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

Furthermore, as a metal adhesion modifier, 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.

The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting it above the lower limit above, the adhesion between the pattern and the metal layer becomes good; by setting it below the upper limit above, the heat resistance and mechanical properties of the pattern become good. There may be only one type of metal adhesion modifier, or there may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

<Metal Adhesion Modifier> The curable resin composition of the present invention preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring. As a metal adhesion modifier, 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 may also be used.

The content of the metal adhesion modifier relative to 100 parts by weight of the polymer precursor containing heterocyclic compounds is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting it above the lower limit above, the adhesion between the pattern and the metal layer after the heating step becomes good; by setting it below the upper limit above, the heat resistance and mechanical properties of the hardened product after the heating step become good. There may be only one type of metal adhesion modifier, or there may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

<Other Additives> The curable resin composition of this invention can be combined with various additives as needed, within the range that achieves the effects of this invention, such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-agglomerates, etc. When incorporating these additives, it is preferable that their total amount is 3% by mass or less of the solid content of the curable resin composition.

[Sensitizer] The curable resin composition of this invention may contain a sensitizer. The sensitizer absorbs specific active radiation to become electronically excited. The electronically excited sensitizer comes into contact with thermosetting accelerators, thermal free radical polymerization initiators, and photofree radical polymerization initiators, thereby generating electron transfer, energy transfer, and heating. Consequently, the thermosetting accelerators, thermal free radical polymerization initiators, and photofree radical polymerization initiators undergo chemical changes and decompose, generating free radicals, acids, or alkalis. 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, and p-dimethylaminophenylenepropyl dihydroindene. p-Dimethylaminobenzyldihydroindone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated 7-dimethyl Aminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-monolinylbenzophenone, isoamyl dimethylaminobenzoate, isoethylaminobenzoate Amyl ester, 2-piperamide, 1-phenyl-5-piperamide, 2-piperamide, 2-benzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetylamine, benzoaniline, N-methylacetylaniline, 3',4'-dimethylacetylaniline, etc. Sensitizing dyes can also be used as sensitizers. For detailed information on sensitizing dyes, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, and this information is incorporated herein by reference.

When the curing resin composition of the present invention contains a sensitizer, the content of the sensitizer relative to the total solid content of the curing resin composition of the present invention is preferably 0.01-20% by mass, more preferably 0.1-15% by mass, and even more preferably 0.5-10% by mass. The sensitizer can be used alone or two or more at the same time.

[Chain Transfer Agent] The curable 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. As chain transfer agents, for example, compounds containing SH, PH, SiH, and GeH within the molecule are used. These compounds can generate free radicals by donating hydrogen to low-activity free radicals or by deprotonation after oxidation. In particular, thiols are preferred.

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

When the curable 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 curable resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 1 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 amount is within the above-mentioned range.

[Surfactant] From the viewpoint of further improving coatability, a surfactant can be added to the curable resin composition of the present invention. Various surfactants, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants, can be used as surfactants. Furthermore, the following surfactants are also preferred. In the following formulas, the parentheses representing the repeating units of the main chain indicate the content (mol%) of each repeating unit, and the parentheses representing the repeating units of the side chains indicate the number of repetitions of each repeating unit. [Chemical Formula 49] Furthermore, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used as surfactants. Fluorinated surfactants can also be fluoropolymers with vinyl unsaturated groups on the side chains. As specific examples, compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION, can be cited.

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

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP341, 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, dehydrated sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), and Solsperse 20000 (Lubrizol Japan). Limited.), 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.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Co., Ltd.) etc.

As cationic surfactants, examples include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co.,LTD.), and W001 (manufactured by Yusho Co.,Ltd.).

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

When the curable resin composition of the present invention contains a surfactant, the content of the surfactant relative to the total solid content of the curable resin composition of the present invention is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be a single type or two or more types. When there are two or more surfactants, their total content is preferably within the above range.

[Higher Fatty Acid Derivatives] In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoic acid amide can be added to the curing resin composition of the present invention, so that they exist unevenly on the surface of the curing resin composition during the drying process after coating.

Furthermore, higher fatty acid derivatives may also use the compounds described in paragraph 0155 of International Publication No. 2015/199219.

When the curable resin composition of the present invention contains higher fatty acid derivatives, the content of higher fatty acid derivatives relative to the total solid content of the curable 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-mentioned range.

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

The average particle size of the aforementioned inorganic particles is preferably 0.01–2.0 μm, more preferably 0.02–1.5 μm, even more preferably 0.03–1.0 μm, and particularly preferably 0.04–0.5 μm. By using inorganic particles containing the above-mentioned average particle size, both the mechanical properties of the hardened film and the suppression of light scattering during exposure can be achieved.

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

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

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

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

As usable organic titanium compounds, those in which the organic group is bonded to titanium atoms via covalent or ionic bonds can be cited. Specific examples of organic titanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are preferred, as they exhibit excellent preservation stability of negative photosensitive resin compositions and can produce good curing patterns. Specific examples include diisopropanol bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropanol bis(2,4-pentanedione) titanium, diisopropanol bis(tetramethylheptanedione) titanium, and diisopropanol bis(ethyl acetoacetate) titanium. II) Tetraalkoxytitanium compounds: Examples include tetra(n-butanol)titanium, tetraethanoltitanium, tetra(2-ethylhexanol)titanium, tetraisobutanoltitanium, tetraisopropanoltitanium, tetraethanoltitanium, tetramethoxypropanoltitanium, tetramethylphenyloxytitanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyltitanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc. III) Titanium diacene compounds: Examples include pentamethylcyclopentadienyltrimethylamine titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium. IV) Monoalkoxy titanium compounds: Examples include tris(dioctyl phosphate)isopropanol titanium and tris(dodecanephenyl sulfonate)isopropanol titanium. V) Titanium oxide compounds: Examples include titanium bis(pentanedione), titanium bis(tetramethylheptanedione), and titanium phthalocyanine oxide. VI) Tetraacetone titanium compounds: Examples include tetraacetone titanium. VII) Titanium ester coupling agents: such as isopropyltridodecylbenzenesulfonate, 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) tetraalkoxy titanium compounds and III) dicene 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 an organotitanium compound is incorporated, the amount incorporated is preferably 0.05 to 10 parts by weight relative to 100 parts by weight of the cyclized resin precursor, and more preferably 0.1 to 2 parts by weight. When the amount incorporated is 0.05 parts by weight or more, the resulting curing pattern exhibits good heat resistance and chemical resistance; on the other hand, when the amount incorporated is 10 parts by weight or less, the composition exhibits excellent storage stability.

