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

Abstract

This invention provides a resin composition that yields a hardened material with excellent adhesion to metals, a hardened material obtained by hardening the resin composition, a laminate containing the hardened material, a method for manufacturing the hardened material, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the laminate, and a semiconductor device containing the hardened material or the laminate. The resin composition comprises a resin and an alkali-generating agent, wherein the alkali-generating agent is a compound represented by formula (1-1); L1 represents an n+m valence linker, R1 independently represents a monovalent organic group, R2 independently represents a monovalent organic group or a hydrogen atom, R1 can be linked together to form a ring structure, m represents an integer of 1 or more, and n represents an integer of 1 or more.

Description

[Technical Field]

[0001] This invention relates to a resin composition, a cured material, a laminate, a method for manufacturing the cured material, a method for manufacturing the laminate, a method for manufacturing a semiconductor device, and a semiconductor device. [Previous Technology]

[0002] Nowadays, resin materials are used in various fields by employing resin compositions containing resins. For example, cyclic resins such as polyimide are used in various applications due to their excellent heat resistance and insulation properties. There are no particular limitations on these applications; for example, in the case of semiconductor devices used for actual mounting, they can be used as insulating films, sealing materials, or protective films. Furthermore, they can also be used as base films or cover films for flexible substrates.

[0003] For example, in the above-described applications, cyclic resins such as polyimide are used in the form of resin compositions containing precursors of cyclic resins such as polyimide precursors. For example, such resin compositions are applied to a substrate by coating to form a photosensitive film, and then exposed, developed, heated, etc., as needed, thereby forming a cured material on the substrate. The precursors of the aforementioned cyclic resins, such as polyimide precursors, are cyclized by heating, thus becoming cyclic resins such as polyimide in the cured material. The resin composition can be applied using known coating methods, etc.; therefore, it can be said that the design freedom in terms of the shape, size, and application location of the applied resin composition is high, and its manufacturing adaptability is excellent. Considering both the high performance of cyclic resins such as polyimide and their excellent manufacturing adaptability, the expansion of industrial applications of the aforementioned resin compositions is increasingly promising.

[0004] For example, Patent Document 1 discloses a photosensitive resin composition containing a polyimide precursor with a specific structure and a photoalkali generating agent. Patent Document 2 discloses a photosensitive resin composition containing a polyimide precursor with a specific structure different from that in Patent Document 1 and a photoalkali generating agent.

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2016-021068 [Patent Document 2] Japanese Patent Application Publication No. 2012-093746

[0006] In the resin composition used to obtain the cured product, it is required that the obtained cured product has excellent adhesion to the metal. [Summary of the Invention]

[0007] The object of the present invention is to provide a resin composition that can obtain a hardened material with excellent adhesion to metal, a hardened material obtained by hardening the resin composition, a laminate containing the hardened material, a method for manufacturing the hardened material, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the laminate, and a semiconductor device containing the hardened material or the laminate.

[0008] The following are examples of representative embodiments of the present invention. <1> A resin composition comprising: a resin; and an alkali generating agent, wherein the alkali generating agent is a compound represented by the following formula (1-1). [Chemical Formula 1] In formula (1-1), L1 represents an n+m valence linker, R1 independently represents a monovalent organic group, R2 independently represents a monovalent organic group or a hydrogen atom, R1 can be linked together to form a ring structure, m represents an integer of 1 or more, and n represents an integer of 1 or more. <2> The resin composition as described in <1>, wherein the L1 in formula (1-1) comprises at least one aromatic ring structure. <3> The resin composition as described in <1> or <2>, wherein the bonding sites of the L1 in formula (1-1) and the m+n carbonyl groups in formula (1-1) are all carbon atoms. <4> A resin composition as described in any one of <1> to <3>, wherein R1 in formula (1-1) is independently a hydrocarbon group that may have substituents, or R1 in formula (1-1) is bonded to each other to form a nitrogen-containing aliphatic heterocyclic structure that may have substituents. <5> A resin composition as described in any one of <1> to <4>, wherein R2 in formula (1-1) is independently a hydrogen atom or a hydrocarbon group that may have substituents. <6> A resin composition as described in any one of <1> to <5>, wherein the resin is at least one resin selected from the group consisting of cyclized resins and their precursors. <7> A resin composition as described in any one of <1> to <6>, wherein the resin contains at least one group selected from the group consisting of groups having vinyl unsaturated bonds, epoxides, cyclobutanes, aldehydes, and ketones. <8> A resin composition as described in any one of <1> to <7>, further comprising a photopolymerization initiator. <9> A resin composition as described in any one of <1> to <8>, further comprising a polymerizable compound. <10> A resin composition as described in any one of <1> to <9>, further comprising an organometallic complex. <11> A resin composition as described in any one of <1> to <10>, comprising a cyclized resin or a precursor thereof as the resin and used to form an interlayer insulating film for a rewiring layer. <12> A cured material formed by curing any one of the resin compositions described in <1> to <11>. <13> A laminate comprising two or more layers composed of the cured material described in <12>, with a metal layer between the layers composed of the cured material. <14> A method for manufacturing a cured material, comprising a film forming step of applying a resin composition described in any one of <1> to <11> to form a film on a substrate. <15> A method for manufacturing a cured material as described in <14>, comprising: an exposure step of selectively exposing the film; and a development step of developing the film using a developer to form a pattern.<16> A method for manufacturing a cured material as described in <14> or <15>, comprising a heating step of heating the film at 50 to 450°C. <17> A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in any one of <14> to <16>. <18> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in any one of <14> to <16> or the method for manufacturing a laminate as described in <17>. <19> A semiconductor device comprising the cured material as described in <12> or the laminate as described in <13>. [Effects of the Invention]

[0009] According to the present invention, a resin composition that can obtain a hardened material with excellent adhesion to metal is provided, a hardened material obtained by hardening the resin composition, a laminate containing the hardened material, a method for manufacturing the hardened material, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the laminate, and a semiconductor device containing the hardened material or the laminate.

Implementation Method

[0010] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments shown. In this specification, the numerical range indicated by the symbol “~” refers to the range including the values ​​before and after “~” as the lower limit and upper limit, respectively. In this specification, the term “step” means not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. In the marking of groups (atomic groups) in this specification, the markings without substituted and unsubstituted include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, “alkyl” includes not only alkyl groups without substituents (unsubstituted alkyl) but also alkyl groups with substituents (substituted alkyl). In this specification, unless otherwise specified, “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 the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" refers to either "acrylate" or "methacrylate," "(meth)acrylic acid" refers to either "acrylic acid" or "methacrylic acid," and "(meth)acrylyl" refers to either "acrylyl" or "methacrylyl." In this specification, Me in the structural formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, total solids content refers to the total mass of all components of the composition excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of components other than the solvent relative to the total mass of the composition. Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​determined by gel permeation chromatography (GPC) and are defined as polystyrene conversion values. For example, this specification uses an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series as a column to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn). Unless otherwise specified, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. When THF has low solubility or is unsuitable as the eluent, NMP (N-methyl-2-pyrrolidone) can be used instead.Furthermore, unless otherwise specified, the detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm. In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that other layers exist above or below the reference layer among the plurality of layers of interest. That is, a third layer or third element may be further sandwiched between the reference layer and the other layers, without the reference layer needing to be in contact with the other layers. Also, unless otherwise specified, the direction of the substrate stacked layers is referred to as "upper," or when a resin composition layer is present, the direction from the substrate towards the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, these vertical and horizontal directions are set for convenience in this specification; in actual practice, the "upper" direction in this specification may differ from the vertical direction. In this specification, unless otherwise specified, each component included in the composition may contain two or more compounds belonging to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds belonging to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, the combination of preferred samples is referred to as the more preferred sample.

[0011] (Resin Composition) The resin composition of the present invention comprises a resin and an alkali generating agent, wherein the alkali generating agent is a compound represented by the following formula (1-1). Hereinafter, the compound represented by the following formula (1-1), i.e., the alkali generating agent, will also be referred to as "specific alkali generating agent". [Chemical Formula 2] In formula (1-1), L1 represents an n+m valence linking group, R1 independently represents a monovalent organic group, R2 independently represents a monovalent organic group or a hydrogen atom, R1 can be linked together to form a ring structure, m represents an integer of 1 or more, and n represents an integer of 1 or more.

[0012] The resin composition of the present invention is preferably used to form photosensitive films for exposure and development, and is preferably used to form films for exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for rewiring layers. In particular, the resin composition of the present invention, which contains a cyclized resin or its precursor as a resin and is used to form an interlayer insulating film for rewiring layers, is also one of the preferred embodiments of the present invention. Furthermore, the resin composition of the present invention can be used to form photosensitive films for positive development and can also be used to form photosensitive films for negative development. In the present invention, in exposure and development, negative development refers to development that removes non-exposed portions by development, and positive development refers to development that removes exposed portions by development. As the above-described exposure method, the above-described developer, and the above-described development method, for example, the exposure method described in the exposure step of the description of the method for manufacturing a cured material described later, and the developer and development method described in the development step can be used.

[0013] According to the resin composition of the present invention, a hardened film with excellent adhesion to metal can be obtained. The mechanism by which the above-mentioned effect is not yet clear, but it is speculated to be as follows.

[0014] According to the specific alkali-generating agent in the resin composition of the present invention, it is believed that a compound containing the structure -C(=O)-NR 2-C(=O)- is generated simultaneously with the generation of the alkali. R2 has the same meaning as R2 in the above formula (1-1). For example, by heating or the like, a compound with the following structure and piperidine as a alkali are generated from the compound represented by A-1 below. [Chemical Formula 3] It is believed that since the above-mentioned compound is a near-neutral compound, when the layer formed by the resin composition comes into contact with the metal layer, the migration of metal ions from the metal layer to the layer formed by the resin composition is suppressed. As a result of the above-mentioned suppression of migration, it is believed that the cured product obtained from the resin composition of the present invention has excellent adhesion to the metal.

[0015] Furthermore, it is believed that since the compounds containing the above-mentioned structures generated simultaneously with the formation of alkali are highly polar, the solvent solubility of the cured product can be reduced, thereby improving the drug resistance. Moreover, it is believed that since the structure of a particular alkali-generating agent is close to neutral both before and after the formation of alkali, it is less likely to hinder the effects caused by the alkali compared to, for example, the use of an alkali-generating agent whose structure before the formation of alkali is close to acidic. For example, when a precursor of a cyclized resin is used as the resin, the cyclization promotion based on the effect of the alkali is less likely to be hindered, thus cyclization is easier to occur, and the elongation at break of the obtained cured product may sometimes be further increased. Furthermore, for example, when a precursor of a cyclized resin is used as the resin, cyclization is easier to occur as described above, and the cyclization rate of the resin in the obtained cured product becomes higher. Therefore, during curing, compounds generated accompanying resin cyclization (e.g., compounds derived from structures containing R 113 and R 114 in formula (2) described later) can be sufficiently volatilized from the cured product. Therefore, it is believed that gas release during the curing process can also be suppressed (e.g., gas release during prolonged use of the curing agent, gas release during use at high temperatures, etc.). Furthermore, especially when using resins with structures similar to the alkali-generating agents of this invention, such as cyclized resins or their precursors (e.g., both containing amide groups), the compatibility between the alkali-generating agent and the resin increases, resulting in the near-uniform generation of alkali in the resin film, which sometimes also improves the pattern shape of the obtained curing material. Furthermore, as described above, the increased compatibility between the alkali-generating agent and the resin also allows for increased freedom in composition design, such as the ability to increase the content of the alkali-generating agent. In the past, organometallic complexes such as organotitanium compounds were sometimes used to improve chemical resistance. Depending on their structure, these organometallic complexes sometimes decompose or deteriorate when used simultaneously with conventional alkali-generating agents with acidic structures, such as carboxylic acids or phenolic hydroxyl groups. However, since the specific alkali-generating agent in this invention has a near-neutral structure, it is considered unlikely that such decomposition or deterioration of organometallic complexes will occur. As a result, it was concluded that a hardened material with excellent lithography properties and excellent chemical resistance could be obtained.

[0016] Herein, patent documents 1 and 2 do not describe resin compositions containing specific alkali generating agents.

[0017] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0018] <Resin> The resin composition of the present invention comprises a resin. There is no particular limitation on the resin; for example, resins used in conventional pattern-forming compositions can be cited. It is preferable to include at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors, and more preferably, a precursor of a cyclized resin. Furthermore, it is preferable that the resin of the present invention includes at least one group selected from the group consisting of groups having ethylene unsaturated bonds, epoxides, cyclobutane, aldehydes, and ketones. In particular, when the specific resin is considered a precursor of a cyclized resin, an addition or insertion reaction occurs between the base generated from the specific base generator and these groups, thereby suppressing the reaction between the cyclized site in the specific resin and the base, and increasing the cyclization rate of the specific resin. Examples of groups having vinyl unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamide, (meth)acryloxy, etc. Groups having an aromatic ring directly bonded to vinyl, (meth)acrylamide or (meth)acryloxy are preferred, and (meth)acryloxy is even more preferred.

[0019] Hereinafter, it is preferred that the resin composition of the present invention satisfies at least one of conditions 1 and 2 below. Furthermore, satisfying both conditions 1 and 2 below is also one of the preferred embodiments of the present invention. Condition 1: The resin has a free radical polymerizable group. Condition 2: It further comprises a polymerizable compound having a free radical polymerizable group.

[0020] Cyclic resins are preferably resins whose main chain structure includes an imine ring structure or an oxazole ring structure. In this invention, the main chain refers to the longest bonded chain in the resin molecule. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamide-imide. The precursor of a cyclized resin refers to a resin whose chemical structure changes due to external stimuli to become a cyclized resin. Resins whose chemical structure changes due to heat to become cyclized resins are preferred, and resins that form a ring structure by utilizing heat to generate a ring-closing reaction to become cyclized resins are even more preferred. Examples of cyclized resin precursors include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors. That is, the resin composition of the present invention preferably includes at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide-imide, and polyamide-imide precursor as the specific resin. It is preferable that the resin composition of the present invention includes polyimide or a polyimide precursor as the specific resin. Furthermore, it is preferable that the specific resin has polymerizable groups, and it is even more preferable that it includes free radical polymerizable groups. When the specific resin has free radical polymerizable groups, it is preferable that the resin composition of the present invention includes the free radical polymerization initiator described later, and it is even more preferable that it includes both the free radical polymerization initiator described later and the free radical crosslinking agent described later. Sensitizers described later can be further included as needed. For example, a negative photosensitive film can be formed from such resin compositions of the present invention. Furthermore, the specific resin may have polar conversion groups such as acid-decomposing groups. When a particular resin has acid-degrading groups, it is preferable that the resin composition of the present invention includes the photoacid-generating agent described later. For example, such resin compositions of the present invention can be used to form chemically amplified positive or negative photosensitive films.

[0021] 〔Polyimine Precursor〕 The type of polyimine precursor used in this invention is not particularly limited, but it is preferable to include repeating units represented by the following formula (2). [Chemical Formula 4] 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.

[0022] 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 straight-chain or branched aliphatic groups, cyclic aliphatic groups, and groups containing aromatic groups. It is preferred to have straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. It is even more preferred to have groups containing aromatic groups with 6 to 20 carbon atoms. The hydrocarbon group in the chain of the above-mentioned straight-chain or branched aliphatic group can be replaced by a group containing heteroatoms, and the hydrocarbon group in the ring members of the above-mentioned cyclic aliphatic group and aromatic group can be replaced by a group containing heteroatoms. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, with groups represented by -Ar-L-Ar- being particularly preferred. In this group, Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. The preferred ranges are as described above.

[0023] R 111 is preferably derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include straight-chain or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, diamines containing a straight-chain or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 3 to 20 carbon atoms, or a combination thereof, are preferred; diamines containing an aromatic group with 6 to 20 carbon atoms are even more preferred. The hydrocarbon group in the chain of the aforementioned straight-chain or branched aliphatic group can be replaced by a group containing a heteroatom, and the hydrocarbon group in the ring members of the aforementioned cyclic aliphatic and aromatic groups can be replaced by a group containing a heteroatom. Examples of groups containing aromatic groups include the following groups.

[0024] [Chemical Formula 5] In the formula, A represents a single bond or a divalent linker. A single bond or a group selected from aliphatic hydrocarbons with 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO 2-, -NHCO-, or combinations thereof is preferred. A group selected from single bonds, alkyl groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO 2- is even more preferred. -CH 2-, -O-, -S-, -SO 2-, -C(CF 3) 2-, or -C(CH 3) 2- is further preferred. * In the formula, * indicates a bonding site with other structures.

[0025] Specifically, as a diamine, examples include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'- and 3,3'-diaminodiphenyl ether, 4,4'- or 3,3'- -Diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 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) guanidine, bis(4-amino-3-hydroxyphenyl) guanidine, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] guanidine, bis[4-(3-aminophenoxy)phenyl] guanidine, bis[4-(2-aminophenoxy)phenyl] guanidine, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl guanidine, 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 sulfonate, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-Dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminophen, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotriphenylamine Fluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-fluoropropane [-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)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl benzoyl, 4, At least one diamine selected from the following: 4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl benzoxane, 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.

[0026] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0027] Alternatively, the diamine having two or more alkyl diol units on the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may also be preferred.

[0028] 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 an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, or a group consisting of -O-, -CO-, -S-, -SO 2-, or -NHCO-, or a combination of two or more of the above. Ar is preferably phenyl, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted by a fluorine atom, or a group consisting of -O-, -CO-, -S-, or -SO 2-. Here, the aliphatic hydrocarbon group is preferably alkyl.

[0029] Furthermore, from the viewpoint of i-ray transmittance, it is preferable that R 111 is a divalent organogroup represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is even more preferable that the divalent organogroup represented by formula (61) is preferred. Formula (51) [Chemical Formula 6] In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organogroup, and at least one of R 50 to R 57 is a fluorine atom, a methyl atom or a trifluoromethyl atom, and * independently represents the bonding site with the nitrogen atom in formula (2). Examples of monovalent organogroups of R 50 to R 57 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 7] In formula (61), R 58 and R 59 are independently fluorine atoms, methyl groups, or trifluoromethyl groups, respectively, and * independently represent bonding sites with nitrogen atoms in formula (2). Examples of diamines that impart the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used.

[0030] R 115 in formula (2) represents a tetravalent organogroup. As a tetravalent organogroup, a tetravalent organogroup containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is even more preferred. In formula (5) or formula (6), * independently represents the bonding site with other structures. [Chemical Formula 8] In Formula (5), R 112 is a single bond or a divalent group. It is preferred that the single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S-, -SO 2- and -NHCO-, and combinations thereof. It is even more preferred that the single bond or a group selected from alkyl groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S- and -SO 2-, and a divalent group selected from the group including -CH 2-, -C(CF 3) 2-, -C(CH 3) 2-, -O-, -CO-, -S- and -SO 2- is further preferred.

[0031] Specifically, R 115 can be a tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride. As a structure belonging to R 115, the polyimide precursor may contain only one tetracarboxylic dianhydride residue, or it may contain two or more. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 9] In formula (O), R 115 represents a tetravalent organic group. R 115 has the same meaning as R 115 in formula (2), and the preferred range is also the same.

[0032] Specific examples of tetracarboxylic dianhydrides include pyrocalcite 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 dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives thereof having 1 to 6 carbon atoms.

[0033] Furthermore, as a better example, one can also cite the tetracarboxylic acid dianhydride (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598.

[0034] In formula (2), at least one of R111 and R115 may have an OH group. More specifically, as R111, residues of diaminophenol derivatives can be cited.

[0035] In formula (2), R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferable to include a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene group. Furthermore, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is even more preferable that both contain polymerizable groups. It is also preferable that at least one of R 113 and R 114 contains two or more polymerizable groups. As a polymerizable group, it is a group that can undergo cross-linking reaction by the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acetomethyl, epoxy, oxybutyl, benzo[a]azolyl, terminal isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having an ethylene unsaturated bond is preferred. Examples of groups having an ethylene unsaturated bond include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl), (meth)acrylamide, (meth)acryloxy, and groups represented by formula (III) below, with groups represented by formula (III) below being preferred.

[0036] [Chemical Formula 10]

[0037] In formula (III), R 200 represents a hydrogen atom, methyl, ethyl, or hydroxymethyl, with hydrogen atom or methyl being preferred. In formula (III), * indicates a bonding site with other structures. In formula (III), R 201 represents an alkyl group having 2 to 12 carbon atoms, -CH 2CH(OH)CH 2-, an cycloalkyl group, or a polyalkylene group. Preferred examples of R 201 include alkyl groups such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH 2CH(OH)CH 2-, and polyalkylene groups; vinyl, propenyl, and other propenyl groups, -CH 2CH(OH)CH 2-, cyclohexyl, and polyalkylene groups are more preferred; vinyl, propenyl, and other propenyl groups or polyalkylene groups are even more preferred. In this invention, a polyalkylene group refers to a group in which two or more alkylene groups are directly bonded. 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 can be random, block-shaped, or alternating. It is preferred that the number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent 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, it is preferred that the number of alkylene groups contained in the polyalkylene group (the number of repetitions of the polyalkylene group) is 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethethyleneoxy, or groups bonded by a plurality of ethyleneoxy and a plurality of propyleneoxy groups are preferred as polyvinyloxy groups, with polyvinyloxy or polypropyleneoxy being more preferred, and polyvinyloxy being even more preferred. Among the aforementioned groups bonded by a plurality of ethyleneoxy and a plurality of propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred state of the number of repetitions of the ethyleneoxy groups, etc., in these groups is as described above.

[0038] In formula (2), when R 113 is a hydrogen atom or R 114 is a hydrogen atom, the polyimide precursor can form a conjugated salt with a tertiary amine compound having an vinyl unsaturated bond. As an example of such a tertiary amine compound having an vinyl unsaturated bond, N,N-dimethylaminopropyl methacrylate can be cited.

[0039] In formula (2), at least one of R 113 and R 114 can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it decomposes by the action of acid to produce a base-soluble group such as a phenolic hydroxyl group or a carboxyl group. Acetal, ketal, silicone, silicone ether, and tertiary alkyl ester are preferred. From the viewpoint of exposure sensitivity, acetal or ketal is more preferred. Specific examples of acid-degradable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropiperanyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tertiary butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0040] Furthermore, it is also preferable that the polyimide precursor has fluorine atoms in its structure. It is preferable that the fluorine atom content in the polyimide precursor is 10% by mass or more, and preferably 20% by mass or less.

[0041] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0042] It is preferable that the repeating unit represented by formula (2) is the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in this invention is a precursor having a repeating unit represented by formula (2-A). By including a repeating unit represented by formula (2-A) in the polyimide precursor, the range of exposure latitude can be further increased. Formula (2-A) [Chemical Formula 11] In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 independently represent divalent organic groups, R113 and R114 independently represent hydrogen atoms or monovalent organic groups, at least one of R113 and R114 is a group containing a polymerizable group, and it is preferable that both are groups containing polymerizable groups.

[0043] A1, A2, R111, R113 and R114 have the same meaning as A1, A2, R111, R113 and R114 in equation (2), and the preferred range is also the same. R112 has the same meaning as R112 in equation (5), and the preferred range is also the same.

[0044] The polyimide precursor may contain one repeating unit represented by formula (2), or it may contain two or more repeating units. It may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2) above, the polyimide precursor may obviously also contain other types of repeating units.

[0045] As one embodiment of the polyimide precursor of the present invention, an example is provided in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. It is more preferable that the total content is 70 mol% or more, further preferably 90 mol% or more, and especially preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal units can be repeating units represented by formula (2).

[0046] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the above-mentioned polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is even more preferred. In this specification, the molecular weight dispersion is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. Furthermore, when the resin composition includes multiple polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated when the multiple polyimide precursors are considered as a single resin are each within the above-mentioned ranges.

[0047] [Polyimide] The polyimide used in this invention may be an alkali-soluble polyimide or a polyimide soluble in a developer solution mainly composed of an organic solvent. In this specification, alkali-soluble polyimide refers to polyimide dissolved in 100g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C at a concentration of 0.1g or more. From the viewpoint of pattern formation, dissolving 0.5g or more of polyimide is preferred, and dissolving 1.0g or more of polyimide is further preferred. The upper limit of the above-mentioned dissolution amount is not particularly limited, but less than 100g is preferred. Furthermore, from the viewpoint of the film strength and insulation of the obtained organic film, polyimide having a plurality of polyimide structures in the main chain is preferred. In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to the bonded chain other than the main chain.

[0048] -Fluorine Atom- From the viewpoint of the membrane strength of the obtained organic membrane, it is preferable that the polyimide has fluorine atoms. It is preferable that the fluorine atom is contained in R132 or R131 in the repeating unit represented by the following formula (4), and it is even more preferable that it is contained as a fluorinated alkyl group in R132 or R131 in the repeating unit represented by the following formula (4). It is preferable that the amount of fluorine atoms relative to the total mass of the polyimide is 5% by mass or more, and preferably 20% by mass or less.

[0049] -Silicon Atoms- From the viewpoint of the strength of the obtained organic membrane, it is preferable that the polyimide contains silicon atoms. It is preferable that the silicon atoms are included, for example, in R 131 of the repeating unit represented by the formula (4) described later, and even more preferably in R 131 of the repeating unit represented by the formula (4) described later as an organic modified (poly)siloxane structure. Furthermore, the aforementioned silicon atoms or the aforementioned organic modified (poly)siloxane structure may be included in the side chain of the polyimide, but it is preferable that they are included in the main chain of the polyimide. It is preferable that the amount of silicon atoms relative to the total mass of the polyimide is 1% by mass or more, and even more preferably 20% by mass or less.

[0050] -Ethylene unsaturated bond- From the viewpoint of the membrane strength of the obtained organic membrane, it is preferable that the polyimide has an ethylene unsaturated bond. The polyimide may have an ethylene unsaturated bond at the end of the main chain or in the side chain, with the side chain having an ethylene unsaturated bond being preferable. It is preferable that the ethylene unsaturated bond has free radical polymerization properties. It is preferable that the ethylene unsaturated bond is contained in R132 or R131 in the repeating unit represented by the following formula (4), and it is even preferable that it is contained as a group having an ethylene unsaturated bond in R132 or R131 in the repeating unit represented by the following formula (4). In these cases, it is preferable that the vinyl unsaturated bond is contained in R 131 of the repeating unit represented by the following formula (4), and it is even more preferable that R 131, as a group having an vinyl unsaturated bond, is contained in the repeating unit represented by the following formula (4). Examples of groups having an vinyl unsaturated bond include vinyl, allyl, vinylphenyl, and other substituted vinyl groups that are directly bonded to an aromatic ring, (meth)acrylamide, (meth)acryloxy, and groups represented by the following formula (IV).

[0051] [Chemical Formula 12]

[0052] In formula (IV), R 20 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred.

[0053] In formula (IV), R 21 represents an alkyl group having 2 to 12 carbon atoms, -O-CH 2CH(OH)CH 2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and especially preferably 2 or 3; preferably 1 to 12 repetitions, more preferably 1 to 6, and especially preferably 1 to 3), or a group formed by combining two or more of these. Furthermore, the alkyl group having 2 to 12 carbon atoms can be any of the following: linear, branched, cyclic, or a combination thereof. As the alkyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 8 carbon atoms is preferred, and an alkyl group having 2 to 4 carbon atoms is even more preferred.

[0054] In these formulations, it is preferable that R21 is a group represented by any one of the following formulas (R1) to (R3), and it is more preferable that the group is represented by formula (R1). [Chemical Formula 13] In formulas (R1) to (R3), L represents a single bond or an alkyl group having 2 to 12 carbon atoms, a (poly)alkylene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these; X represents an oxygen atom or a sulfur atom; * represents a bonding site with other structures; and ● represents a bonding site with the oxygen atom bonded to R21 in formula (IV). In formulas (R1) to (R3), the preferred form of the alkyl group having 2 to 12 carbon atoms or the (poly)alkylene group having 2 to 30 carbon atoms in L is the same as the preferred form of the alkyl group having 2 to 12 carbon atoms or the (poly)alkylene group having 2 to 30 carbon atoms in R21. In formula (R1), it is preferable that X is an oxygen atom. In formulas (R1) to (R3), * has the same meaning as in formula (IV), and the preferred state is also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide with hydroxyl groups such as phenolic hydroxyl groups with a compound having isocyanate groups and vinyl unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide with carboxyl groups with a compound having hydroxyl groups and vinyl unsaturated bonds (e.g., hydroxyethyl 2-methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide with hydroxyl groups such as phenolic hydroxyl groups with a compound having glycidyl groups and vinyl unsaturated bonds (e.g., glycidyl methacrylate).

[0055] In formula (IV), * indicates the bonding site with other structures, and the bonding site with the main chain of polyimide is preferred.

[0056] The amount of vinyl unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0057] - Polymerizable groups other than those with vinyl unsaturated bonds- Polyimide may contain polymerizable groups other than those with vinyl unsaturated bonds. Examples of polymerizable groups other than those with vinyl unsaturated bonds include cyclic ether groups such as epoxy groups and cyclobutane groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. For example, it is preferable that the polymerizable groups other than those with vinyl unsaturated bonds are included in R 131 in the repeating unit represented by formula (4) described later. It is preferable that the amount of polymerizable groups other than those with vinyl unsaturated bonds relative to the total mass of polyimide is 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0058] -Polar conversion group- Polyimide may have polar conversion groups such as acid-degrading groups. The acid-degrading groups in polyimide are the same as those described in R 113 and R 114 of the above formula (2), and the preferred form is also the same. Polar conversion groups are included, for example, in R 131, R 132, the end of polyimide, etc., in the repeating unit represented by the following formula (4).

[0059] -Acid Value- When polyimide is used for alkaline development, from the viewpoint of improving developability, an acid value of 30 mg KOH / g or higher is preferred, 50 mg KOH / g or higher is more preferred, and 70 mg KOH / g or higher is even more preferred. Furthermore, an acid value of 500 mg KOH / g or lower is preferred, 400 mg KOH / g or lower is more preferred, and 200 mg KOH / g or lower is even more preferred. Also, when polyimide is used in development with a developer primarily composed of organic solvents (e.g., "solvent development" described below), an acid value of 1 to 35 mg KOH / g is preferred, 2 to 30 mg KOH / g is more preferred, and 5 to 20 mg KOH / g is even more preferred. The above acid values ​​are determined by known methods, for example, by the method described in JIS K 0070:1992. Furthermore, considering both storage stability and developability, acid groups included in polyimide preferably have a pKa of 0 to 10, and more preferably 3 to 8. pKa is the equilibrium constant Ka, expressed as the negative logarithm of the dissociation reaction of the acid releasing hydrogen ions. In this specification, unless otherwise specified, pKa is set to a value calculated based on ACD / ChemSketch (registered trademark). Alternatively, the values ​​described in the "5th Revised Edition of the Chemical Handbook: Basic Chemicals" compiled by the Chemical Society of Japan can be consulted. Also, when the acid group is, for example, a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As such acid groups, polyimide preferably contains at least one group selected from the group including carboxyl and phenolic hydroxyl groups, and more preferably contains phenolic hydroxyl groups.

[0060] -Phenolic hydroxyl group- From the viewpoint of achieving an appropriate development speed based on alkaline developer, it is preferable that the polyimide has phenolic hydroxyl groups. The polyimide may have phenolic hydroxyl groups at the end of the main chain or in the side chain. It is preferable that the phenolic hydroxyl groups are contained, for example, in R 132 or R 131 in the repeating unit represented by formula (4) described later. It is preferable that the amount of phenolic hydroxyl groups relative to the total mass of the polyimide is 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0061] The polyimide used in this invention is not particularly limited as long as it is a polymer compound having a polyimide structure, but it is preferred to include repeating units represented by the following formula (4). [Chemical Formula 14] In formula (4), R 131 represents a divalent organic group and R 132 represents a tetravalent organic group. When a polymerizable group is present, the polymerizable group may be located on at least one of R 131 and R 132, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1) [Chemical Formula 15] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meaning as in formula (4). Formula (4-2) [Chemical Formula 16] At least one of R 134 and R 135 is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).

[0062] As a polymerizable group, examples include groups containing the aforementioned vinyl unsaturated bonds or crosslinking groups other than groups containing the aforementioned vinyl unsaturated bonds. R 131 represents a divalent organic group. Examples of divalent organic groups are those identical to R 111 in formula (2), and the preferred range is also the same. Furthermore, as R 131, examples include diamine residues remaining after the amino group of a diamine has been removed. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. As a specific example, examples include R 111 in formula (2) of polyimide precursors.

[0063] From the viewpoint of more effectively suppressing warping during firing, R 131 is preferably a diamine residue having at least two alkyl diol units in the main chain. More preferably, it is a diamine containing a total of two or more ethylene glycol chains, propylene glycol chains, or both in a molecule; even more preferably, it is the above-mentioned diamine without containing diamine residues of an aromatic ring.

[0064] As a diamine containing a total of two or more ethylene glycol chains or propylene glycol chains in one molecule, examples include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., but not limited to these.

[0065] R 132 represents a tetravalent organogroup. As a tetravalent organogroup, it can be exemplified as the same as R 115 in formula (2), and the preferred range is also the same. For example, the four bonds of the tetravalent organogroup exemplified as R 115 are bonded to the four -C (=O)- portions in the above formula (4) to form a condensation ring.