[Antioxidant] The composition of this invention may include an antioxidant. By including an antioxidant as an additive, the elongation properties and adhesion to metal materials of the cured film can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds can be mentioned. Compounds having a substituent at the site (orthoside) adjacent to the phenolic hydroxyl group are preferred. As the aforementioned substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both phenolic and phosphite groups within the same molecule are also preferred as antioxidants. Furthermore, phosphorus-based antioxidants can be used more effectively as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxanephosphine-heptacyclohepta-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxanephosphine-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 be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967. 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. These compounds exert their antioxidant activity by heating at 100–250°C or heating at 80–200°C in the presence of an acid/base catalyst to remove the protective group. Examples of potential antioxidants include compounds described in International Publication Nos. 2014/021023, 2017/030005, and Japanese Patent Application Publication No. 2017-008219. Commercially available potential antioxidants include ADEKA ARKLSGPA-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 general formula (3).

【Chemical Formula 50】

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

The compound represented by general formula (3) inhibits the oxidative degradation of aliphatic and phenolic hydroxyl groups in resins. Furthermore, it can inhibit metal oxidation by preventing rust on 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 the following general formula (3) are given, but are not limited to the following structures.

【Chemical Formula 51】

【Chemical Formula 52】

【Chemical Formula 53】

【Chemical Formula 54】

The optimal amount of antioxidant added relative to the resin is 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight. When the amount added is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the elongation properties of the film after reliability testing and the adhesion to metal materials. Furthermore, when the amount added is more than 10 parts by weight, there is a concern that the sensitivity of the resin composition may decrease due to interaction with the photosensitizer. Only one antioxidant may be used, or two or more antioxidants may be used. When using two or more antioxidants, the total amount within the above-mentioned range is preferred.

<Regarding other limitations on contained substances> From the viewpoint of coating properties, it is preferable that the moisture content of the curing resin composition of the present invention is less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass. Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the container.

From an insulation perspective, it is preferable that the metal content of the curing 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, chromium, and nickel. When multiple metals are included, it is preferable that the total amount of these metals is within the above-mentioned range.

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

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

As a container for the curing resin composition of the present invention, previously known containers can be used. Furthermore, as a container, in order to suppress the contamination of impurities into the raw materials or the curing resin composition, 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.

<Uses of the Curing Resin Composition> The curing resin composition of this invention is preferably used for forming interlayer insulating films for redistribution layers. Furthermore, it can also be used to form insulating films for semiconductor devices or stress-absorbing films, etc.

<Preparation of Curing Resin Compositions> The curing resin composition of the present invention can be prepared by mixing the above-mentioned components. There are no particular limitations on the mixing method, and it can be carried out by previously known methods.

Furthermore, filtration using a filter is preferable to remove foreign matter such as dust or particles from the hardened resin composition. A filter pore size of 1 μm or less is preferred, 0.5 μm or less is even better, and 0.1 μm or less is still preferable. From a productivity perspective, 5 μm or less is preferred, 3 μm or less is even better, and 1 μm or less is still even better. Filter materials such as polytetrafluoroethylene, polyethylene, or nylon are preferred. Filters 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. Furthermore, various materials can be filtered multiple times. Multiple filtrations constitute circulating filtration. Alternatively, filtration can be performed after pressurization. When filtration is performed after pressurization, a pressure of 0.05 MPa or higher and 0.3 MPa or lower is preferred. From a productivity perspective, a pressure of 0.01 MPa or higher and 1.0 MPa or lower is preferred, 0.03 MPa or higher and 0.9 MPa or lower is more preferred, and 0.05 MPa or higher and 0.7 MPa or lower is even more preferred. 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.

(Curing film, laminate, semiconductor device and manufacturing method thereof) Next, the curing film, laminate, semiconductor device and manufacturing method thereof will be described.

The cured film of this invention is a cured film formed by curing the resin composition of this invention. A patterned cured film is preferred. The thickness of the cured film of this invention can be, for example, 0.5 μm or more, or 1 μm or more. Furthermore, as an upper limit, it can be 100 μm or less, or 30 μm or less.

The curing film of the present invention can be laminated in two or more layers, or further in three to seven layers, to form a laminate. The laminate of the present invention comprises two or more curing films, and it is preferable that any of the aforementioned curing films contain a metal layer between them. For example, a laminate comprising at least three layers sequentially laminated: a first curing film, a metal layer, and a second curing film is preferred. Both the first curing film and the second curing film are curing films of the present invention; for example, it is preferable that both the first curing film and the second curing film are films formed by curing the resin composition of the present invention. The resin composition of the present invention used to form the first hardened film and the resin composition of the present invention used to form the second hardened film can be composed of the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

Examples of curing films applicable to this invention include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress-relief films. Other examples include sealing films, substrate materials (base films or cover films for 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 Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimide”, April 2008; Masaaki Kakimoto, supervised; CMC Technical Library, “Basic and Development of Polyimide Materials”, November 2011; Japan Polyimide/Aromatic Polymer Research Association, ed., “Latest Polyimide Basics and Applications”, NTS, August 2010, etc.

Furthermore, the hardening film of this invention can also be used in the manufacture of offset printing plates or screen printing plates, in the application of etching and forming components, and in the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

The method for manufacturing the curing film of the present invention (hereinafter also referred to as "the method of manufacturing the present invention") preferably includes a film formation step of applying the resin composition of the present invention onto a substrate to form a film (resin film). The method of manufacturing the curing film of the present invention preferably includes the above-described film formation step and a heating step of heating the film at a temperature of 80–450°C. The method of manufacturing the curing film of the present invention preferably includes the above-described film formation step, an exposure step of exposing the film, and a developing step of developing the film. By means of the above-described exposure and developing steps, a pattern of the curing film can be obtained. Furthermore, the method for manufacturing the curing film of the present invention includes the above-described film formation step and, as needed, the above-described developing step, and preferably includes a heating step of heating the film at 80–450°C. Specifically, steps (a) to (d) below are also preferred. (a) A film-forming step of applying a resin composition to a substrate to form a film (resin composition layer). (b) An exposure step of exposing the film after the film-forming step. (c) A developing step of developing the exposed film. (d) A heating step of heating the developed film at 80–450°C. By heating in the above-described heating step, the resin layer that has been cured by exposure can be further cured. In this heating step, for example, the aforementioned thermal alkali generator decomposes, thereby obtaining sufficient curability.