[0066] Furthermore, R 132 can be a tetracarboxylic acid residue remaining after the anhydride group is removed from a tetracarboxylic acid dianhydride. As a specific example, R 115 in formula (2) of a polyimide precursor can be cited. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0067] It is also preferable that at least one of R 131 and R 132 has an OH group. More specifically, as R 131, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above-mentioned (DA-1) to (DA-18) are preferred examples, and as R 132, the above-mentioned (DAA-1) to (DAA-5) are more preferred examples.

[0068] Furthermore, it is also preferable that the polyimide has fluorine atoms in its structure. It is preferable that the fluorine atom content in the polyimide precursor is 10% by mass or more, and preferably 20% by mass or less.

[0069] Furthermore, in order to improve adhesion to the substrate, polyimide can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0070] Furthermore, in order to improve the storage stability of the resin composition, it is preferable to end-cap the main chain of the polyimide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochloro compounds, and active monoester compounds. Among these, monoamines are preferred, and preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminenaphthalene, 1-hydroxy-6-aminenaphthalene, 1-hydroxy-5-aminenaphthalene, 1-hydroxy-4-aminenaphthalene, 2-hydroxy-7-aminenaphthalene, 2-hydroxy-6-aminenaphthalene, 2-hydroxy-5-aminenaphthalene, 1-carboxy-7-aminenaphthalene, 1-carboxy-6-aminenaphthalene, and 1-carboxy-5-aminenaphthalene. Examples of amino acids include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, and 4-aminobenzenethiophenol. Two or more of these can be used, or multiple different end groups can be introduced by reacting multiple end-capping agents.

[0071] - Acrylimization Rate (Ring-Closed Rate)- From the perspective of the obtained organic film's strength and insulation properties, a acetilimization rate (also known as "ring-closed rate") of 70% or higher for polyimide is preferred, 80% or higher is even better, and 90% or higher is even better. There is no specific upper limit to the above acetilimization rate; 100% or lower is acceptable. For example, the above acetilimization rate can be determined by the following method: Measure the infrared absorption spectrum of the polyimide and determine the peak intensity P1 near 1377 cm⁻¹, which is the absorption peak originating from the acetilimide structure. Next, after heat-treating the polyimide at 350°C for 1 hour, measure the infrared absorption spectrum again and determine the peak intensity P2 near 1377 cm⁻¹. Using the obtained peak intensities P1 and P2, the acetilimization rate of the polyimide can be determined according to the following formula. Acrylimide content (%) = (peak intensity P1 / peak intensity P2) × 100

[0072] Polyimide may have repeating units represented by the above formula (4) which includes only one type of R 131 or R 132, or it may have repeating units represented by the above formula (4) which includes two or more different types of R 131 or R 132. In addition to repeating units represented by the above formula (4), polyimide may also include other types of repeating units. For example, repeating units represented by the above formula (2) can be cited as other types of repeating units.

[0073] For example, polyimide can be produced by reacting tetracarboxylic dianhydride with diamine (with a portion replaced by a monoamine, i.e., a capping agent) at low temperature; by reacting tetracarboxylic dianhydride (with a portion replaced by an anhydride, a monochloro compound, or an active monoester compound, i.e., a capping agent) with diamine at low temperature; by obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting it in the presence of diamine (with a portion replaced by a monoamine, i.e., a capping agent) and a condensing agent; by using tetracarboxylic dianhydride... Polyamide precursors are obtained by methods such as esterification of dianhydrides and alcohols, followed by acetylation of the remaining dicarboxylic acid and reaction with a diamine (partially replaced by a monoamine, i.e., a capping agent). These precursors are then synthesized using conventional acetylation reactions, either by complete acetylation or by stopping the acetylation reaction midway and introducing a partial acetylation structure, or by further mixing the fully acetylated polymer with the polyamide precursor to introduce a partial acetylation structure. Other known methods for synthesizing polyamides are also applicable.

[0074] The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. For obtaining an organic film with excellent mechanical properties (e.g., elongation at break), a weight average molecular weight of 15,000 or more is particularly preferred. Furthermore, the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the above-mentioned polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of polyimides; for example, 7.0 or less is preferred, 6.5 or less is even more preferred, and 6.0 or less is further preferred. Furthermore, when the resin composition contains multiple polyimides as a specific resin, it is preferred that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyimide are within the above-mentioned ranges. Also, it is preferred that the weight average molecular weight, number average molecular weight, and dispersion calculated when the multiple polyimides are considered as a single resin are each within the above-mentioned ranges.

[0075] [Polybenzoxazole precursor] As a polybenzoxazole precursor, compounds described in paragraphs 0049 to 0074 of International Publication No. 2021 / 172420 may be used. This content is incorporated in this specification.

[0076] [Manufacturing Method of Polyimide Precursors, etc.] For example, polyimide precursors, etc., can be obtained by the following methods: a method of reacting tetracarboxylic dianhydride with diamine at low temperature; a method of obtaining polyamide by reacting tetracarboxylic dianhydride with diamine at low temperature and then esterifying it with a condensing agent or an alkylating agent; a method of obtaining a diester by tetracarboxylic dianhydride and alcohol and then reacting it in the presence of diamine and a condensing agent; a method of obtaining a diester by tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine, etc. Of the above manufacturing methods, the method of obtaining a diester by tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and then reacting it with diamine is more preferred. Examples of condensing agents include dicyclohexanediimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of halogenating agents include thionyl chloride, oxalyl chloride, and phosphatidyl chloride. In the method for manufacturing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used. As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the manufacturing method of polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound can be one type or two or more types. The basic compound can be appropriately determined according to the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diacrylbicyclo[5.4.0]undecyl-7-ene, N,N-dimethyl-4-aminepyridine, etc.

[0077] -End-capping agent- In the manufacture of polyimide precursors, etc., it is preferable to block the carboxylic anhydride, anhydride derivative, or amine groups remaining at the ends of the resin, etc., in order to further improve storage stability. When blocking the carboxylic anhydride and anhydride derivatives remaining at the resin ends, the end-capping agent described in paragraph 0131 of International Publication No. 2021 / 100768 can be cited as an example. This content is incorporated in this specification.

[0078] - Solid Precipitation - When manufacturing polyimide precursors, a solid precipitation step may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, thereby precipitating it as a solid and drying it to obtain the polyimide precursor, etc. To improve the purification degree, the polyimide precursor, etc., may be repeatedly subjected to operations such as redissolving, redepositing, and drying. A step of removing ionic impurities using an ion exchange resin may also be included.

[0079] [Content] The content of the specific resin in the resin composition of the present invention, relative to the total solid content of the resin composition, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of the resin in the resin composition of the present invention, relative to the total solid content of the resin composition, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less. The resin composition of the present invention may contain only one specific resin, or it may contain two or more. When containing two or more, it is preferable that the total amount is within the above-mentioned range.

[0080] Furthermore, it is preferable that the resin composition of the present invention contains at least two types of resins. Specifically, the resin composition of the present invention may contain two or more types of specific resins and other resins described below, or it may contain two or more types of specific resins, and it is preferable that it contains two or more types of specific resins. When the resin composition of the present invention contains two or more types of specific resins, it is preferable that it contains, for example, two or more polyimide precursors with different structures derived from dianhydrides (R 115 in formula (2) above).

[0081] <Other Resins> The resin composition of the present invention may also include other resins (hereinafter, also referred to as "other resins") that are different from the specific resins described above, or may replace the specific resins described above. Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic amide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, polyester resins, etc. In particular, by using (meth)acrylic resins having acid-degradable groups, the resin composition can be used as a composition for pattern forming. Examples of (meth)acrylic resins having such acid-degradable groups include, for example, the resin (B) described in paragraphs 0069 to 0170 of Japanese Patent Application Publication No. 2019-174549. Furthermore, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can also be obtained. For example, by adding (meth)acrylic resin to the resin composition to replace the polymerizable compound described later, or by adding (meth)acrylic resin in addition to the polymerizable compound described later, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc., can be improved. The (meth)acrylic resin has a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the content of polymerizable groups in 1g of resin is 1×10⁻³ moles / g or more).

[0082] When the resin composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, the content of other resins in the resin composition of the present invention relative to the total solid content of the resin composition is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less. Also, as a preferred embodiment of the resin composition of the present invention, it is also possible to set it to a state with a low content of other resins. In the above-described samples, the content of other resins relative to the total solids content of the resin composition is preferably 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. The lower limit of the above content is not particularly limited; 0% by mass or more is acceptable. The resin composition of the present invention may contain only one type of other resin, or it may contain two or more types. When containing two or more types, it is preferable that the total amount is within the above-described range.

[0083] <Specific alkali generating agent> The resin composition of the present invention contains a specific alkali generating agent.

[0084] The specific base generating agent of the present invention is a compound represented by the following formula (1-1). [Chemical Formula 17] In formula (1-1), L1 represents an n+m valence linker, R1 independently represents a monovalent organic group, R2 independently represents a monovalent organic group or a hydrogen atom, R1 can be linked together to form a ring structure, m represents an integer of 1 or more, and n represents an integer of 1 or more. Regarding the compound represented by formula (1-1), as long as the structural formula is the same, it is not limited to geometric isomers, optical isomers, or other stereoisomers.

[0085] 〔L 1〕 L 1 is preferably a hydrocarbon group or a group represented by a hydrocarbon group and a combination of at least one structure selected from the group including -O-, -C(=O)-, -S-, -S(=O) 2- and -NR N-, and more preferably a hydrocarbon group or a group represented by a hydrocarbon group and a combination of at least one structure selected from the group including -O-, -C(=O)- and -NR N-, and even more preferably a hydrocarbon group.

[0086] The above RNs independently represent hydrogen atoms or monovalent organic groups, with hydrogen atoms or hydrocarbon groups being preferred, hydrogen atoms, alkyl or aromatic hydrocarbon groups being preferred, hydrogen atoms, alkyl or phenyl groups having 1 to 10 carbons being more preferred, hydrogen atoms, alkyl or phenyl groups having 1 to 4 carbons being even more preferred, and hydrogen atoms being particularly preferred.

[0087] The aforementioned hydrocarbon group can be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these. Furthermore, the aforementioned hydrocarbon group can have substituents. There are no particular limitations on the substituents; examples include groups with polymerizable groups. Among groups with polymerizable groups, groups with free radical polymerizable groups are preferred. Examples of free radical polymerizable groups include vinyl, allyl, vinylphenyl, (meth)acryloxy, maleic anhydride, and (meth)acrylamide, with (meth)acryloxy, (meth)acrylamide, or vinylphenyl being preferred. From a reactivity point of view, (meth)acryloxy is more preferred. Furthermore, when L1 has a free radical polymerizable group, it is preferable that the resin has a free radical polymerizable group or the resin composition contains at least one of the free radical crosslinking agents described later. Based on this type of pattern, it is believed that because an alkali-generating agent is added to the polymer formed by polymerization, the distribution of the alkali-generating agent within the composition is in a near-uniform state, and the rectangularity of the pattern is further improved.

[0088] From the viewpoints of easy formation of alkali and close contact, it is preferable that L1 contains an aromatic ring structure. As for the aromatic ring structure, there is no particular limitation, but an aromatic hydrocarbon ring structure is preferred, a naphthalene ring structure or a benzene ring structure is more preferred, and a benzene ring structure is even more preferred.

[0089] From the perspective of easy formation of alkali and drug resistance, it is preferable that the carbonyl groups of L1 that are directly bonded to the nitrogen atom of R2 in formula (1-1) are all carbon atoms, and it is even preferable that the carbonyl groups of L1 that are directly bonded to the nitrogen atom of R2 in formula (1-1) are all carbon atoms.

[0090] In L 1, the number of atoms (linkage chain length) in the shortest path of the linking chain between the carbonyl group directly bonded to the nitrogen atom of R 2 in formula (1-1) and the carbonyl group directly bonded to the nitrogen atom of R 1 in formula (1-1) is preferably 2 to 5, and 2 or 3 is more preferred. When at least one of m and n is 2 or more, the linking chain length between one of the m carbonyl groups directly bonded to the nitrogen atom of R 2 in formula (1-1) and one of the n carbonyl groups directly bonded to the nitrogen atom of R 1 in formula (1-1) is within the above range. For example, in the following compound A-1, the above linking chain length is 2. [Chemical Formula 18]

[0091] Specific examples of L1 are shown below, but the present invention is not limited thereto. In the following specific examples, * indicates the carbonyl group directly bonded to the nitrogen atom of R2 in formula (1-1), and # indicates the carbonyl group directly bonded to the nitrogen atom of R1 in formula (1-1). In this specification, the bond that crosses the edge of the ring structure refers to the substitution of any hydrogen atom omitted from the description in the ring structure. [Chemical Formula 19]

[0092] [R 1] In formula (1-1), R 1 is preferably an independent hydrocarbon group that can have substituents, or R 1 in formula (1-1) is bonded to each other to form a nitrogen-containing aliphatic heterocyclic structure that can have substituents. As a hydrocarbon group in the case where R 1 can have substituents, alkyl, aromatic hydrocarbon groups or groups represented by combinations thereof are more preferred, alkyl groups having 1 to 10 carbons, aromatic hydrocarbon groups having 6 to 20 carbons or groups represented by combinations thereof are further preferred, and alkyl groups having 1 to 10 carbons are particularly preferred. As the above-mentioned alkyl group, it can be any of straight-chain, branched, or cyclic. From the viewpoint of improving elongation at break, branched alkyl groups (e.g., isopropyl, isobutyl, 2-ethylhexyl, etc.) or cyclic alkyl groups (e.g., cyclohexyl, etc.) are preferred. There are no particular limitations on the substituents in the aforementioned hydrocarbon groups, and examples include halogen atoms, alkoxy groups, aryloxy groups, alkyl carbonyl groups, aryl carbonyl groups, and hydroxyl groups.

[0093] Furthermore, the R1 atoms in formula (1-1) can be linked together to form a ring structure. In the above-described state, it is preferable that the R1 atoms bonded to the same nitrogen atom are linked together to form a ring structure. As the formed ring structure, a nitrogen-containing aliphatic heterocyclic structure is preferred; for example, pyrrolidine rings, piperidine rings, α-porphyrin rings, and nortropine rings, in which the nitrogen atom directly bonded to the aforementioned R1 is a ring member, are examples. These ring structures can further have substituents. As substituents, groups identical to the substituents in the aforementioned hydrocarbon groups can be cited.

[0094] Furthermore, in formula (1-1), it is preferable that at least one of R1 is a structure represented by formula (R-1). By having at least one of R1 be a structure represented by formula (R-1), the volume around the nitrogen atom of the amine group in the generated base increases, thus enabling steric hindrance to suppress the reaction with the resin in the film. Consequently, the base diffuses more uniformly within the film. Therefore, it is believed that the difference in film shrinkage between the surface side and the substrate side is easily suppressed, resulting in excellent rectangularity of the obtained pattern. [Chemical Formula 20] In formula (R-1), R 11 independently represents a monovalent organic group. Two R 11 or R 11 and another R 1 in formula (1-1) (that is, the other R 1 in formula (1-1) when one of the two R 1 in formula (1-1) is represented by formula (R-1). The other R 1 can also be a structure represented by formula (R-1)) can be linked to form a ring structure. In formula (R-1), it is preferable that R 11 is a hydrocarbon group, more preferably an alkyl group, an aromatic hydrocarbon group, or a combination thereof, and even more preferably an alkyl group having 1 to 10 carbons, an aromatic hydrocarbon group having 6 to 20 carbons, or a combination thereof, and especially preferably an alkyl group having 1 to 10 carbons. The alkyl group described above can be linear, branched, or cyclic. From the viewpoint of improving elongation at break, branched alkyl groups (e.g., isopropyl, isobutyl, 2-ethylhexyl, etc.) or cyclic alkyl groups (e.g., cyclohexyl, etc.) are preferred. As a ring structure formed by linking two R11s to each other or R11 to another R1 in formula (1-1), examples include pyrrolidine rings, piperidine rings, α-porphyrin rings, and nortropine rings, where the nitrogen atom directly bonded to the aforementioned R1 is a ring member. These ring structures may further have substituents. Substituents can be groups identical to the substituents in the aforementioned hydrocarbon groups.

[0095] Furthermore, at least one of R1 is the structure represented by the above formula (R-1), and it is preferable that either the structure represented by formula (R-1) or any one of the other R1 in formula (1-1) has a heteroatom and an aromatic group. Examples of the heteroatom include oxygen, sulfur, and nitrogen atoms, with oxygen being preferred. The aromatic group can be a heteroaromatic group or an aromatic hydrocarbon group, with aromatic hydrocarbon groups being preferred. Examples of the aromatic hydrocarbon group are aromatic hydrocarbon groups with 6 to 20 carbon atoms, with aromatic hydrocarbon groups having 6 carbon atoms being more preferred. Examples of the heteroatom in the heteroaromatic group include oxygen, sulfur, and nitrogen atoms, with oxygen being preferred. It is preferable that the heteroaromatic group is a 5-membered ring, a 6-membered ring, or a condensation ring of a 5-membered and a 6-membered ring.