The preferred embodiment of the present invention includes a method for manufacturing a hardened film. Regarding the method for manufacturing a laminate according to the present invention, after forming a hardened film according to the above-described method, steps (a), (a) to (c), or (a) to (d) are performed again. In particular, it is preferable to perform each of the above steps sequentially multiple times, for example, 2 to 5 times (i.e., a total of 3 to 6 times). By thus building a hardened film, a laminate can be formed. In the present invention, it is particularly preferable to provide a metal layer on the portion where the hardened film is disposed, between the hardened films, or at these two locations. Furthermore, in the fabrication of the laminate, it is not necessary to repeat all the steps (a) to (d). The laminate of the hardened film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) multiple times, as described above.

<Film Formation Step (Layer Formation Step)> The preferred embodiment of the present invention includes a film formation step (layer formation step) of adapting a resin composition to a substrate to form a film (layer).

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; paper; SOG (Spin-On Glass); TFT (Thin Film Transistor) array substrates; and electrode plates for plasma display panels (PDPs). Furthermore, a bonding layer or oxide layer can be disposed on the surface of these substrates. In this invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and mold substrates being even more preferred. Furthermore, a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS) or similar materials may be provided on the surface of such substrates. Also, a plate-shaped substrate (substrate) may be used as the substrate. The shape of the substrate is not particularly limited; it can be circular or rectangular, but a rectangular shape is preferred. As for 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, when a resin composition layer is formed on the surface of a resin layer or a metal layer, the resin layer or the metal layer becomes the substrate.

As a method of applying resin composition 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, narrow-slit coating, and inkjet coating. From the perspective of uniform resin composition thickness, spin coating, narrow-slit coating, spray coating, and inkjet coating are preferred. By adjusting the appropriate solid content or coating conditions according to the method, a resin layer 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, or inkjet coating are preferred. For rectangular substrates, slit coating, spray coating, or inkjet coating are preferred. In the case of spin coating, a speed of 500–2,000 rpm is suitable for approximately 10 seconds to 1 minute. Also, depending on the viscosity of the resin composition and the desired film thickness, a speed of 300–3,500 rpm is preferred for 10–180 seconds. Furthermore, to obtain uniform film thickness, multiple speeds can be combined for coating. Furthermore, the method of transferring a coating pre-applied to a dummy support using the aforementioned application method onto a substrate is also applicable. Regarding the transfer method, the present invention preferably utilizes the manufacturing methods described in Japanese Patent Application Publication No. 2006-023696, paragraphs 0023, 0036-0051, or Japanese Patent Application Publication No. 2006-047592, paragraphs 0096-0108. Furthermore, a step of removing excess film from the ends of the substrate can be performed. Examples of such a step include edge bead rinsing (EBR), air knife, 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 to the substrate.

<Drying Step> The manufacturing method of this invention may include a drying step after the film formation step (layer formation step) to remove the solvent. A preferred drying temperature is 50–150°C, more preferably 70–130°C, and further preferably 90–110°C. As for the drying time, examples include 30 seconds to 20 minutes, 1 minute to 10 minutes are preferred, and 3 minutes to 7 minutes are even more preferred.

<Exposure Steps> The manufacturing method of this invention may include an exposure step of exposing the above-mentioned film (resin composition layer). Regarding the exposure amount, there are no particular limitations as long as it is sufficient to harden the resin composition. For example, an exposure energy of 100–10,000 mJ/ ^cm² at a wavelength of 365 nm is preferred, and 200–8,000 mJ/ ^cm² is even more preferred.

The exposure wavelength should be appropriately set within the range of 190–1,000 nm, with 240–550 nm being preferable. Furthermore, it is preferable that the exposure light includes light with a wavelength of 365 nm or 405 nm, with light including a wavelength of 405 nm being even better.

Regarding the exposure wavelength, if we explain it in relation to the light source, we can cite (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (the 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) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. Regarding the resin composition of this invention, exposure to high-pressure mercury lamps is particularly preferred, especially exposure to i-rays. This allows for particularly high exposure sensitivity. Furthermore, from a processing and productivity perspective, a broadband (g, h, i-ray wavelengths) high-pressure mercury lamp light source or a 405nm semiconductor laser is also preferred.

Furthermore, the exposure method is not particularly limited, as long as it involves exposing at least a portion of the film (photosensitive film) containing the curing resin composition. However, examples include exposure using a photomask and exposure based on direct laser imaging. In this invention, the exposure step using direct laser imaging is one of the preferred methods.

<Developing Step> The manufacturing method of this invention may include a developing step of developing an exposed film (resin composition layer). Development removes unexposed portions (non-exposed areas). The developing method is not particularly limited as long as the desired pattern can be formed; examples include dispensing developer from a nozzle, spraying with a sprayer, and immersing the substrate in developer, with dispensing from a nozzle being preferred. The developing step may employ steps such as continuously supplying developer to the substrate, keeping the developer substantially still on the substrate, vibrating the developer using ultrasound, or a combination of these steps.

Development is performed using a developer. A developer can be used without particular restrictions as long as it can remove the unexposed areas (non-exposed portions). Developers containing organic solvents or alkaline solutions can be used.

In this invention, it is preferable that the developing solution contains an organic solvent with a ClogP value of -1 to 5, and even more preferable that it contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated by inputting the structural formula into ChemBioDraw.

When the developing solution contains an organic solvent, the organic solvent, preferably an ester, includes 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, and alkyl alkoxyacetic acids (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate)). Alkyl esters (such as esters, ethyl ethoxylates, etc.), alkyl esters of 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc., such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl esters of 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc., such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.). Ethyl propionate), 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, 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 dimethyl ether, etc. Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and as ionides, dimethyl ionide, etc., are preferably given, and mixtures of these organic solvents are also preferably given.

In the case where the developing solution contains an organic solvent, cyclopentanone and γ-butyrolactone are particularly preferred in this invention, with cyclopentanone being even more preferred. Furthermore, when the developing solution contains an organic solvent, one or more organic solvents can be used, or a mixture of two or more organic solvents can be used.

When the developing solution contains an organic solvent, it is preferable that 50% or more by mass of the developing 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 developing solution may also be an organic solvent.

The developing solution may also contain other ingredients. Other ingredients include, for example, well-known surfactants and well-known defoamers.

When the developing solution is an alkaline aqueous solution, examples of alkaline compounds that can be contained in the alkaline aqueous solution include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), and sodium carbonate, with TMAH being preferred. For example, when using TMAH, the content of alkaline compounds in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

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

The optimal development time is 5 seconds to 10 minutes, with 10 seconds to 5 minutes being even better. There is no particular limitation on the temperature of the developing solution during development; it can usually be carried out at 10 to 45°C, with 20 to 40°C being the preferred temperature.

Rinsing can also be performed after treatment with the developer. Alternatively, a rinsing solution can be supplied before the developer in contact with the pattern is completely dry. Rinsing is preferably performed in a solvent different from the developer. For example, a solvent contained in the resin composition can be used for rinsing. When the developer contains an organic solvent, examples of rinsing solutions include PGMEA (propylene glycol monoethyl ether acetate) and IPA (isopropanol), with PGMEA being preferred. Furthermore, water is preferred as a rinsing solution for developing with a developer containing an alkaline aqueous solution. The rinsing time is preferably 10 seconds to 10 minutes, even better is 20 seconds to 5 minutes, and even better is 5 seconds to 1 minute. There is no particular limitation on the temperature of the rinsing solution, but it is preferably carried out at 10 to 45°C, and even more preferably at 18°C to 30°C.

When the rinsing solution contains organic solvents, the organic solvents, preferably esters, include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3-alkyl...). Methyl hydroxypropionate, 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 propionate, 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. And, as ketones, such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, such as toluene, xylene, anisole, limonene, etc., as iones, such as dimethyl iones, as alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., and as amides, such as N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

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

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

Rinsing solutions may also contain other ingredients. Other ingredients include, for example, well-known surfactants and well-known defoamers.

[Rinsing Solution Supply Method] Regarding the rinsing solution supply method, there are no particular limitations as long as the desired pattern can be formed. Methods include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate via a liquid tray, supplying the rinsing solution to the substrate 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 that the rinsing step involves supplying or continuously supplying the rinsing solution to the exposed film using a straight nozzle, and even better that it is supplied using a spray nozzle. Furthermore, as a method for supplying the rinsing solution in the rinsing step, methods such as continuously supplying the rinsing solution to the substrate, keeping the rinsing solution substantially still on the substrate, vibrating the rinsing solution on the substrate using ultrasound or the like, and combinations thereof can be used.

<Heating Step> The manufacturing method of this invention preferably includes a step of heating the developed film at 80–450°C (heating step). It is preferable to include a heating step after the film formation step (layer formation step), drying step, and developing step. In the heating step, for example, a cyclization reaction, serving as a precursor to a specific resin, is carried out by generating alkali through the decomposition of the aforementioned thermal alkali generator. Furthermore, the resin composition of this invention may contain free radical polymerizable compounds other than those serving as precursors to a specific resin, but curing of free radical polymerizable compounds other than those serving as unreacted precursors to a specific resin can also be performed in this step. As the heating temperature (maximum heating temperature) in the middle layer of the heating process, 50℃ or above is preferred, 80℃ or above is better, 140℃ or above is even better, 150℃ or above is even better, 160℃ or above is still better, and 170℃ or above is still better. As the upper limit, below 500℃ is preferred, below 450℃ is better, below 350℃ is even better, below 250℃ is even better, and below 220℃ is still even better.

Regarding heating, a heating 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 further preferred. Setting the heating rate to 1 °C/min or higher ensures productivity and prevents excessive amine volatilization, while setting the heating rate to 12 °C/min or lower helps to mitigate residual stress in the hardened film. Furthermore, in the case of an oven capable of rapid heating, a heating rate of 1–8 °C/sec from the initial heating temperature to the maximum heating temperature is preferred, 2–7 °C/sec is even better, and 3–6 °C/sec is further preferred.

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 to a substrate and allowing it to dry, it is the temperature of the dried film (layer), preferably starting from a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the resin composition and gradually increasing the temperature.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, even better is 20 to 300 minutes, and even better is 30 to 240 minutes.

In particular, when forming multilayered bodies, from the viewpoint of the interlayer adhesion of the hardened film, heating at a temperature of 180°C to 320°C is preferred, and heating at 180°C to 260°C is even better. Although the reason is not yet clear, it is believed that the reason lies in the cross-linking reaction between the acetylene groups of specific resins between the layers at this temperature.

Heating can be performed in stages. For example, a pretreatment step can be performed as follows: increasing the temperature from 25°C to 180°C at a rate of 3°C/min and holding at 180°C for 60 minutes, then increasing the temperature from 180°C to 200°C at a rate of 2°C/min and holding at 200°C for 120 minutes. A heating temperature of 100–200°C is preferred for this pretreatment step, 110–190°C is more preferred, and 120–185°C is even more preferred. In this pretreatment step, as described in U.S. Patent No. 9159547, it is also preferable to perform the treatment while being irradiated with ultraviolet light. This pretreatment step can improve the properties of the membrane. Pretreatment can be carried out in a short time of about 10 seconds to 2 hours, with 15 seconds to 30 minutes being better. Pretreatment can be a two-stage or more process. For example, pretreatment step 1 can be carried out in the range of 100 to 150°C, followed by pretreatment step 2 in the range of 150 to 200°C.

Furthermore, cooling can be performed after heating, and a cooling rate of 1-5°C/minute is preferable at this time.

In terms of preventing 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 during the heating step. An oxygen concentration of 50 ppm (by volume) or less is preferred, and 20 ppm (by volume) or less is even better. The heating mechanism is not particularly limited, but examples include heating plates, infrared furnaces, electric ovens, and hot air ovens.

<Metal Layer Formation Step> The manufacturing method of this invention preferably includes a metal layer formation step of forming a metal layer on the surface of a film (resin composition layer) after development.