[0096] As an example of a preferred state of R1, the following structure can be cited, but it is not limited to this. The nitrogen atom in the structure of the following specific examples refers to the nitrogen atom of R1 directly bonded to formula (1-1). In the following specific examples, * indicates the bonding site with the carbonyl group. [Chemical Formula 21] Furthermore, the dimethylpiperidine ring and dimethyl uridine ring in the above structure can be either cis or trans. Here, from the viewpoint of the elongation at break of the obtained cured product, the cis is preferred. Compared to the cis, the trans has a slightly larger volume around the nitrogen atom. Therefore, it is believed that the matrix compound can more easily approach the nitrogen atom of the active site in the base produced by the cis, and the acetylation promotion effect is improved. On the other hand, it is believed that since it has a sufficiently large volume to the extent that it does not react with the resin, the rectangularity of the pattern can also be maintained. Therefore, it is speculated that compared to the trans, the cis maintains other properties while having an excellent elongation at break. Furthermore, for structures not listed in the specific examples above but with geometric isomers, the cis configuration is preferred for the same reason when the volume around the nitrogen atom increases.

[0097] [R 2] R 2 is preferably a hydrogen atom or a hydrocarbon group that may have substituents; from the viewpoint of closeness, a hydrocarbon group that may have substituents is more preferred. As the aforementioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of a saturated aliphatic hydrocarbon group and an aromatic hydrocarbon group is more preferred. As the aforementioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is more preferred, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferred, and a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms is even more preferred. As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms can be cited; a group formed by removing one or more hydrogen atoms from a benzene ring or a naphthalene ring is more preferred, and a group formed by removing one or more hydrogen atoms from a benzene ring is more preferred. As a group represented by a combination of a saturated aliphatic hydrocarbon group and an aromatic hydrocarbon group, an aralkyl group having 7 to 20 carbon atoms is more preferred, and an aralkyl group having 7 to 10 carbon atoms is more preferred. The preferred forms of the saturated aliphatic hydrocarbon group and the aromatic hydrocarbon group in the group represented by the combination of saturated aliphatic hydrocarbon group and the aromatic hydrocarbon group are the same as the preferred forms when R2 is a saturated aliphatic hydrocarbon group and when R2 is an aromatic hydrocarbon group, respectively. Furthermore, the aforementioned hydrocarbon group may have substituents. There are no particular limitations on the substituents; examples include halogen atoms, alkoxy groups, aryloxy groups, alkyl carbonyl groups, aryl carbonyl groups, and hydroxyl groups.

[0098] As an example of a preferred state of R2, the following structure can be cited, but it is not limited to this. In the following specific examples, * indicates the bonding site with the nitrogen atom. [Chemical Formula 22]

[0099] 〔m〕 m is preferably an integer from 1 to 10, even better is an integer from 1 to 4, 1 or 2 is even better, and 1 is especially good.

[0100] 〔n〕 It is preferable that n is an integer from 1 to 10, even more preferable that it is an integer from 1 to 4, further preferable that it is 1 or 2, and especially preferable that it is 1. Furthermore, the state in which m and n are the same number is also one of the preferred states of the present invention.

[0101] [Conditions for base formation] It is preferable that a specific base-generating agent produces an amine-containing base by cleaving between the nitrogen atom directly bonded to R1 and the carbonyl group directly bonded to the nitrogen atom. Furthermore, it is preferable that the specific base-generating agent of the present invention produces a base by heating to 250°C, more preferably by heating to 220°C, further preferably by heating to 200°C, particularly preferably by heating to 190°C, and most preferably by heating to 180°C. There is no particular limitation on the lower limit of the temperature for base formation; from the viewpoint of the storage stability of the composition, for example, 100°C or higher is preferable. Whether a compound A exhibits the property of producing a base at a certain temperature X°C is determined by the following method. One mol of compound A is heated at 1 atmosphere in a sealed container at X°C for 3 hours. The amount of decomposition is then quantified using methods such as HPLC (High Performance Liquid Chromatography). If 0.01 mol or more of a base is produced, it is determined that compound A has produced a base through heating at X°C. Whether the produced compound is a base is confirmed, for example, by using 1H-NMR. A base production of 0.1 mol or more is preferred, and 0.5 mol or more is even more preferred. There is no particular upper limit to the base production amount; for example, it can be set to 1000 mol or less.

[0102] [Base] The base produced by a specific base generating agent is preferably a compound having an amino group. The base can be a compound having two or more amino groups, but a compound having only one amino group is preferred. The amino group is preferably a secondary amino group. Furthermore, the base of the compound having the above-mentioned amino group can be an aliphatic amine or an aromatic amine, with aliphatic amines being preferred. It is believed that since aliphatic amines are more basic than aromatic amines, they have a greater hardening promoting effect. Furthermore, the base is preferably a cyclic aliphatic amine such as pyrrolidine, piperidine, succinyl, nortropinol, or those in which part of the hydrogen atom is substituted with a substituent. As for the substituent, there is no particular limitation, but alkyl, aromatic hydrocarbon, and hydroxyalkyl are preferred, alkyl with 1 to 10 carbons, aromatic hydrocarbon with 6 to 20 carbons, and hydroxyalkyl with 1 to 10 carbons are more preferred, and alkyl with 1 to 4 carbons, phenyl, or hydroxyalkyl with 2 to 4 carbons are even more preferred. Aliphatic amines refer to amines in which all carbon atoms bonded to the nitrogen atom of the amine group are carbon atoms contained in an aliphatic hydrocarbon group. Aromatic amines refer to amines in which at least one carbon atom bonded to the nitrogen atom of the amine group is contained as a ring member in an aromatic group. Furthermore, cyclic aliphatic amines refer to aliphatic amines in which the nitrogen atom of the amine group is contained within an aliphatic ring structure.

[0103] Furthermore, the base generated from the specific base generating agent is preferably one in which at least one carbon atom directly bonded to a nitrogen atom on at least one of the amino groups contained in the amine is bonded to two or more organic groups, and has at least one heteroatom and at least one aromatic group in the molecule after the amino group is removed. As the above-mentioned organic group, an organic group whose bonding site with the above-mentioned carbon atom is a carbon atom is preferred, and it is more preferably a hydrocarbon group having a substituent or a group represented by -C(=O)-RC. Furthermore, examples of the above-mentioned heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc., with oxygen atoms being preferred. As the hydrocarbon group in the above-mentioned organic group, alkyl, aromatic hydrocarbon groups, or groups represented by combinations thereof are more preferred, and alkyl groups having 1 to 10 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, or groups represented by combinations thereof are further preferred, with alkyl groups having 1 to 10 carbon atoms being particularly preferred. The substituents in the aforementioned hydrocarbon groups are not particularly limited, and examples include hydroxyl, carboxyl, groups containing ketone groups (-C(=O)-), groups containing ester groups (-C(=O)O-), groups containing ether groups (-O-), groups containing amide groups (-C(=O)NR N-), groups containing amide groups (-C(=O)NR NC(=O)-), groups containing thioether groups (-S-), and groups containing ketoxime groups (-C(=N(-OH)-). RN represents a hydrogen atom or a monovalent organic group, with hydrogen atom or hydrocarbon group being more preferred. In this invention, when simply referred to as an ester group, amide group, etc., its bonding orientation is not particularly limited. For example, in an ester group, an oxygen atom can be directly bonded to the aforementioned hydrocarbon group, or a carbonyl group can be directly bonded to the aforementioned hydrocarbon group. Examples of RC groups represented by -C(=O)-RC in the above-mentioned organic groups include alkyl groups (preferably with 1 to 20 carbon atoms, more preferably 1 to 10), alkoxy groups (preferably with 1 to 20 carbon atoms, more preferably 1 to 10), aryl groups (preferably with 4 to 20 carbon atoms, more preferably 4 to 10), aryloxy groups (preferably with 6 to 20 carbon atoms, more preferably 6 to 10), with alkoxy groups being more preferred.

[0104] Furthermore, the base generated from a specific base generating agent can form a ring structure having a nitrogen atom contained in an amine group as a ring member. The aforementioned ring structure can be an aliphatic ring structure or an aromatic ring structure, with an aliphatic ring structure being preferred, and a saturated aliphatic ring structure being even more preferred. A 5-membered or 6-membered ring structure is preferred. Furthermore, the aforementioned ring structure can be a monocyclic or polycyclic ring. Examples of polycyclic rings include condensed rings, cross-linked rings, and spirocyclic rings. The aforementioned ring structure is also preferably a ring structure containing at least one group selected from the group consisting of ketone, ester, ether, amide, amide, thioether, and ketoxime groups, or a ring structure formed by hydroxyl or carboxyl groups. Furthermore, when geometric isomers exist in the aforementioned ring structure, the cis-isomer is preferred from the viewpoint of the elongation at break of the obtained cured product. Compared to the cis-isomer, the trans-isomer has a slightly larger volume around the nitrogen atom. Therefore, it is believed that the matrix compound can more easily access the nitrogen atom at the active site of the base produced by the cis-form, thus enhancing the acetylation promoting effect. On the other hand, it is believed that due to its sufficiently large volume that does not react with the resin to a certain extent, the rectangularity of the pattern can also be maintained. Therefore, it is speculated that compared to the trans-form, the cis-form maintains other properties while exhibiting superior elongation at break.

[0105] The molecular weight of the base produced by the specific base-generating agent is preferably 70 to 1,000, more preferably 80 to 800, and further preferably 85 to 500. The base produced by the specific base-generating agent is preferably a conjugate acid with a pKa of 0 or higher, more preferably 3 or higher, and more preferably 6 or higher. There is no particular upper limit to the pKa of the aforementioned conjugate acid, but 30 or lower is preferred. pKa is the equilibrium constant Ka, which is expressed by the negative logarithm of the dissociation reaction of the acid releasing hydrogen ions. In this specification, unless otherwise specified, the pKa is set to a value calculated based on ACD / ChemSketch (registered trademark). When there are multiple pKas of the aforementioned conjugate acids, at least one is preferably within the above range.

[0106] There are no particular limitations on the specific examples of the base produced. For example, bases with the following structures can be cited. [Chemical Formula 23] Furthermore, the dimethylpiperidine and dimethyl uridine in the above structure exist in both cis and trans forms, and can be either one. Here, from the viewpoint of the elongation at break of the obtained cured product, the cis form is preferred. Compared to the cis form, the trans form has a slightly larger volume around the nitrogen atom. Therefore, it is speculated that the matrix compound in the cis form is more likely to approach the nitrogen atom of the active site, thus improving the amide imidization promotion effect. On the other hand, it is speculated that since it has a sufficiently large volume to the extent that it does not react with the resin, the rectangularity of the pattern can also be maintained. Therefore, it is considered that the cis form maintains other properties while having an excellent elongation at break compared to the trans form. Furthermore, regarding structures not listed in the above specific examples but which have geometric isomers, when the volume around the nitrogen atom increases in the cis form, the cis form is preferred for the same reason.

[0107] 〔Molecular weight〕 It is preferred that the molecular weight of the specific base generating agent is 150 to 1,500, more preferably 180 to 1,000, and even more preferably 200 to 800.

[0108] [Synthetic Method] Certain base-generating agents can be synthesized, for example, by reacting a condensing agent such as carbodiimide with an amine to a monocarboxylic acid-monoacetamide compound obtained by reacting a carboxylic anhydride with an amine. Alternatively, other known synthetic methods can also be used; the synthetic method is not particularly limited.

[0109] There are no particular limitations on the specific examples of the base generating agent, but examples A-1 to A-34 used in the examples can be cited.

[0110] The content of the specific alkali generating agent relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass. A lower limit of 0.2% by mass or more is more preferred, 0.5% by mass or more is further preferred, and 2% by mass or more is particularly preferred. An upper limit of 20% by mass or less is more preferred, 15% by mass or less is further preferred, and 10% by mass or less is particularly preferred. One specific alkali generating agent may be used alone, or two or more may be used simultaneously. When two or more are used simultaneously, their total content is preferably within the above-mentioned range. Furthermore, when the resin composition of the present invention includes the specific alkali generating agent and the alkali generating agent described later (an alkali generating agent different from the specific alkali generating agent), the total content of the specific alkali generating agent and the alkali generating agent (an alkali generating agent different from the specific alkali generating agent) is preferably 0.1 to 30% by mass. A lower limit of 0.2% by mass or more is more preferred, 0.5% by mass or more is further preferred, and 2% by mass or more is particularly preferred. It is preferable that the content is 20% by mass or less, further preferably 15% by mass or less, and especially preferably 10% by mass or less. Furthermore, it is preferable that the content of the specific alkali-generating agent in the resin composition of the present invention, relative to 100 parts by mass of a specific resin, is 0.1 to 30 parts by mass, and even more preferably 0.5 to 20 parts by mass.

[0111] <Organometallic Complexes> From the viewpoint of drug resistance, it is preferable that the resin composition of the present invention includes organometallic complexes. The organometallic complex is any organic complex compound containing a metal atom; a complex compound containing both a metal atom and an organic group is preferred; a compound in which the organic group is coordinated to a metal atom is even more preferred; and a metallocene compound is further preferred. In the present invention, a metallocene compound refers to an organometallic complex containing two cyclopentadienyl anionic derivatives, which may have substituents, as n5-ligands. The organic group is not particularly limited; a hydrocarbon group or a group composed of a hydrocarbon group and a heteroatom is preferred. As heteroatoms, oxygen, sulfur, and nitrogen atoms are preferred. In the present invention, at least one of the organic groups is preferably a cyclic group; at least two cyclic groups are even more preferred. The cyclic group is preferably selected from 5-membered and 6-membered cyclic groups, with 5-membered cyclic groups being more preferred. The aforementioned cyclic group can be a hydrocarbon ring or a heterocycle, with a hydrocarbon ring being preferred. As a 5-membered ring cyclic group, a cyclopentadienyl group is preferred. Furthermore, the organometallic complex used in this invention preferably contains 2 to 4 cyclic groups per molecule.

[0112] The metal contained in the organometallic complex is not particularly limited, but it is preferred to be a metal belonging to Group 4 elements, more preferably to be selected from at least one metal from the group including titanium, zirconium and hafnium, and even more preferably to be selected from at least one metal from the group including titanium and zirconium, with titanium being particularly preferred.

[0113] Organometallic complexes may contain two or more metal atoms, or they may contain only one metal atom, but it is preferred that they contain only one metal atom. When organometallic complexes contain two or more metal atoms, they may contain only one type of metal atom or they may contain two or more types of metal atoms.

[0114] The organometallic complex is preferably a ferrocene compound, a titanium diacene compound, a zirconium diacene compound, or a hafnium diacene compound, more preferably a titanium diacene compound, a zirconium diacene compound, or a hafnium diacene compound, further preferably a titanium diacene compound or a zirconium diacene compound, and especially preferably a titanium diacene compound.

[0115] The organometallic complex possessing photoradical polymerization initiation capability is also one of the preferred embodiments of the present invention. In the present invention, photoradical polymerization initiation capability refers to the ability to generate free radicals capable of initiating free radical polymerization through light irradiation. For example, when a composition containing a free radical crosslinking agent and an organometallic complex is irradiated with light in the wavelength region where the organometallic complex absorbs light and the free radical crosslinking agent does not absorb light, the presence or absence of photoradical polymerization initiation capability can be confirmed by checking whether the free radical crosslinking agent disappears. When confirming whether it disappears, an appropriate method can be selected according to the type of free radical crosslinking agent, such as by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography). When the organometallic complex possesses photoradical polymerization initiation capability, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconium diacene compound, or a hafnium diacene compound, further preferably a titanocene compound or a zirconium diacene compound, and especially preferably a titanocene compound. When the organometallic complex does not possess photoradical polymerization initiation ability, it is preferable that the organometallic complex is selected from at least one compound from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, acetylated titanium compounds, chelated titanium compounds, zirconium diacene compounds, and hafnium diacene compounds; it is even more preferable that the compound is selected from at least one compound from the group consisting of titanocene compounds and zirconium diacene compounds; it is further preferable that the compound is selected from at least one compound from the group consisting of titanocene compounds and zirconium diacene compounds; and titanocene compounds are particularly preferred.

[0116] The molecular weight of the organometallic complex is preferably 50 to 2,000, and even more preferably 100 to 1,000.

[0117] As organometallic complexes, compounds represented by the following formula (P) are preferably exemplified. [Chemical Formula 24] In formula (P), M is a metal atom, and R are each independently a substituent. It is preferred that the R are each independently selected from aromatic groups, alkyl groups, halogen atoms, and alkylsulfonyloxy groups.