As a metal layer, there are no particular limitations, and existing metal types can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten. Copper, aluminum and alloys containing these metals 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 Nos. 2007-157879, 2001-521288, 2004-214501, and 2004-101850 can be used. For example, photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electrolytic plating can be cited.

Regarding the thickness of the metal layer, 0.01–100 μm is preferred for the thickest part of the wall, 0.1–50 μm is even better, and 1–10 μm is even better.

<Lamination Step> The manufacturing method of this invention also includes a lamination step, which is preferred.

The lamination process includes a series of steps performed sequentially on the surface of the hardened film (resin layer) or metal layer: (a) film formation step (layer formation step), (b) exposure step, (c) development step, and (d) heating step. It is permissible to repeat only the (a) film formation step. Alternatively, it is permissible to perform the (d) heating step at the end or in the middle of the lamination process. That is, it is permissible to repeat steps (a) to (c) a predetermined number of times, followed by heating in (d), thereby curing the deposited resin composition layer. Furthermore, the metal layer formation step (e) can be included after the development step (c). In this case, the heating step (d) can be performed each time, or the heating step (d) can be performed collectively after a predetermined number of laminations. It is beyond doubt that the above-mentioned drying and heating steps can be appropriately included in the lamination steps.

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

Performing the above lamination steps 2 to 20 times is preferable, 2 to 5 times is even better, and 3 to 5 times is still preferable. Furthermore, the layers in the lamination steps can be layers with the same composition, shape, and film thickness, or they can be different layers.

For example, a structure with 3 or more but less than 7 resin layers is preferred, and 3 or more but less than 5 layers is even more preferred.

In this invention, it is particularly preferred that the hardened film (resin layer) of the resin composition is formed by further covering the metal layer after the metal layer is applied. Specifically, examples include repeating (a) the film formation step, (b) the exposure step, (c) the development step, (e) the metal layer formation step, and (d) the heating step in sequence, or repeating (a) the film formation step, (b) the exposure step, (c) the development step, and (e) the metal layer formation step in sequence, with the heating step (d) being applied last or in the middle. By alternating the lamination steps of resin composition layers (resin layers) and the metal layer formation steps, it is possible to alternately laminate resin composition layers (resin layers) and metal layers.

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

This invention also discloses semiconductor devices incorporating the hardened film or 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 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description in Figure 1, and such contents are incorporated herein by reference.

(Thermosetting Resin) The thermosetting resin of the present invention comprises at least one repeating unit selected from the group consisting of repeating units represented by formula (4) and repeating units represented by formula (5) below, and at least one repeating unit selected from the group consisting of repeating units represented by any one of formulas (2-1) to (2-3) above. The thermosetting resin of the present invention comprises an isoimidin structure and a polymerizable group. Therefore, it is considered to be easy to cure even when curing at low temperatures. [Chemical Formula 55] In formula (4), ^A1 and ^A2 independently represent oxygen atoms or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and ^R114 independently represent hydrogen atoms or monovalent organic groups, and at least one of ^R113 and ^R114 contains the group represented by formula (III) above; In formula (5), ^R117 represents a trivalent organic group, ^R111 represents a divalent organic group containing a polymerizable group, ^A2 represents an oxygen atom or -NH-, and ^R113 represents a hydrogen atom or a monovalent organic group;

The repeating unit represented by formula (4), except that at least one of R ¹¹³ and R ¹¹⁴ contains the group represented by formula (III) above, has the same meaning as the repeating unit represented by formula (2), and the preferred state is also the same. The repeating unit represented by formula (5), except that R ¹¹¹ contains a polymerizable group, has the same meaning as the repeating unit represented by formula (3), and the preferred state is also the same. Furthermore, the preferred state of the thermosetting resin of the present invention is the same as the preferred state of the thermosetting resin contained in the thermosetting resin composition of the present invention described above. [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.

(Synthetic Example 1: Synthesis of Polymer P-1) 15.00 g (51.0 mmol) of 4,4'-biphenyltetracarboxylic dianhydride (dried at 140°C for 12 hours) was dissolved in 150 mL of N-methylpyrrolidone. Then, 10.11 g (51.0 mmol) of 4,4'-diaminodiphenyl ether was added while ice-cold, and the mixture was stirred for 30 minutes while ice-cold, followed by further stirring at 50°C for 3 hours. Next, 1.21 g (10.2 mmol) of phenyl isocyanate was added as an end-sealing component, and the mixture was stirred at 50°C for 3 hours. Next, 21.50 g (112.2 mmol) of EDC·HCl (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride) was added at 50°C and stirred for 4 hours while maintaining the temperature at 50°C. Then, 13.27 g (102.0 mmol) of hydroxyethyl methacrylate was added to the reaction solution and stirred for another 4 hours. The resulting polymer solution was added dropwise to a 4-liter mixture of water/methanol (3/1 volume ratio) and reprecipitated. The polymer was then collected by filtration and dried at 45°C for 3 days. The polyimide precursor (A-1) has a weight-average molecular weight of 12,500, and the isoimidide content, determined by ¹³ C-NMR, is 0.004 mmol/g. Specifically, 0.1 g of the polymer was dissolved in 0.9 g of heavy DMSO (dimethyl sulfoxide) using ¹³ C-NMR (reverse gate decoupling method), and the content was determined based on the ratio of nitrogen atoms to carbon atoms in the isoimidide structure.

(Synthesis Examples 2-8: Synthesis of Polymers P-2-P-8) Polymers P-2-P-8 were synthesized using the same method as polymer P-1, except that the raw materials used and the reaction time before the addition of the end-sealing component were appropriately modified. The end-sealing component was phenyl isocyanate, the same as that used in polymer P-1. The structure of the polymer core, weight-average molecular weight (Mw), and content (mmol/g) of isoimidin structures in polymers P-2-P-8 are described in the tables below.