[0118] In formula (P), iron, titanium, zirconium, or hafnium atoms are preferred as the metal atom represented by M; titanium, zirconium, or hafnium atoms are even more preferred; titanium or zirconium atoms are further preferred; and titanium atoms are particularly preferred. As the aromatic group in R of formula (P), aromatic groups having 6 to 20 carbon atoms are preferred, and aromatic hydrocarbon groups having 6 to 20 carbon atoms are preferred, such as phenyl, 1-naphthyl, or 2-naphthyl. As the alkyl group in R of formula (P), alkyl groups having 1 to 20 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are even preferred, such as methyl, ethyl, propyl, octyl, isopropyl, tributyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl. As the halogen atom in the above-mentioned R, F, Cl, Br, and I are examples. As the alkyl group constituting the alkyl sulfonyloxy group in the above-mentioned R, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Examples include methyl, ethyl, propyl, octyl, isopropyl, tributyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. The above-mentioned R may further have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acetyl, alkoxycarbonyl, aryloxycarbonyl, acetyloxy, monoalkylamino, dialkylamino, monoarylamino, and diarylamino.

[0119] Specific examples of organometallic complexes are not particularly limited, but may include tetraisopropoxy titanium, tetra(2-ethylhexyloxy) titanium, diisopropoxybis(ethyl acetate) titanium, tetraacetyl acetone titanium, diisopropoxybis(acetyl acetone) titanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium, pentamethylcyclopentadientrimethoxy titanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) titanium, and the following compounds. [Chemical Formula 25]

[0120] In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 may also be used, but are not limited thereto.

[0121] The content of the organometallic complex relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass. A lower limit of 1.0% by mass or more is more preferred, 1.5% by mass or more is further preferred, and 3.0% by mass or more is particularly preferred. An upper limit of 25% by mass or less is more preferred. One or more organometallic complexes can be used. When two or more are used, the total amount within the above-mentioned range is preferred.

[0122] <Polymerizable Compound> It is preferable that the resin composition of the present invention contains a polymerizable compound. Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0123] [Free Radical Crosslinking Agent] It is preferable that the resin composition of the present invention includes a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As a free radical polymerizable group, it is preferable that it includes a group having an ethylene unsaturated bond. Examples of groups having an ethylene unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acrylyl, maleicadiimino, (meth)acrylamide, etc. Among these, (meth)acrylyl, (meth)acrylamide, and vinylphenyl are preferred as groups having an ethylene unsaturated bond, and (meth)acrylyl is more preferred from the viewpoint of reactivity.

[0124] It is preferable that the free radical crosslinking agent is a compound having one or more ethylene unsaturated bonds, and even more preferable that it is a compound having two or more ethylene unsaturated bonds. The free radical crosslinking agent may have three or more ethylene unsaturated bonds. As a compound having two or more of the above-mentioned ethylene unsaturated bonds, a compound having 2 to 15 ethylene unsaturated bonds is preferable, a compound having 2 to 10 ethylene unsaturated bonds is more preferable, and a compound having 2 to 6 ethylene unsaturated bonds is even more preferable. Furthermore, from the viewpoint of the film strength of the obtained pattern (cured material), it is also preferable that the resin composition of the present invention includes a compound having two ethylene unsaturated bonds and a compound having three or more of the above-mentioned ethylene unsaturated bonds.

[0125] It is preferable that the molecular weight of the free radical crosslinking agent is 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. It is preferable that the lower limit of the molecular weight of the free radical crosslinking agent is 100 or more.

[0126] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Additionally, as another example, compounds substituted with unsaturated phosphonic acids, styrene, vinylbenzene derivatives, vinyl ethers, or allyl ethers can be used instead of the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0127] Furthermore, it is preferable that the free radical crosslinking agent is a compound having a boiling point of 100°C or higher at normal pressure. Examples of compounds having a boiling point of 100°C or higher at normal pressure include compounds described in paragraph 0203 of International Patent Publication No. 2021 / 112189. This content is incorporated into this specification.

[0128] As a preferred free radical crosslinking agent other than those described above, examples include free radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0129] As a free radical crosslinking agent, 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.), dinepentylenetetroxide hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which the (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. Oligopolymer types such as these can also be used.

[0130] Commercially available free radical crosslinking agents include, for example, compounds described in paragraph 0211 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0131] As a free radical crosslinking agent, compounds described in paragraph 0211 of International Publication No. 2021 / 112189 may also be used. This content is incorporated in this specification. Uraforme 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 urethane ester compounds having 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 crosslinking agent, compounds with an amino group structure or a thioether structure 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.

[0132] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups and phosphate groups. It is preferable that the free radical crosslinking agent having acid groups is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and even more preferable is a free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Particularly preferred are compounds in which the aliphatic polyhydroxy compound is neopentyl tetrol or dinepentyl tetrol in the free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Commercially available examples include, for instance, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO.,LTD.

[0133] The preferred acid value of the free radical crosslinking agent containing acid groups is 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and, consequently, excellent developability. Furthermore, it demonstrates good polymerizability. The above acid value was determined according to the description in JIS K 0070:1992.

[0134] From the viewpoint of pattern resolution and film elasticity, it is preferable to use difunctional methacrylates or acrylates as the resin composition. Specific compounds that can be used include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol diacrylate. Dimethacrylates, dimethyloltricyclodecane diacrylates, dimethyloltricyclodecane dimethacrylates, ethylene oxide (EO) adduct diacrylates of bisphenol A, EO adduct dimethacrylates of bisphenol A, PO adduct diacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylates, EO-modified diacrylates of isocyanuric acid, isocyanuric acid-modified dimethacrylates, other difunctional acrylates having urethane bonds, and difunctional methacrylates having urethane bonds. Two or more of these can be mixed as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylates with a molecular weight of approximately 200. From the viewpoint of suppressing warping caused by controlling the elastic modulus of the accompanying pattern (cured material), the resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as a free radical crosslinking agent. As monofunctional free radical crosslinking agents, 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 (meth)acrylamide, glycidyl methacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinylpyrrolidone, N-vinylcaprolactone, and allyl glycidyl ether. For monofunctional free radical crosslinking agents, compounds with a boiling point of 100°C or higher at ambient pressure are also preferred to suppress pre-exposure volatilization. Furthermore, as multifunctional or higher free radical crosslinking agents, allyl compounds such as diallyl phthalate and triallyl trimellitate are also suitable.

[0135] When a free radical crosslinking agent is contained, it is preferable that its content relative to the total solids content of the resin composition of the present invention is more than 0% by mass and less than 60% by mass. A lower limit of 5% by mass or more is more preferred. An upper limit of 50% by mass or less is more preferred, and 30% by mass or less is further preferred.

[0136] A single free radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more are used simultaneously, it is preferable that their total dosage be within the range mentioned above.

[0137] [Other Crosslinking Agents] It is preferable that the resin composition of the present invention includes other crosslinking agents different from the free radical crosslinking agents described above. In the present invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents described above. It is preferable that the compound has a plurality of groups within the molecule that promote the reaction (forming covalent bonds between the compound and other compounds in the composition or their reaction products) by photosensitization by the photoacid generator or photobase generator described above. It is even preferable that the compound has a plurality of groups within the molecule that promote the reaction (forming covalent bonds between the compound and other compounds in the composition or their reaction products) by the action of an acid or base. It is preferable that the acid or base described above is an acid or base generated from the photoacid generator or photobase generator during the exposure step. As other crosslinking agents, it is preferable that the compound has at least one group selected from the group including acetoxymethyl, hydroxymethyl and alkoxymethyl, and it is even preferable that the compound has a structure in which at least one group selected from the group including acetoxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having the following structure: a structure in which an amine-containing compound such as melamine, acetylenurea, urea, alkylurea, or benzoguanidine is reacted with formaldehyde, or formaldehyde is reacted with an alcohol, and the hydrogen atoms of the aforementioned amine groups are replaced with acetoxymethyl, hydroxymethyl, or alkoxymethyl groups. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, it can be an oligomer formed by the self-condensation of the hydroxymethyl groups of these compounds. As the aforementioned amine-containing compounds, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using acetylenurea, urea, or alkylurea are called urea-based crosslinking agents, crosslinking agents using alkylurea are called alkylurea-based crosslinking agents, and crosslinking agents using benzoguanidine are called benzoguanidine-based crosslinking agents. In these embodiments, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and it is even more preferable that it contains at least one compound selected from the group consisting of acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0138] As a compound containing at least one of alkoxymethyl and acetoxymethyl in the present invention, examples of compounds in which the alkoxymethyl or acetoxymethyl is directly substituted on the nitrogen atom or trimethylol group of the aromatic group or the urea structure described below are provided as structural examples. Regarding the alkoxymethyl or acetoxymethyl group in the above-mentioned compound, 2 to 5 carbon atoms are preferred, 2 or 3 carbon atoms are more preferred, and 2 carbon atoms are further preferred. The total number of alkoxymethyl and acetoxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above-mentioned compound is preferably 1500 or less, and preferably 180 to 1200.

[0139] [Chemical Formula 26]

[0140] R 100 represents an alkyl or acetyl group. R 101 and R 102 each independently represent a monovalent organic group that can bond with each other to form a ring.

[0141] As compounds in which alkoxymethyl or acetomethyl is directly substituted on an aromatic group, examples of compounds with the following general formula can be given.

[0142] [Chemical Formula 27]

[0143] In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl or acetyl group, R 103 represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to generate a base-soluble group (e.g., a group that is released by the action of an acid, or a group represented by -C(R 4) 2COOR 5 (R 4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is released by the action of an acid.)). Each R 105 independently represents an alkyl or alkenyl group, a, b, and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Regarding groups that decompose and generate base-soluble groups by the action of acid, groups that are released by the action of acid, and groups represented by -C(R4)2COOR5, examples of R5 include -C(R36)(R37)(R38), -C(R36)(R37)(OR39), and -C(R01)(R02)(OR39). In these formulas, R36 to R39 independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups. R36 and R37 can be bonded together to form a ring. Alkyl groups with 1 to 10 carbon atoms are preferred, and alkyl groups with 1 to 5 carbon atoms are more preferred. The alkyl groups can be either straight-chain or branched. Cycloalkyl groups with 3 to 12 carbon atoms are preferred, and cycloalkyl groups with 3 to 8 carbon atoms are more preferred. The cycloalkyl groups can be monocyclic or polycyclic structures such as condensed rings. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and phenyl is more preferred. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferred, and an alkyl group having 7 to 16 carbon atoms is more preferred. The aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred states of these alkyl and aryl groups are the same as those of the alkyl and aryl groups mentioned above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and an alkenyl group having 3 to 16 carbon atoms is more preferred. Furthermore, these groups may further have known substituents within the scope of obtaining the effects of the present invention.

[0144] R 01 and R 02 independently represent a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl or alkenyl.

[0145] The group that decomposes and generates a base-soluble group by the action of an acid, or that is removed by the action of an acid, is preferably a trialkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably a trialkyl ester group or an acetal group.

[0146] Specific examples of compounds having an alkoxymethyl group include the following structures. Examples of compounds having an acetoxymethyl group include compounds in which the alkoxymethyl group of the following compounds is replaced with an acetoxymethyl group. Examples of compounds having an alkoxymethyl group or an acetoxymethyl group within the molecule include the following compounds, but are not limited to these.

[0147] [Chemical Formula 28]

[0148] [Chemical Formula 29]

[0149] Compounds containing at least one of alkoxymethyl and acetoxymethyl can be commercially available or synthesized by known methods. From the viewpoint of heat resistance, compounds in which the alkoxymethyl or acetoxymethyl is directly substituted on the aromatic ring or trihalomethane ring are preferred.

[0150] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0151] Specific examples of urea-based crosslinking agents include, for instance, monohydroxymethylated acetylenoid, dihydroxymethylated acetylenoid, trihydroxymethylated acetylenoid, tetrahydroxymethylated acetylenoid, monomethoxymethylated acetylenoid, dimethoxymethylated acetylenoid, trimethoxymethylated acetylenoid, tetramethoxymethylated acetylenoid, monoethoxymethylated acetylenoid, diethoxymethylated acetylenoid, triethoxymethylated acetylenoid, tetraethoxymethylated acetylenoid, monopropoxymethylated acetylenoid, dipropoxymethylated acetylenoid, tripropoxymethylated acetylenoid, tetrapropoxymethylated acetylenoid, monobutoxymethylated acetylenoid, dibutoxymethylated acetylenoid, tributoxymethylated acetylenoid, or tetrabutoxymethylated acetylenoid, etc.; urea-based crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea, etc. Vinylurea crosslinking agents such as monohydroxymethylated vinylurea or dihydroxymethylated vinylurea, monomethoxymethylated vinylurea, dimethoxymethylated vinylurea, monoethoxymethylated vinylurea, diethoxymethylated vinylurea, monopropoxymethylated vinylurea, dipropoxymethylated vinylurea, monobutoxymethylated vinylurea or dibutoxymethylated vinylurea, etc.; propylene urea crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea, etc.; 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidineone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone, etc.

[0152] Specific examples of benzoguanidine-based crosslinking agents include, for example, monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, tetrabutoxymethylated benzoguanidine, etc.

[0153] Furthermore, as a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring) may also be preferred. Specific examples of such compounds include dimethylbenzene, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenylbenzene Ketones, methoxymethylbenzoic acid, 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.

[0154] As other crosslinking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (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, 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.), NIKALAC (registered trademark, same below) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO.,LTD), etc.

[0155] Furthermore, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, cyclobutane compounds and benzo[a] compounds as other crosslinking agents.

[0156] -Epoxy compound (a compound having epoxy groups)- As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy groups undergo cross-linking reactions below 200°C and do not trigger dehydration reactions due to cross-linking, thus minimizing the risk of film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition of the present invention can be effectively suppressed.

[0157] It is preferable that the epoxy compound contains polyethylene oxide. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide refers to ethylene oxide with 2 or more repeating units, preferably 2 to 15 repeating units.

[0158] Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and polysiloxanes containing epoxy groups such as polymethyl (epoxypropoxypropyl)siloxane, but are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, 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, and EPICLON (registered trademark) N-740 (these are product names, DIC). (Manufactured by Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by 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 trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. Furthermore, the following compounds may also be used preferentially.

[0159] [Chemical Formula 30]

[0160] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0161] In the above structure, considering both heat resistance and improved elongation, n is 1 to 2 and m is 3 to 7, which is better.

[0162] -Oxycyclobutane compounds (compounds having an oxycyclobutane ring)- Examples of oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethyloxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxycyclobutane)methyl] ester. Specifically, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO.,LTD. is preferred; these can be used alone or in mixtures of two or more.

[0163] -Benzozoline compounds (compounds with benzozoline groups)-Benzozoline compounds are preferred because the cross-linking reaction caused by the ring-opening addition reaction does not produce gas release during hardening, thereby reducing thermal shrinkage and inhibiting warping.

[0164] Preferred examples of benzo[a]benzyl compounds include Pd-type benzo[a]benzyl, Fa-type benzo[a]benzyl (trade names, manufactured by Shikoku Chemicals Corporation), benzo[a]benzyl adducts of polyhydroxystyrene resins, and phenolic varnish-type dihydrobenzo[a]benzyl compounds. These can be used alone or in combination of two or more.

[0165] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and especially preferably 1.0 to 10% by mass. The other crosslinking agents may be only one type or may contain two or more types. When two or more other thermal crosslinking agents are contained, it is preferable that their total content is within the above-mentioned range.

[0166] [Photopolymerization Initiator] It is preferable that the resin composition of the present invention contains a polymerization initiator capable of initiating polymerization by light and / or heat. In particular, it is preferable to contain a photopolymerization initiator. It is preferable that the photopolymerization initiator is 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, it is preferable that the photoradical polymerization initiator is photosensitive to light in the ultraviolet to visible regions. In addition, it can be an active agent that interacts with the photoexcited sensitizer and generates active free radicals.

[0167] The photoradical polymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 L·mol⁻¹·cm⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). The molar absorptivity of the compound can be determined using known methods. For example, it is preferable to determine it using an ethyl acetate solvent at a concentration of 0.01 g / L with a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer).

[0168] As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a trimethylolamine skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl skeleton, etc.), acetylphosphine compounds such as acetylphosphine oxide, hexaaryl diimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For details regarding these compounds, 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, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are incorporated herein by reference.

[0169] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0170] 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 described in Japanese Patent Application Publication No. 10-291969 and amide phosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, as described herein.

[0171] As an α-hydroxy ketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0172] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0173] As an aminoacetophenone-based initiator, a phenylphosphine oxide-based initiator, or a metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 are also preferably used. This content is incorporated herein by reference.

[0174] Oxime compounds are even better examples of photoradical polymerization initiators. By using oxime compounds, the exposure latitude can be further improved more effectively. Oxime compounds are particularly good because they have a wide exposure latitude and also act as photocuring accelerators.