(Synthesis Example 9: Synthesis of Polymer P-9) 15.00 g (48.4 mmol) of 4,4'-oxophthalic anhydride, 12.58 g (96.7 mmol) of hydroxyethyl methacrylate, and 14.91 g (212.8 mmol) of pyridine were suspended in 100 mL of N-methylpyrrolidone and dried using a molecular sieve. The suspension was then heated at 60 °C for 3 hours. The reaction mixture was cooled to room temperature, and then 90 mL of N-methylpyrrolidone was added. The reaction mixture was then cooled to -10 °C, and while maintaining the temperature at -10 ± 4 °C, 11.50 g (96.7 mmol) of _SOCl₂ was added over 30 minutes. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours, and 15.00 g (48.4 mmol) of 0.45 g (1.29 mmol) of 4,4'-oxophthalic anhydride was added. Next, a solution obtained by dissolving 10.16 g (50.8 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes while maintaining the temperature at -5 to 0 °C. Then, after reacting the mixture at 0 °C for 1 hour, 2.03 g (9.6 mmol) of acetic anhydride was added, and the mixture was stirred at 70 °C for 3 hours. Afterward, the mixture was cooled to room temperature, 70 g of ethanol was added, and the mixture was stirred overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, and the mixture was stirred again in 4 liters of water for 30 minutes and filtered again. The obtained polyimide precursor was then dried at 45°C for 3 days under reduced pressure. The polyimide precursor had a weight-average molecular weight of 14,100, and the isoimidide content, determined by the same method as in Synthesis Example 1, was 0.027 mmol/g.

(Synthesis Examples 10-12: Synthesis of Polymers P-10-P-12) Polymers P-10-P-12 were synthesized by means of the same method as that used in the synthesis of polymer P-9, except that the raw materials used were appropriately modified. The structure of the polymer core, the weight-average molecular weight (Mw), and the content (mmol/g) of the isoimidin structure of polymers P-10-P-12 are described in the tables below.

(Synthetic Example 13: Synthesis of Polymer P-13) 15.00 g (51.0 mmol) of 4,4'-biphenyltetracarboxylic dianhydride (dried at 140 °C for 12 hours), 14.60 g (112.2 mmol) of hydroxyethyl methacrylate, and 17.74 g (224.3 mmol) of pyridine were suspended in 100 mL of N-methylpyrrolidone and dried using a molecular sieve. The suspension was then heated at 60 °C for 3 hours. Next, the reaction mixture was cooled to -10 °C, and while maintaining the temperature at -10 ± 4 °C, 12.74 g (107.1 mmol) of _SOCl₂ was added over 30 minutes. Next, a solution obtained by dissolving 10.21 g (51.0 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 40 minutes while maintaining the temperature at -5 to 0 °C. Then, after reacting the reaction mixture at 0 °C for 1 hour, 70 g of ethanol was added, and the mixture was stirred overnight at room temperature. Next, the polyimide precursor was precipitated in 5 L of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, and the mixture was stirred again in 4 L of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45°C for 3 days under reduced pressure. The weight-average molecular weight of the polyimide precursor was 12,200, and no peaks from the isoimidide structure were detected by measuring the molecular weight using the same method as in Synthesis Example 1.

(Synthesis Examples 14 and 15: Synthesis of Polymers P-14 to P-15) Polymers P-14 to P-15 were synthesized using the same method as polymer P-1, except that the raw materials used and the reaction time before the addition of the end-sealing component were appropriately modified. The end-sealing component was phenyl isocyanate, the same as that used in polymer P-1. The structure of the polymer core, weight-average molecular weight (Mw), and content (mmol/g) of isoimidin structures in polymers P-14 to P-15 are described in the tables below.

(Synthesis Example 16: Synthesis of Polymer P-16) P-16 was obtained by changing the raw materials, but otherwise synthesizing it in the same way as polymer P-13.

[Table 1] polymer Polymer nucleus Synthesis method Mw Content of isoimidin structure (mmol/g) P-1 A-1 Path 2 12500 0.004 P-2 A-1 Path 2 13000 0.007 P-3 A-1 Path 2 12700 0.056 P-4 A-1 Path 2 12400 0.111 P-5 A-1 Path 2 12400 0.209 P-6 A-2 Path 2 13200 0.170 P-7 A-2 Path 2 13600 0.250 P-8 A-3 Path 2 13000 0.138 P-9 A-4 Path 1 14100 0.027 P-10 A-5 Path 1 14900 0.182 p-11 A-6 Path 1 14600 0.060 P-12 A-7 Path 1 14000 0.813 P-13 A-1 - 12200 No detection P-14 A-1 Path 2 12800 0.001 P-15 A-1 Path 2 12500 0.402 P-16 A-4 - 14000 No detection

In the table above, A-1 to A-7 in the "Polymer Core" column represent the structures represented by formulas (A-1) to (A-7) respectively. Furthermore, among the acetic acid structures contained in these structures, the amount recorded in the "Isoimimine Structure Content (mmol/g)" column of the table constitutes the isoimimine structure. The "Synthetic Method" column in the table indicates which of the above-mentioned routes 1 and 2 was used for synthesis. [Chemical Formula 56] 【Chemical Formula 57】

<Examples and Comparative Examples> In each embodiment, the components listed in the table below were mixed to obtain various curing resin compositions. Similarly, in each comparative example, the components listed in the table below were mixed to obtain comparative compositions. Specifically, the content of each component listed in the table is assumed to be the amount recorded in the "parts by mass" column of the table. Furthermore, in the table, "none" indicates that the corresponding component is not present.

[Table 2] Resin polymeric compounds Radiation-inducing polymerization initiator Alkali-producing agents Polymerization inhibitors Migration inhibitors Metal adhesion modifier solvent Kind mass Kind mass Kind mass Kind mass Kind mass Kind mass Kind mass Kind mass Kind mass Hardened resin composition 1 P-1 33.6 C-1 5.88 D-1 1.26 without F-1 0.084 G-1 0.126 H-1 0.63 I-1 45 I-2 15 Hardened resin component 2 P-2 33.6 C-1 5.88 D-1 1.26 without F-1 0.084 G-1 0.126 H-1 0.63 I-1 45 I-2 15 Hardened resin components 3 P-3 33.6 C-1 5.88 D-1 1.26 without F-1 0.084 G-1 0.126 H-1 0.63 I-1 45 I-2 15 Hardened resin components 4 P-4 33.6 C-1 5.88 D-1 1.26 without F-1 0.084 G-1 0.126 H-1 0.63 I-1 45 I-2 15 Hardened resin components 5 P-5 33.6 C-1 5.88 D-1 1.26 without F-1 0.084 G-1 0.126 H-1 0.63 I-1 45 I-2 15 Hardened resin components 6 P-6 33.6 C-2 5.88 D-2 1.26 without F-1 0.084 G-2 0.126 H-2 0.63 I-1 45 I-2 15 Hardened resin components 7 P-7 33.6 C-2 5.88 D-2 1.26 without F-1 0.084 G-2 0.126 H-2 0.63 I-1 45 I-2 15 Hardened resin components 8 P-8 33.6 C-3 5.88 D-2 1.26 E-1 2.26 F-1 0.084 G-1 0.126 H-1 0.63 I-1 45 I-2 15 Hardened resin components 9 P-9 33.6 C-1 5.88 D-2 1.26 without F-1 0.084 G-3 0.126 H-2 0.63 I-1 45 I-2 15 10 Hardened resin components P-10 33.6 C-1 5.88 D-1 1.26 E-2 2.26 F-2 0.084 G-2 0.126 without I-1 45 I-2 15 Hardened resin composition 11 p-11 33.6 C-1 5.88 D-1 1.26 without F-2 0.084 G-1 0.126 without I-1 45 I-2 15 Hardened resin composition 12 P-12 33.6 C-2 5.88 D-1 1.26 E-1 2.26 F-2 0.084 G-1 0.126 without I-1 45 I-2 15 Hardened resin composition 13 P-3 /P-9 22.4 / 11.2 C-3 5.88 D-2 1.26 without F-2 0.084 G-1 0.126 H-2 0.63 I-1 45 I-2 15 Hardened resin components 14 P-14 33.6 C-1 5.88 D-1 1.26 without F-1 0.084 G-1 0.126 H-1 0.63 I-1 45 I-2 15 Hardened resin composition 15 P-15 33.6 C-1 5.88 D-1 1.26 without F-1 0.084 G-1 0.126 H-1 0.63 I-1 45 I-2 15 Hardened resin composition 16 P-5 /P-9 16.8 / 16.8 C-1 5.88 D-3 1.26 without F-3 0.084 without H-1 /H-3 0.315 / 0.315 I-3 45 I-4 15 Comparison of component 1 P-13 /P-16 16.8 / 16.8 C-1 5.88 D-3 1.26 without F-3 0.084 without H-1 /H-3 0.315 / 0.315 I-3 45 I-4 15

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

[Resin] • P-1 to P-16: Polymers P-1 to P-16 obtained by the above synthesis example

[Polymerizable compounds] • C-1 to C-3: Compounds with the following structures (the numbers in parentheses indicate repetition.) [Chemical Formula 58]

[Radiosensitive polymerization initiators] • D-1 and D-3: Compounds with the following structure [Chemical Formula 59]

[Alkali-producing agents (thermal alkali-producing agents)] • E-1～E-2: Compounds with the following structures [Chemical Formula 60]

[Polymerization Inhibitors] • F-1 to F-3: Compounds with the following structures (Me represents methyl). [Chemical Formula 61]

[Migration Inhibitors] • G-1 to G-3: Compounds with the following structures. [Chemical Formula 62] [Metal adhesion modifier] • H-1 to H-3: Compounds with the following structure (Et represents ethyl.) [Chemical Formula 63] [Solubilizers] • I-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) • I-2: Dimethyl monoxide (manufactured by FUJIFILM Wako Pure Chemical Corporation) • I-3: N-methylpyrrolidone • I-4: Ethyl lactate

<Fabrication of the Cured Film> In each embodiment and comparative example, the curable resin composition or comparative composition listed in the table was pressurized and filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm. The filtered resin was then applied to a silicon wafer by spin coating, thereby forming a resin layer. The silicon wafer with the resin layer formed was dried on a heated plate at 100°C for 4 minutes, thereby forming a resin composition layer with a uniform thickness of 20 μm on the silicon wafer. A broadband exposure machine (manufactured by Ushio Inc.: UX-1000SN-EH01) was used to expose the resin composition layer on a silicon wafer at an exposure energy of 400 mJ/ ^cm² . The exposed resin composition layer was then heated in a nitrogen atmosphere at a heating rate of 5°C/min, reaching 180°C and remaining at that temperature for 2 hours. The heated resin composition layer and the silicon wafer were then immersed in a 3% (w/w) hydrofluoric acid solution, and the heated resin composition layer was peeled off from the silicon wafer. The peeled-off heated resin composition layer was designated as a hardening film.

<Evaluation of Elongation at Break> In each embodiment and comparative example, the elongation at break of the obtained hardened films was evaluated. The elongation at break of the obtained hardened films was measured. Regarding the elongation at break of the hardened films, a tensile testing machine (Tensilon) was used with a crosshead speed of 300 mm/min, a sample width of 10 mm, and a sample length of 50 mm. Measurements were taken in both the length and width directions of the film at 25°C and 65% RH (relative humidity) according to JIS K 6251:2017 (Japanese Industrial Standard). Regarding elongation at break, it was calculated using Eb(%) = (Lb-L0)/L0 (Eb: elongation at break, L0: length of the test piece before testing, Lb: length of the test piece when cut). For evaluation, the elongation at break was measured 10 times in each direction, and the average value was used (the arithmetic mean of 20 measurements, 10 in the length direction and 10 in the width direction). Evaluation was conducted according to the following criteria, and the results are recorded in the "Elongation at Break" column of the table below. Generally speaking, a higher elongation at break indicates better elongation at break of the hardened film, and also better mechanical strength. -Evaluation Criteria- A: Elongation at break is 60% or higher. B: Elongation at break is 50% or more but less than 60%. C: Elongation at break is 40% or more but less than 50%. D: Elongation at break is less than 40%.