[0175] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science and... The compounds described in Technology (1995, pp. 202-232), Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2017-019766, Japanese Patent No. 6065596, International Publication No. 2015 / 152153, International Publication No. 2017 / 051680, Japanese Patent Application Publication No. 2017-198865, International Publication No. 2017 / 164127 (paragraphs 0025-0038), and International Publication No. 2013 / 167515 are included in this specification.

[0176] Examples of preferred oxime compounds include 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 resin composition of the present invention, it is particularly preferred to use oxime compounds (oxime-based photoradical polymerization initiators) as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have an intramolecular linker >C=NOC(=O)-.

[0177] [Chemical Formula 31]

[0178] 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 described in Japanese Patent Application Publication No. 2012-014052) are also suitable. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) are also suitable. Additionally, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) are also suitable. Furthermore, oxime compounds with the following structure can also be used. [Chemical Formula 32]

[0179] As a photoradical polymerization initiator, for example, oxime compounds having a cyclohexane ring, oxime compounds having at least one benzene ring forming a naphthalene ring skeleton, or oxime compounds having a fluorine atom can also be used, as described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189. These contents are incorporated herein by reference.

[0180] Furthermore, as photopolymerization initiators, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl substituent bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, can also be used. These contents are incorporated herein by reference.

[0181] As a photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic cyclic group Ar OX1 with an electron-withdrawing group introduced into the aromatic ring can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cyclic group Ar OX1 include acetyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano. Acetyl and nitro are preferred, and acetyl is more preferred from the perspective of easily forming a film with excellent lightfastness, while benzoyl is further preferred. Benzyl may have substituents. As substituents, halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkyl hydrogen sulfide, aryl hydrogen sulfide, acetyl or amino are preferred, alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkyl hydrogen sulfide, aryl hydrogen sulfide or amino are even more preferred, and alkoxy, alkyl hydrogen sulfide or amino are further preferred.

[0182] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), with the compound represented by formula (OX2) being more preferred. [Chemical Formula 33] In this formula, RX1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylhydrothio, arylhydrothio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetyl, acetoxy, amino, phosphinyl, aminomethyl, or aminosulfonyl; RX2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylhydrothio, arylhydrothio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetoxy, or amino; and RX3 to RX14 each independently represent a hydrogen atom or a substituent. At least one of RX10 to RX14 is an electron-withdrawing group.

[0183] In the above formula, RX12 is an electron-withdrawing group, and RX10, RX11, RX13, and RX14 are preferably hydrogen atoms.

[0184] As a specific example of an oxime compound OX, the compound described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 is cited, the contents of which are incorporated in this specification.

[0185] Examples of preferred oxime compounds include those with specific substituents disclosed in Japanese Patent Application Publication No. 2007-269779 and those with thioaryl groups disclosed in Japanese Patent Application Publication No. 2009-191061, the contents of which are incorporated herein by reference.

[0186] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethane trihalomethane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetophosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyl diazole compounds, and 3-aryl substituted coumarin compounds.

[0187] It is even more preferable that the free radical polymerization initiator is a trihalomethane trihalomethane compound, an α-amino ketone compound, an acetophosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, and is selected from at least one compound in the group including trihalomethane trihalomethane compound, α-amino ketone compound, metallocene compound, oxime compound, triarylimidazolium dimer, and benzophenone compound, and is even more preferable to use a metallocene compound or an oxime compound.

[0188] Furthermore, as a photoradical polymerization initiator, compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359 may also be used. This content is incorporated in this specification.

[0189] Furthermore, the photoradical polymerization initiator may also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, which is incorporated herein by reference.

[0190] As a photoradical polymerization initiator, a photoradical polymerization initiator with two or more functionalities can be used. By using such a photoradical polymerization initiator, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, thus obtaining good sensitivity. Furthermore, when a compound with an asymmetric structure is used, the crystallinity decreases while the solubility in solvents increases, making it less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and compounds described in Japanese Patent Application Publication No. 2013-522445. (G) Cmpd1 to 7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators as described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342 (A), and oxime ester photoinitiators as described in Japanese Patent Application Publication No. 6469669, etc., are included in this specification.

[0191] When a photopolymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are included, the total amount within the above range is preferred. Furthermore, sometimes the photopolymerization initiator also functions as a thermal polymerization initiator; therefore, heating by an oven, heating plate, etc., can sometimes further promote crosslinking based on the photopolymerization initiator.

[0192] 〔Senser〕 The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., and produces electron transfer, energy transfer, heating, etc. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or bases. As usable sensitizers, compounds such as benzophenone, milchnerone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthrene, pyrrolopyrazolomethene, phthalocyanine, benzo[a]piperan, and indigo compounds can be used. Examples of sensitizers include milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallyl dihydroindone, and p-dimethylaminophenylallyl dihydroindone. Methylaminophenylmethylene dihydroindone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-hydroxylinylbenzophenone, isoamyl dimethylaminobenzoate The following pigments are used: isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzo[a]azole, 2-(p-dimethylaminostyrene)benzo[a]thiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzo[a]aniline, N-methylacetamide, 3',4'-dimethylacetamide, etc. Other sensitizing pigments may also be used. For detailed information on sensitizing pigments, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0193] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used simultaneously.

[0194] [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO-2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having thiocarbonyl sulfhydryl groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. Thiol compounds are particularly preferred.

[0195] Furthermore, the chain transfer agent may also be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0196] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids content of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and further preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, it is preferable that their total content is within the above-mentioned range.

[0197] <Alkali Generating Agent> The resin composition of the present invention may contain an alkali generating agent. Here, an alkali generating agent refers to a compound capable of generating an alkali through physical or chemical action. Examples of preferred alkali generating agents for the resin composition of the present invention include thermal alkali generating agents and photo-alkali generating agents. However, alkali generating agents belonging to the aforementioned specific alkali generating agents are not considered alkali generating agents as described herein. In particular, it is preferable that the resin composition contains an alkali generating agent when it contains a precursor of a cyclized resin. By containing a thermal alkali generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, resulting in improved mechanical properties and chemical resistance of the cured material, for example, improved performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. The alkali generating agent can be either an ionic or a nonionic type. Examples of alkalis generated from the alkali generating agent include, for example, secondary amines and tertiary amines. The alkali generating agent of the present invention is not particularly limited, and known alkali generating agents can be used. As known base-generating agents, for example, aminomethyloxime compounds, aminomethylhydroxylamine compounds, carbamic acid compounds, methylamine compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimine compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimine compounds, phthalimine derivative compounds, acetoylimine compounds, etc., can be used. As a nonionic alkali generating agent, compounds represented by formula (B1) or formula (B2) as described in paragraphs 0275 to 0285 of International Publication No. 2021 / 112189, compounds represented by formula (N1) as described in paragraphs 0102 to 00162 of International Publication No. 2020 / 066416, or hot alkali generating agents as described in paragraphs 0013 to 0041 of International Publication No. 2020 / 054226 are preferred. These contents are incorporated herein by reference.

[0198] Examples of alkali-generating agents can be given below, but the present invention should not be interpreted as limiting.

[0199] [Chemical Formula 34]

[0200] It is preferable for the molecular weight of the nonionic alkali generator to be below 800, more preferably below 600, and further preferably below 500. As a lower limit, it is preferable to have a molecular weight of 100 or above, more preferably above 200, and further preferably above 300.

[0201] Specific examples of preferred compounds as ionic base generating agents include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0202] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 35]

[0203] Specific examples of imine salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 36]

[0204] When the resin composition of the present invention contains an alkali generating agent, the content of the alkali generating agent is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of resin in the resin composition of the present invention. The lower limit is preferably 0.3 parts by mass or more, and 0.5 parts by mass or more is further preferred. The upper limit is preferably 30 parts by mass or less, 20 parts by mass or less is further preferred, 10 parts by mass or less is even more preferred, and it can be 5 parts by mass or less, or 4 parts by mass or less. One or more alkali generating agents can be used. When two or more are used, it is preferable that the total amount is within the above-mentioned range. Furthermore, the resin composition of the present invention can also be configured to substantially not contain any alkali generating agents other than the specific alkali generating agent. Specifically, the content of the alkali generating agent other than the specific alkali generating agent is preferably 1% by mass or less relative to the total mass of the resin composition, more preferably 0.5% by mass or less, and further preferred to be 0.1% by mass or less. The lower limit is not particularly limited and can be 0% by mass.

[0205] <Solvent> It is preferable that the resin composition of the present invention contains a solvent. Any known solvent may be used. The solvent is preferably an organic solvent. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfides, amides, ureas, alcohols, and other compounds.

[0206] Specific examples of solvents include those described in International Publication No. 2021 / 112189. Other examples include ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and N-cyclohexyl-2-pyrrolidone.

[0207] Regarding solvents, from the perspective of improving the properties of the coating surface, it is better to mix two or more forms.

[0208] In this invention, a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib 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, propylene glycol methyl ether acetate, L-glucanone, and dihydro-L-glucanone, or a mixture of two or more solvents, is preferred. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone, or the simultaneous use of N-methyl-2-pyrrolidone and ethyl lactate, is particularly preferred.

[0209] Regarding the solvent content, from the viewpoint of coatability, it is preferable that the total solids concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, further preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the required thickness of the coating and the coating method.

[0210] The resin composition of the present invention may contain only one solvent or may contain two or more solvents. When containing two or more solvents, it is preferable that their total amount is within the above-mentioned range.

[0211] <Metal Adhesion Modifier> The resin composition of the present invention preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesives, titanium-based adhesives, compounds having sulfonylurea structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0212] [Silane Coupling Agent] Examples of silane coupling agents include, for instance, compounds described in paragraph 0316 of International Patent Publication No. 2021 / 112189 and compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. 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. Additionally, it is preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0213] [Chemical Formula 37]

[0214] Other silane coupling agents include compounds described in paragraph 0318 of International Publication No. 2021 / 112189. This content is incorporated in this specification. These compounds can be used alone or in combination of two or more.

[0215] 〔Aluminum-based adhesive aid〕 Examples of aluminum-based adhesive aids include tri(acetyl ethyl acetate) aluminum, tri(acetyl acetone) aluminum, and acetyl ethyl acetate diisopropyl aluminum.

[0216] Furthermore, as other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 may also be used, and such contents are incorporated in this specification.

[0217] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting it to the lower limit or above, the adhesion between the pattern and the metal layer becomes better; by setting it to the upper limit or below, the heat resistance and mechanical properties of the pattern become better. There may be only one type of metal adhesion modifier, or there may be two or more types. When two or more types are used, it is preferable that their total content is within the above range.

[0218] <Migration Inhibitor> It is preferable that the resin composition of the present invention further includes a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively suppressed.

[0219] As a migration inhibitor, there are no particular limitations, and examples include compounds with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, succinazole ring, thiazole ring, pyrazole ring, isosuccinazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyrazine ring, pyridine ring, piperidine ring, piperidine ring, piperidine ring, 2H-piperanium ring and 6H-piperanium ring, triazine ring), compounds with thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acehydrazine derivative compounds. In particular, it is possible to use triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, as well as tetraazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

[0220] Alternatively, ion trapping agents that capture anions such as halide ions can also be used.

[0221] Other migration inhibitors include, for example, compounds described in paragraph 0304 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0222] The following compounds can be cited as specific examples of migration inhibitors.

[0223] [Chemical Formula 38]

[0224] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0225] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the above range.

[0226] <Polymerization Inhibitor> It is preferable that the resin composition of the present invention contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0227] Specific compounds that can be used as polymerization inhibitors include those described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 2,2,6,6-tetramethylpiperidine 1-oxy radical, and phenazine, etc. This content is included in this specification.

[0228] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0229] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0230] <Other Additives> The resin composition of the present invention can be formulated with various additives as needed within the scope of achieving the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). Furthermore, the resin composition of the present invention may contain urea compounds, carbodiimide compounds, or isourea compounds. By appropriately containing these components, the physical properties of the membrane and other properties can be adjusted. Regarding these components, reference can be made to, for example, to paragraph 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and to paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein. When incorporating these additives, it is preferable that their total amount is set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0231] 〔Surfactant〕 As a surfactant, various surfactants such as fluorinated surfactants, polysiloxane surfactants, and hydrocarbon surfactants can be used. The surfactant can be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0232] By including a surfactant in the resin composition of the present invention, the liquid properties (especially flowability) when preparing the coating liquid can be further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and improving the coating properties of the coated surface. Therefore, it is possible to further and better form a film with a uniform thickness and less thickness unevenness.

[0233] As fluorinated surfactants, compounds described in paragraph 0328 of International Publication No. 2021 / 112189 can be cited as examples. This content is incorporated herein by reference. Fluorinated surfactants can also preferably use fluorinated polymers (including repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propyleneoxy groups), and the following compounds can also be cited as fluorinated surfactants used in this invention. [Chemical Formula 39]

[0234] The weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Regarding fluorinated surfactants, fluoropolymers with vinyl unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Furthermore, commercially available products include, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0235] The fluorine content in fluorinated surfactants is preferably 3-40% by mass, more preferably 5-30% by mass, and especially preferably 7-25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniform coating thickness and liquid saving, and also have good solubility in the composition.

[0236] Compounds described in paragraphs 0329 to 0334 of International Patent Publication No. 2021 / 112189 can be cited as polysiloxane-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants, respectively. These contents are incorporated herein by reference.

[0237] Only one type of surfactant may be used, or two or more types may be used in combination. The surfactant content relative to the total solid content of the composition is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass.

[0238] [Higher fatty acid derivatives] In order to prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoic acid amide may be added to the resin composition of the present invention so that they are biased to the surface of the resin composition of the present invention during the drying process after coating.

[0239] Furthermore, higher fatty acid derivatives may also use compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0240] When the resin composition of the present invention contains higher fatty acid derivatives, the content of higher fatty acid derivatives relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above-mentioned range.

[0241] [Thermal Polymerization Initiator] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy, thereby initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, thus further improving solvent resistance. Furthermore, sometimes the aforementioned photopolymerization initiator also has the function of initiating polymerization by heat, and can sometimes be added as a thermal polymerization initiator.

[0242] As a thermal free radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 are examples, which are incorporated in this specification.

[0243] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may contain only one type, or it may contain two or more types. When two or more thermal polymerization initiators are included, the total amount within the above-mentioned range is preferred.

[0244] [Inorganic Particles] The resin composition of the present invention may contain inorganic particles. Specifically, the 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, boron nitride, etc.

[0245] The average particle size of the aforementioned inorganic particles is preferably 0.01–2.0 μm, more preferably 0.02–1.5 μm, further preferably 0.03–1.0 μm, and particularly preferably 0.04–0.5 μm. The aforementioned average particle size of the inorganic particles is a primary particle size and a volume average particle size. The volume average particle size can be determined by dynamic light scattering based on a Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO.,LTD.). When the above determination is difficult to perform, it can also be determined by centrifugal sedimentation transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0246] [Ultraviolet Absorber] The composition of the present invention may include an ultraviolet absorber. As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. Specific examples of ultraviolet absorbers include compounds described in paragraphs 0341-0342 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0247] In this invention, the various ultraviolet absorbers described above 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 ultraviolet absorbers are included, the content of ultraviolet absorbers 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.

[0248] [Organotitanium compound] The resin composition of this embodiment may contain an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0249] As usable organotitanium compounds, examples include those in which the organic group is bonded to titanium atoms via covalent or ionic bonds. Specific examples of organotitanium compounds include those described in paragraphs 0345-0346 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0250] When compounding with organotitanium compounds, the amount of the compounding relative to 100 parts by weight of a specific resin is preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 2 parts by weight. When the amount of the compounding is 0.05 parts by weight or more, the resulting hardened pattern more effectively exhibits good heat resistance and chemical resistance; on the other hand, when the amount of the compounding is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0251] [Antioxidant] The composition of the present invention may include an antioxidant. By including an antioxidant as an additive, the tensile properties of the cured film and its adhesion to metallic materials can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0252] The amount of antioxidant added relative to the resin is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, it is easy to obtain the effects of tensile properties and improved adhesion to metal materials even under high temperature and high humidity environments. Furthermore, by setting it to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved by utilizing the interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above-mentioned range.

[0253] [Anti-coagulant] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0254] In this invention, one type of anti-coagulant may be used alone, or two or more may be used in combination. The composition of this invention may or may not contain an anti-coagulant, but when it does contain an anti-coagulant, the content of the anti-coagulant relative to the total solid content of the composition of this invention is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.

[0255] [Phenolic Compounds] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (trade names, manufactured by ASAHI YUKIZAI CORPORATION), etc.

[0256] In this invention, a single phenolic compound may be used alone, or two or more may be used in combination. The composition of this invention may or may not contain phenolic compounds, but when phenolic compounds are included, the content of phenolic compounds relative to the total solid content of the composition of this invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

[0257] 〔Other polymeric compounds〕 Examples of other polymeric compounds include silicone resins, (meth)acrylic acid polymers copolymerized with (meth)acrylic acid, phenolic varnish resins, methyl phenolic resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may be modified forms incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0258] In this invention, one or more other polymeric compounds may be used alone or in combination. The composition of this invention may or may not contain other polymeric compounds, but when they are included, the content of other polymeric compounds relative to the total solid content of the composition of this invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

[0259] <Characteristics of the Resin Composition> The viscosity of the resin composition of the present invention can be adjusted according to the concentration of the solid components of the resin composition. From the viewpoint of coating film thickness, 1,000 mm² / s to 12,000 mm² / s is preferred, 2,000 mm² / s to 10,000 mm² / s is more preferred, and 2,500 mm² / s to 8,000 mm² / s is even more preferred. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000 mm² / s or more, it is easy to coat with the film thickness required as an insulating film for rewiring, and if it is 12,000 mm² / s or less, a coating film with excellent surface finish can be obtained.

[0260] <Limitations on the Contents of the Resin Composition> It is preferable that the moisture content of the resin composition of the present invention is less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. As a method to maintain the moisture content, examples include humidity adjustment under storage conditions and reducing the porosity of the storage container during storage.

[0261] From the viewpoint of insulation, it is preferable that the metal content of the resin composition of the present invention is less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, it is preferable that the total amount of such metals is within the above-mentioned range.

[0262] Furthermore, as a method to reduce metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0263] Regarding the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, it is preferable that the halogen atom content is less than 500 ppm by mass, more preferably less than 300 ppm by mass, and further preferably less than 200 ppm by mass. Of these, it is preferable that the content of halide ions is less than 5 ppm by mass, more preferably less than 1 ppm by mass, and further preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromide ions, is within the above-mentioned ranges. As a method for adjusting the halogen atom content, ion exchange treatment is a preferred example.

[0264] Conventionally known containers can be used as the container for the resin composition of the present invention. Furthermore, for the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, it is preferable to use a multi-layer bottle with an inner wall composed of six types of six-layer resins, or a bottle with a seven-layer structure formed by six types of resins. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0265] <Curved Product of Resin Composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the first aspect of the present invention is a cured product obtained by curing the resin composition of the present invention. Curing of the resin composition is preferably carried out by heating, preferably at a heating temperature in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C.

[0266] The cured product of the second state of the present invention comprises a cyclized resin and a carbonate compound. Preferably, the cyclized resin is a cyclized resin contained in the resin composition or a precursor of a cyclized resin modified by heating (e.g., cyclized from a precursor of a cyclized resin, or polymerized from a polymeric group contained in a resin with other resins or polymeric compounds). The preferred state of the carbonate compound is the same as that described in the resin composition of the first state of the present invention. According to this state, the cured product exhibits excellent chemical resistance. As mentioned above, it is believed that because carbonate compounds are highly polar, they are not easily soluble in organic solvents, and cured products containing such carbonate compounds exhibit excellent chemical resistance. In the present invention, the cured products of the first state and the second state are also simply referred to as "cured products". Furthermore, the cured product of the first state of the present invention may contain a carbonate compound.

[0267] From the viewpoint of good adhesion to metal, the content of carbonate compound relative to the total mass of the cured product of the present invention is preferably 0.001 to 0.100% by mass, more preferably 0.003 to 0.080% by mass, and even more preferably 0.005 to 0.050% by mass.

[0268] The form of the cured material of the present invention is not particularly limited, and it can be selected in the form of film, rod, sphere, granules, etc., depending on the application. In the present invention, the cured material is preferably in the form of film. Furthermore, by pattern processing of the resin composition, the shape of the cured material can also be selected according to the application such as forming a protective film on the wall surface, forming conductive through holes, adjusting impedance, electrostatic capacitance or internal stress, and imparting heat dissipation function. The thickness of the cured material (the film composed of the cured material) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate of the resin composition of the present invention during curing is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated according to the following formula: Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0269] <Characteristics of Cured Resin Compositions> It is preferable that the amide reaction rate of the cured resin composition of the present invention is 70% or more, more preferably 80% or more, and further preferably 90% or more. If it is 70% or more, it may sometimes result in a cured composition with excellent mechanical properties. It is preferable that the elongation at break of the cured resin composition of the present invention is 30% or more, more preferably 40% or more, and further preferably 50% or more. It is preferable that the glass transition temperature (Tg) of the cured resin composition of the present invention is 180°C or more, more preferably 210°C or more, and further preferably 230°C or more.

[0270] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed using conventionally known methods. Mixing can be performed using stirring blades, ball milling, or by rotating the container itself. A mixing temperature of 10–30°C is preferred, and 15–25°C is more preferred.

[0271] Furthermore, for the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration using a filter is preferable. Regarding the filter pore size, examples include 5 μm or less, 1 μm or less is preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is further preferred. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is preferred. The filter can be pre-cleaned with an organic solvent. In the filtration step, multiple filters can be used in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be combined. As an example of connection, for example, an HDPE filter with a 1 μm pore size can be used as the first stage, and an HDPE filter with a 0.2 μm pore size can be used as the second stage, connected in series. Furthermore, various materials can be filtered multiple times. Multiple filtrations can be performed as circulating filtration. Also, pressure filtration can be performed. When performing pressure filtration, for example, the applied pressure can be 0.01 MPa or higher and 1.0 MPa or lower, preferably 0.03 MPa or higher and 0.9 MPa or lower, more preferably 0.05 MPa or higher and 0.7 MPa or lower, and even more preferably 0.05 MPa or higher and 0.5 MPa or lower. In addition to filtration using a filter, impurity removal treatment using an adsorbent material can also be performed. Filtration using a filter and impurity removal treatment using an adsorbent material can also be combined. Known adsorbent materials can be used as the adsorbent material. For example, inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon can be used. After filtration using a filter, a further step can be performed where the resin composition filled in the bottle is placed under reduced pressure for degassing.

[0272] (Method for Manufacturing Cured Material) The method for manufacturing cured material of the present invention preferably includes a film forming step in which a resin composition is applied to a substrate to form a film. Furthermore, the method for manufacturing cured material of the present invention is more preferably including the above-described film forming step, an exposure step in which the film formed by the film forming step is selectively exposed, and a development step in which a pattern is formed by developing the film exposed by the exposure step using a developing solution. The method for manufacturing cured material of the present invention is particularly preferably including at least one of the above-described film forming step, the above-described exposure step, the above-described development step, a heating step in which the pattern obtained by the development step is heated, and a post-development exposure step in which the pattern obtained by the development step is exposed. Furthermore, the method for manufacturing cured material of the present invention is also preferably including the above-described film forming step and the step of heating the above-described film. The details of each step will be described below.

[0273] <Film Forming Step> The resin composition of the present invention can be used in a film forming step for forming a film on a substrate. The method for manufacturing the cured material of the present invention preferably includes a film forming step in which the resin composition is applied to a substrate to form a film.

[0274] 〔Substrate〕 The type of substrate can be appropriately determined according to the application. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, the substrate and metal layer formed by metal can be any of the substrates formed by plating, deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). There are no particular limitations. In this invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are even more preferred. Furthermore, a close-bonding layer, an oxide layer, etc., formed of hexamethyldisilazane (HMDS) can be provided on the surface of such substrates. Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular. Regarding the dimensions of the substrate, if it is circular, the diameter is, for example, 100–450 mm, preferably 200–450 mm. If it is rectangular, the length of the shorter side is, for example, 100–1000 mm, preferably 200–700 mm. Furthermore, the substrate can be plate-shaped, and a panel-shaped substrate (substrate) is preferred.

[0275] Furthermore, when a resin composition is applied to the surface of the resin layer (e.g., a layer composed of a hardened material) or the surface of the metal layer to form a film, the resin layer and the metal layer become substrates.

[0276] As a method for applying the resin composition of the present invention to a substrate, coating is preferred.

[0277] As applicable methods, examples include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating is preferred. From the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for about 10 seconds to 3 minutes. Furthermore, the method of transferring a coating formed by pre-applying it to a dummy support using the aforementioned method onto a substrate is also applicable. Regarding the transfer method, in this invention, 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, are also preferred. Furthermore, a step of removing excess film at the ends of the substrate can also be performed. Examples of such steps include edge bead rinse (EBR) and back-side rinse. Furthermore, a pre-wetting step can also be employed whereby, before applying the resin composition to the substrate, various solvents are applied to the substrate to improve its wettability, and then the resin composition is applied.

[0278] <Drying Step> The above-mentioned film can be used in a drying step (drying step) after the film formation step (layer formation step) to remove solvent from the formed film (layer). That is, the method for manufacturing the cured product of the present invention may include a drying step for drying the film formed by the film formation step. Furthermore, it is preferable that the above-mentioned drying step is performed after the film formation step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and further preferably 90 to 110°C. Furthermore, drying can be performed by reduced pressure. As for the drying time, 30 seconds to 20 minutes, 1 minute to 10 minutes are preferred, and 2 minutes to 7 minutes are more preferred.

[0279] <Exposure Step> The above-described film can be used in an exposure step for selective exposure of the film. That is, the method for manufacturing the cured material of the present invention may include an exposure step for selectively exposing the film formed by the film forming step. Selective exposure refers to exposing a portion of the film. Furthermore, by selective exposure, exposed areas (exposed portions) and unexposed areas (non-exposed portions) are formed on the film. The exposure amount is not particularly limited as long as it is sufficient to cure the resin composition of the present invention. For example, 50 to 10,000 mJ / cm² is preferred, and 200 to 8,000 mJ / cm² is more preferred, based on the exposure energy at a wavelength of 365 nm.

[0280] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0281] Regarding the exposure wavelength, in terms of its relationship with the light source, examples include (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h rays (wavelength 405nm), i rays (wavelength 365nm), wide wavelengths (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 the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and exposure based on i rays is even more preferred. Therefore, high exposure sensitivity can be obtained. Furthermore, the exposure method is not particularly limited, as long as at least a portion of the film composed of the resin composition of the present invention is exposed, such as exposure using a photomask or exposure based on direct laser imaging.

[0282] <Post-exposure heating step> The above-mentioned film can be used in a post-exposure heating step. That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, it is preferably 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C / minute, and further preferably 3 to 10°C / minute. Furthermore, the heating rate can be appropriately changed during the heating process. There is no particular limitation on the heating method in the post-exposure heating step, and known heating plates, ovens, infrared heaters, etc., can be used. Furthermore, it is better to conduct the heating process in an environment with low oxygen concentration by circulating inert gases such as nitrogen, helium, or argon.

[0283] <Developing Step> The exposed film can be used in a developing step to form a pattern by developing it with a developing solution. That is, the method for manufacturing the cured material of the present invention may include a developing step in which a pattern is formed by developing the film exposed by the exposure step with a developing solution. By developing, one of the exposed and non-exposed portions of the film is removed, forming a pattern. Here, the development that removes the non-exposed portion of the film by the developing step is called negative development, and the development that removes the exposed portion of the film by the developing step is called positive development.

[0284] 〔Developer solution〕 Examples of developers used in the developing step include alkaline aqueous solutions or developers containing organic solvents.

[0285] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred alkaline compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylamine hydroxide, tetrabutylamine hydroxide, tetrapentylamine hydroxide, tetrahexylamine hydroxide, tetraoctylamine hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is also mentioned. For example, when using TMAH, it is preferable that the content of alkaline compounds in the developer is 0.01 to 10% by mass of the total amount of developer, even better that it is 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass.

[0286] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph 0387 of International Publication No. 2021 / 112189. This content is incorporated in this specification. Furthermore, preferred examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; preferred examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0287] Furthermore, when the developer contains an organic solvent, one type of organic solvent or two or more types of organic solvent may be used. In this invention, it is particularly preferred that the developer contains at least one type selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone; it is even more preferred that the developer contains at least one type selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide; and it is most preferably a developer containing cyclopentanone.

[0288] When the developer contains organic solvent, it is preferable that the content of organic solvent relative to the total mass of the developer is 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more. Furthermore, the above content can also be 100% by mass.

[0289] The developer may further contain other components. Examples of other components include, for instance, known surfactants and known defoamers.

[0290] [Developer Supply Method] The developer supply method is not particularly limited as long as the desired pattern can be formed. Methods include: immersing the substrate with the film formed in the developer; swirling immersion development using a nozzle to supply the developer to the film formed on the substrate; or continuous development. The type of nozzle is not particularly limited; examples include direct-flow nozzles, spray nozzles, and atomizing nozzles. From the viewpoints of developer penetration, removal of non-image areas, and manufacturing efficiency, the method of supplying the developer using a direct-flow nozzle or the method of continuous supplying it using a spray nozzle is preferable. From the viewpoint of developer penetration into the image area, the method of supplying it using a spray nozzle is more preferable. Alternatively, the following steps can be used: after continuously supplying the developer using a direct-flow nozzle, rotating the substrate to remove the developer from the substrate; after drying by rotation, continuously supplying the developer again using a direct-flow nozzle; rotating the substrate to remove the developer from the substrate; or repeating this step several times. Furthermore, as a method for supplying the developer in the developing step, steps such as continuously supplying the developer to the substrate, maintaining the developer on the substrate in a substantially static state, vibrating the developer on the substrate using ultrasound or the like, and combining these methods are possible.

[0291] The preferred development time is 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. There is no particular limitation on the temperature of the developer during development, but it is preferred to be carried out at 10 to 45°C, and more preferably at 18°C ​​to 30°C.

[0292] In the developing step, the pattern can be further cleaned (rinsed) based on the rinsing solution after treatment with the developing solution. Alternatively, a method can be adopted such as supplying the rinsing solution before the developing solution in contact with the pattern is completely dry.

[0293] 〔rinsing solution〕 When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0294] When the rinsing solution contains an organic solvent, the same organic solvent as the organic solvent exemplified when the developer solution contains an organic solvent can be cited.

[0295] When the rinsing solution contains an organic solvent, one type of organic solvent or two or more types of organic solvent 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.

[0296] When the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains 50% or more by mass of an organic solvent, more preferably 70% or more by mass of an organic solvent, and even more preferably 90% or more by mass of an organic solvent. Alternatively, the rinsing solution may contain 100% by mass of an organic solvent.

[0297] The rinsing solution may further contain other components. Examples of other components include, for instance, known surfactants and known defoamers.

[0298] [Method for supplying rinsing solution] As long as the desired pattern can be formed, the method of supplying the rinsing solution is not particularly limited, and the following methods are available: immersing the substrate in the rinsing solution; supplying the rinsing solution by swirling and immersing the substrate; supplying the rinsing solution to the substrate using a spray nozzle; and continuously supplying the rinsing solution to the substrate using a direct current nozzle, etc. From the viewpoints of the rinsing solution's permeability, the removal of non-image areas, and manufacturing efficiency, methods such as using spray nozzles, direct current nozzles, and aerosol nozzles to supply the rinsing solution are preferred. The method of continuous supply using a aerosol nozzle is preferable, and from the viewpoint of the rinsing solution's permeability to the image area, the method of supplying using a aerosol nozzle is even better. There is no particular limitation on the type of nozzle; direct current nozzles, spray nozzles, and aerosol nozzles are examples. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing solution to the exposed film using a direct current nozzle, and a step of supplying the rinsing solution using a aerosol nozzle is even better. Furthermore, as a method for supplying the rinsing fluid in the rinsing step, one can employ a step of continuously supplying the rinsing fluid to the substrate, a step of keeping the rinsing fluid on the substrate in a substantially static state, a step of vibrating the rinsing fluid on the substrate using ultrasound or the like, and a combination of these methods.

[0299] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. There is no particular limitation on the temperature of the rinsing solution, but it is preferably carried out at 10 to 45°C, and more preferably at 18 to 30°C.

[0300] <Heating Step> The pattern obtained by the developing step (or the washed pattern if a rinsing step is performed) can be used in a heating step to heat the pattern obtained by the developing step. That is, the method for manufacturing the cured product of the present invention may include a heating step to heat the pattern obtained by the developing step. Furthermore, the method for manufacturing the cured product of the present invention may also include a heating step to heat a pattern obtained by other methods without a developing step, or a film obtained by a film forming step. In the heating step, a resin such as a polyimide precursor is cyclized into a resin such as polyimide. Furthermore, crosslinking of unreacted crosslinking groups in a specific resin or a crosslinking agent other than a specific resin is also performed. As the heating temperature (maximum heating temperature) in the heating step, 50–450°C is preferred, 150–350°C is more preferred, 150–250°C is further preferred, 160–250°C is even more preferred, and 160–230°C is particularly preferred.