<Evaluation of Storage Stability> In each embodiment or comparative example, 10g of the components listed in the table were pressurized and filtered using a polytetrafluoroethylene filter with a pore width of 0.8μm. The filtered products were then sealed in a container (material: light-proof glass, capacity: 100mL) and allowed to stand for one week at 25°C, in the dark, and at a relative humidity of 65%. For each component before and after the above-mentioned standing period, viscosity was measured at 25°C using a RE-85L (manufactured by TOKI SANGYO CO.,LTD), and the absolute value of the rate of viscosity change was calculated. The absolute value of the rate of viscosity change was calculated as the absolute value of (E1-E0)/E0×100. E1 represents the viscosity after standing, and E0 represents the viscosity before standing. The lower the rate of change, the higher the stability of the photosensitive resin composition, and the better the result. Evaluations were conducted according to the following criteria, and the results are recorded in the "Storage Stability" column of the table below. -Evaluation Criteria- A: Absolute value of viscosity change rate is 0% or more and less than 5% B: Absolute value of viscosity change rate is 5% or more and less than 8% C: Absolute value of viscosity change rate is 8% or more and less than 10% D: Absolute value of viscosity change rate is 10% or more

<Evaluation of Filtration Performance> In each embodiment or comparative example, the components listed in the table below were filtered for 60 minutes at a pressure of 0.15 MPa using a PTFE (polytetrafluoroethylene) filter (47 mm diameter, Merck Millipore Cat.FHLP04700). A grade of A was given for components with a mass of 15 g or more filtered by the above 60-minute filtration; a grade of B was given for components with a mass less than 15 g but more than 10 g; and a grade of C was given for components with a mass less than 10 g. The evaluation results are recorded in the "Filtration Performance" column of the table below.

[Table 3] Components Elongation at break Maintain stability Filtration Implementation Example 1 Hardened resin composition 1 C A A Implementation Example 2 Hardened resin component 2 B A A Implementation Example 3 Hardened resin components 3 A A A Implementation Example 4 Hardened resin components 4 A B A Implementation Example 5 Hardened resin components 5 A B A Implementation Example 6 Hardened resin components 6 A B B Implementation Example 7 Hardened resin components 7 A C A Implementation Example 8 Hardened resin components 8 A B A Implementation Example 9 Hardened resin components 9 A A A Implementation Example 10 10 Hardened resin components A B A Implementation Example 11 Hardened resin composition 11 A A A Implementation Example 12 Hardened resin composition 12 A A A Implementation Example 13 Hardened resin composition 13 A A A Implementation Example 14 Hardened resin components 14 C A A Implementation Example 15 Hardened resin composition 15 A D A Implementation Example 16 Hardened resin composition 16 A A A Comparative example 1 Comparative Example Composition 1 D C B

The results above show that the curable resin composition of this invention has excellent mechanical strength when cured at low temperature.

<Example 101> The curable 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 (manufactured by Nikon Co., Ltd., NSR1505 i6). Exposure was performed using a mask (a binary mask with a 1:1 line-space pattern and a linewidth of 10 μm) at a wavelength of 365 nm. After exposure, it was heated at 100°C for 4 minutes. After heating, it was developed with cyclohexanone for 2 minutes and washed with PGMEA for 30 seconds to obtain the layer pattern. Next, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C/min, reaching 180°C, and then maintained at 180°C for 2 hours, thereby forming an interlayer insulating film for the redistribution layer. This interlayer insulating film for the redistribution layer exhibits excellent insulation properties. Furthermore, semiconductor devices were fabricated using these interlayer insulating films for the redistribution layer, and normal operation was confirmed.

Claims (13)

A curable resin composition comprising a thermosetting resin having a polymerizable group and an isoimidine structure and a radiation-sensitive polymerization initiator, wherein the content of the isoimidine structure contained in the thermosetting resin is 0.001~0.3 mmol/g, wherein the thermosetting resin has a repeating unit represented by formula (2) or a repeating unit represented by formula (3); 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 (3), ^R117 represents a trivalent organic group, ^R111 represents a divalent organic group, ^A2 represents oxygen atoms or -NH-, and ^R113 represents hydrogen atoms or monovalent organic groups. The thermosetting resin composition as described in claim 1, wherein the aforementioned thermosetting resin is a polyimide precursor. The thermosetting resin composition as described in claim 1 or claim 2, wherein the aforementioned thermosetting resin comprises a polyamide structure or a polyamide ester structure. The curing resin composition as described in claim 1 or claim 2, wherein at least one of R ¹¹³ and R ¹¹⁴ in the aforementioned formula (2) contains a polymeric group. The curing resin composition as described in claim 1 or claim 2, wherein at least one of R ¹¹³ and R ¹¹⁴ in the aforementioned formula (2) comprises a free radical polymerizable group. The curable resin composition as described in claim 1 or claim 2 is used to form an interlayer insulating film for a redistribution layer. A hardened film formed by hardening any one of the hardening resin compositions described in claims 1 to 6. A laminate comprising two or more hardened films as described in claim 7, wherein a metal layer is included between at least one of the aforementioned hardened films. A method for manufacturing a hardened film, comprising a film formation step of adapting a hardened resin composition described in any one of claims 1 to 6 onto a substrate to form a film. The method for manufacturing the hardened film as described in claim 9 further includes a heating step of heating the aforementioned film at a temperature of 80-450°C. The method for manufacturing the hardened film as described in claim 9 further includes an exposure step of exposing the aforementioned film and a developing step of developing the aforementioned film. A semiconductor device comprising the hardened film described in claim 7. A thermosetting resin comprising at least one repeating unit selected from a group comprising repeating units represented by formula (4) and repeating units represented by formula (5) below, and at least one repeating unit selected from a group comprising repeating units represented by any one of formulas (2-1) to (2-3) below, and wherein the content of the isoimidin structure contained in the aforementioned thermosetting resin is 0.001 to 0.3 mmol/g; In formula (4), ^A1 and ^A2 independently represent oxygen atoms or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and ^R114 independently represent hydrogen atoms or monovalent organic groups, and at least one of ^R113 and ^R114 contains the group represented by formula (III) below; In formula (5), ^R117 represents a trivalent organic group, ^R111 represents a divalent organic group containing a polymerizable group, ^A2 represents an oxygen atom or -NH-, and ^R113 represents a hydrogen atom or monovalent organic group; In equations (2-1) to (2-3), ^A1 represents an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R114 represents a hydrogen atom or a monovalent organic group, ^{and R117} represents a trivalent organic group. In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, R ²⁰¹ represents an hydrocarbon or a group represented by a bond between an hydrocarbon and at least one structure selected from the group consisting of -O-, -CO-, -S-, _-SO2- or ^-NRN- , * represents a bond site with other structures, and ^RN represents a hydrogen atom or a hydrocarbon.