[0301] The heating step is preferably performed as follows: by utilizing the effect of the alkali generated from the above-mentioned alkali generating agent through heating, the cyclization reaction of the above-mentioned polyimide precursor is promoted within the above-mentioned pattern.

[0302] Regarding the heating step, it is preferable to increase the temperature at a rate of 1 to 12°C / minute from the initial temperature to the maximum heating temperature. A rate of 2 to 10°C / minute is more preferable, and 3 to 10°C / minute is even more preferable. By setting the heating rate to 1°C / minute or higher, productivity can be ensured while preventing excessive evaporation of acid or solvent. By setting the heating rate to 12°C / minute or lower, residual stress in the hardened material can be mitigated. Furthermore, in the case of an oven capable of rapid heating, it is preferable to increase the temperature at a rate of 1 to 8°C / second from the initial temperature to the maximum heating temperature, 2 to 7°C / second is more preferable, and 3 to 6°C / second is even more preferable.

[0303] The initial heating temperature is preferably 20–150°C, more preferably 20–130°C, and further preferably 25–120°C. The initial heating temperature refers to the temperature at which the step of heating to the maximum heating temperature begins. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the dried film (layer) is preferred; for example, it is preferable to start heating from a temperature 30–200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0304] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0305] In particular, when forming a multilayered body, from the viewpoint of interlayer adhesion, a heating temperature of 30°C or higher is preferred, 80°C or higher is more preferred, 100°C or higher is even more preferred, and 120°C or higher is especially preferred. The upper limit of the above temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0306] Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at a rate of 3°C / minute and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at a rate of 2°C / minute and holding at 180°C for 120 minutes. Furthermore, as described in U.S. Patent No. 9,159,547, it is also preferable to perform the treatment while irradiating with ultraviolet light. Such pretreatment steps can improve the properties of the membrane. The pretreatment step can be performed in a short time of approximately 10 seconds to 2 hours, with 15 seconds to 30 minutes being more preferred. The pretreatment can be set as a two-stage or more step; for example, the first stage of the pretreatment step can be performed in the range of 100 to 150°C, and then the second stage of the pretreatment step can be performed in the range of 150 to 200°C. Furthermore, cooling can be performed after heating, with a cooling rate of 1 to 5°C / minute being preferred.

[0307] Regarding the heating step, from the perspective of preventing the decomposition of specific resins, it is preferable to carry out the process under reduced pressure using inert gases such as nitrogen, helium, or argon, in an environment with a low oxygen concentration. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even better. There are no particular limitations on the heating method used in the heating step; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0308] <Post-development exposure step> The pattern obtained by the development step (or the washed pattern in the case of a washing step) can be used instead of the heating step described above, or in addition to the heating step described above, for exposing the pattern after the development step in a post-development exposure step. That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the development step. The method for manufacturing the cured product of the present invention may include a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step. In the post-development exposure step, for example, a cyclization reaction of polyimide precursors, etc., can be promoted by photosensitive alkali generating agent, or a reaction of decomposing acidic groups by photosensitive acid generating agent. In the post-development exposure step, it is sufficient for at least a portion of the pattern obtained in the development step to be exposed, but it is preferable for all of the above pattern to be exposed. Based on the exposure energy conversion at the wavelength where the photosensitive compound has sensitivity, the exposure amount in the post-development exposure step is preferably 50–20,000 mJ / cm², and more preferably 100–15,000 mJ / cm². Regarding the post-development exposure step, the light source used in the above-mentioned exposure step can be used, and broadband light is preferred.

[0309] <Metal Layer Forming Step> A metal layer forming step in which the pattern obtained by the developing step (preferably the user in at least one of the heating step and the post-development exposure step) can be used to form a metal layer on the pattern. That is, the method for manufacturing the cured material of the present invention preferably includes a metal layer forming step in which a metal layer is formed on the pattern obtained by the developing step (preferably the user in at least one of the heating step and the post-development exposure step).

[0310] As a metal layer, there are no particular limitations. Existing metal types can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing such metals. Copper and aluminum are preferred, with copper being even more preferred.

[0311] There is no particular limitation on the method for forming the metal layer, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical deposition), CVD (chemical vapor deposition), lift-off, 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. As a preferred example of electroplating, electrolytic plating using copper sulfate plating solution and copper cyanide plating solution can be cited.

[0312] As for the thickness of the metal layer, 0.01 to 50 μm is preferred, and 1 to 10 μm is even better, based on the thickest part.

[0313] <Applications> Examples of applications applicable to the manufacturing method of the cured material of the present invention or the cured material of the present invention include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress-relief films, etc. Other examples include sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or patterns formed on insulating films used for practical mounting purposes, such as those described above. For these applications, references can be made to Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimide,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and the Japan Polyimide & Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010, etc.

[0314] Furthermore, the method for manufacturing the hardened material of the present invention or the hardened material of the present invention can also be used in the manufacture of offset printing plates or screen printing plates, the use of forming parts in etching, and the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0315] (Laminated body and method for manufacturing laminated body) The laminated system of the present invention refers to a structure having a plurality of layers composed of the curing material of the present invention. The laminated system of the present invention comprises a laminated body having two or more layers composed of curing material, and may also be a laminated body composed of three or more layers. Among the two or more layers composed of curing material included in the above-mentioned laminated body, at least one layer is composed of the curing material of the present invention. From the viewpoint of suppressing the shrinkage of the curing material or the deformation of the curing material that occurs with the shrinkage, it is also preferable that all the layers composed of curing material included in the above-mentioned laminated body are composed of the curing material of the present invention.

[0316] That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the hardened material of the present invention, and it is even more preferable to include the steps of repeating the method for manufacturing the hardened material of the present invention a plurality of times.

[0317] The laminate of the present invention comprises two or more layers made of a hardened material, and it is preferable that any of the layers made of the hardened material contains a metal layer between them. It is preferable that the metal layer is formed by the metal layer forming step. That is, it is preferable that the method for manufacturing the laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layers made of the hardened material between the methods for manufacturing a plurality of hardened materials. The preferred form of the metal layer forming step is as described above. As the laminate, for example, a laminate containing at least three layers in which a layer made of a first hardened material, a metal layer, and a layer made of a second hardened material are sequentially laminated is preferred. It is preferable that both the layer made of the first hardened material and the layer made of the second hardened material are layers made of the hardened material of the present invention. The resin composition of the present invention used to form the layer made of the first hardened material and the resin composition of the present invention used to form the layer made of the second hardened material can be composed of the same composition or different compositions. The metal layer in the multilayer of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0318] <Lamination Step> The method for manufacturing the laminate of the present invention preferably includes a lamination step. The lamination step includes performing at least one of the following steps sequentially on the surface of a pattern (resin layer) or a metal layer: (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step. It is possible to repeat at least one of (a) the film formation step, (d) the heating step, and the post-development exposure step. Furthermore, (e) the metal layer formation step may be included after at least one of (d) the heating step and the post-development exposure step. The lamination step may obviously and appropriately further include the aforementioned drying step, etc.

[0319] When performing a further deposition step after the deposition step, a surface activation treatment step may be performed after the above-mentioned exposure step, the above-mentioned heating step, or the above-mentioned metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details regarding the surface activation treatment will be explained later.

[0320] It is preferable to perform the above-described lamination steps 2 to 20 times, and more preferably 2 to 9 times. For example, a structure with 2 or more but less than 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure with 2 or more but less than 9 layers is even more preferred. The composition, shape, film thickness, etc. of each of the above layers can be the same or different.

[0321] In this invention, it is particularly preferred that, after the metal layer is formed, a hardened form (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, examples include repeating at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and post-development exposure step, and (e) metal layer formation step in that order, or repeating at least one of (a) film formation step, (d) heating step, and post-development exposure step, and (e) metal layer formation step in that order. By alternately performing the deposition step of the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately deposited.

[0322] (Surface Activation Treatment Step) The method for manufacturing the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the metal layer and the resin composition layer. The surface activation treatment step is generally performed after the metal layer formation step, but it can also be performed after the development step (preferably after at least one of the heating step and the post-development exposure step), and after the surface activation treatment step of the resin composition layer. The surface activation treatment can be performed only on at least a portion of the metal layer, only on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. Thus, by performing a surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on its surface can be improved. Furthermore, it is preferable that the surface activation treatment is also performed on a portion or all of the exposed resin composition layer (resin layer). Thus, by performing a surface activation treatment on the surface of the resin composition layer, the adhesion between the resin composition layer and the metal layer or resin layer disposed on the surface-activated surface can be improved. In particular, in cases such as negative development where the resin composition layer has hardened, it is less likely to be damaged by the surface treatment, thus easily improving adhesion. The surface activation treatment can be performed, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0323] (Semiconductor Device and Manufacturing Method Thereof) Furthermore, the present invention also discloses a semiconductor device comprising the cured material of the present invention or the multilayer of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device comprising a method for manufacturing the cured material of the present invention or the method for manufacturing the multilayer of the present invention. As a specific example of a semiconductor device using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description in Figure 1, the contents of which are incorporated herein by reference. [Examples]

[0324] Hereinafter, embodiments will be provided to further illustrate the present invention in detail. The materials, amounts, proportions, processing contents, processing order, etc., shown in the following embodiments can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass standards.

[0325] <Preparation Method of Cyclic Resin Precursor> 〔Synthetic Example 1: Synthesis of Cyclic Resin Precursor (Resin 1)〕 23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of bis(phthalic dianhydride) (BPDA) were placed in a separating flask, and 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of tetrahydrofuran were added. The mixture was stirred at room temperature (25°C), and 24.66 g of pyridine was added simultaneously with the stirring to obtain the reaction mixture. The mixture was allowed to cool naturally to room temperature after the exothermic reaction and left to stand for 16 hours. Next, while chilled and with stirring, a solution of 62.46 g of dicyclohexanediimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes. Then, while stirring, 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of tetrahydrofuran was added over 60 minutes. After further stirring at room temperature for 2 hours, 7.17 g of ethanol was added and stirring for 1 hour, followed by the addition of 136.83 g of tetrahydrofuran. The precipitate formed in the reaction mixture was removed by filtration, thus obtaining the reaction solution. The obtained reaction solution was added to 716.21 g of ethanol, generating a precipitate composed of crude polymer. The crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer. After filtering, the precipitate was vacuum dried to obtain 80.3 g of powdered resin 1. The molecular weight of resin 1 was determined by gel permeation chromatography (conversion to standard polystyrene), and the weight average molecular weight (Mw) was 20,000. The structure of resin 1 is presumed to be represented by the following formula (P-1).

[0326] 〔Synthetic Example 2: Synthesis of Precursor to Cyclic Resin (Resin 2)〕 21.2 g of 4,4'-oxophthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diethylene glycol dimethyl ether were mixed and stirred at 60 °C for 4 hours to synthesize a diester of 4,4'-oxophthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10 °C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10 ± 5 °C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10 ± 5 °C, and the mixture was stirred at room temperature for 2 hours. Next, 10.0 g of ethanol was added, and the mixture was stirred at room temperature for 1 hour. Then, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered off and dissolved in 500 g of tetrahydrofuran. 6000 g of water (a poor solvent) was added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered off again and dried under reduced pressure at 45°C for 3 days. 46.6 g of the dried powder was dissolved in 419.6 g of tetrahydrofuran, and 2.3 g of triethylamine was added, followed by stirring at room temperature for 35 minutes. Then, 3000 g of ethanol was added, and the precipitate was filtered off. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by Ambertech Limited) were added, and the mixture was stirred for 4 hours. Afterwards, the ion exchange resin was removed by filtration, and the resulting polymer solution was poured into 5,600 g of water to obtain a precipitate. The precipitate was filtered off and dried under reduced pressure at 45°C for 24 hours, yielding 45.1 g of resin 2. The structure of resin 2 is presumed to be represented by the following formula (P-2). The molecular weight of resin 2 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 20,000. Furthermore, by appropriately adjusting the equivalent of 4,4'-diaminodiphenyl ether, resins 2 with Mw of 5,000, 10,000, and 30,000 were also synthesized.

[0327] [Synthesis Examples 3-10: Synthesis of Precursors of Cyclic Resins (Resin 3-Resin 10)] Except for appropriate changes to the compounds used, resins 3-10, with structures represented by any one of the following formulas (P-3) to (P-10), were synthesized by the same method as in Synthesis Example 2. The Mw of resin 3 is 20,000, the Mw of resin 4 is 20,000, the Mw of resin 5 is 20,000, the Mw of resin 6 is 20,000, the Mw of resin 7 is 20,000, the Mw of resin 8 is 20,000, the Mw of resin 9 is 20,000, and the Mw of resin 10 is 20,000.

[0328] [Chemical Formula 40][Chemical Formula 41]

[0329] 〔Synthesis of Resin 11〕 In a flask equipped with a condenser and a stirrer, 18.0 g (40.5 mmol) of 4,4'-(hexafluoroisopropylidene) phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP) while removing moisture. Next, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours, and further stirred at 45°C for 3 hours. Then, 12.8 g (160 mmol) of pyridine, 10.3 g (101 mmol) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours. Finally, 50 g of N-methylpyrrolidone (NMP) was added and diluted. The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The obtained resin was dried under reduced pressure at 40°C for 1 day to obtain resin 11. The molecular weight of resin 11 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight average molecular weight (Mw) was 20,000. The structure of resin 11 is presumed to be represented by the following formula (P-11). [Chemical Formula 42]

[0330] 〔Synthesis of Resin 12〕 30.78 parts by mass of cyclohexanone were heated to 80°C under a nitrogen atmosphere. While stirring the liquid, a mixed solution of 10.21 parts by mass of 2-tetrahydrofuran-3-ylmethacrylate, 11.78 parts by mass of 1-isopropylcyclopentylmethacrylate, 57.17 parts by mass of cyclohexanone, and 0.44 parts by mass of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation] was added dropwise over 6 hours. After the addition was complete, the mixture was stirred further at 80°C for 2 hours. After the reaction solution was allowed to cool naturally, it was reprecipitated with a large amount of methanol / water (mass ratio 9:1), filtered, and vacuum dried to obtain 18.69 parts by mass of an acid-degradable resin, namely resin 9. It is presumed that the structure of resin 12 is represented by the following formula (P-12). The molecular weight of resin 12 was determined using gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 20,000. [Chemical Formula 43]

[0331] <Examples and Comparative Examples> In each example, the components listed in the table below were mixed to obtain each resin composition. In the comparative examples, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content (combination amount) of each component other than the solvent listed in the table was set to the amount (parts by mass) listed in the "parts by mass" column of each column in the table. The content (combination amount) of the solvent was set to the solid component concentration of the composition being the value (mass %) of the "solid component concentration" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent was set to the ratio listed in the "ratio" column of the table. The obtained resin compositions and comparative compositions were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm. Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding component.

[0332] [Table 1] Implementation example Comparative example Example Example Example Example Example Example Example Example Example 1 1 2 3 4 5 6 7 8 9 10 composition resin type Resin 1 Resin 1 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 polymerization initiator or Photoacid generator type I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generating agent type A-1 AR-1 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 Quality 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - Quality - - - - - - - - - - - Polymer inhibitors type B-2 B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-2 C-2 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 migration inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type E-1 E-1 - - - - - - - - - Quality 2.4 2.4 - - - - - - - - - type E-2 E-2 - - - - - - - - - Quality 0.9 0.9 - - - - - - - - - solvent type NMP NMP GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 45 45 40 40 40 40 40 40 40 40 40 type EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 evaluate Adhesion to copper substrate A D A A A A A A B B B Drug resistance C D C C C A B B A A A

[0333] [Table 2] Example Example Example Example Example Example Example Example Example Example Example 11 12 13 14 15 16 17 18 19 20 twenty one composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 polymerization initiator or Photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generating agent type A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 Quality 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - Quality - - - - - - - - - - - Polymer inhibitors type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 migration inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - Quality - - - - - - - - - - - type - - - - - - - - - - - Quality - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 evaluate Adhesion to copper substrate B A B C C C C A C C A Drug resistance A B A A A A A A C C A

[0334] [Table 3] Example Example Example Example Example Example Example Example Example Example Example twenty two twenty three twenty four 25 26 27 28 29 30 31 32 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 polymerization initiator or Photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generating agent type A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 Quality 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - Quality - - - - - - - - - - - Polymer inhibitors type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 migration inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - Quality - - - - - - - - - - - type - - - - - - - - - - - Quality - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 evaluate Adhesion to copper substrate A A A A A A A A A A A Drug resistance C B C C C B B B B B C

[0335] [Table 4] Example Example Example Example Example Example Example Example Example Example Example 33 34 35 36 37 38 39 40 41 42 43 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 polymerization initiator or Photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generating agent type A-32 A-33 A-34 A-1 A-25 A-1 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 3 10 1 0.1 1 1 1 1 type - - - - - - - A-4 AX-1 AX-2 AX-3 Quality - - - - - - - 1 1 1 1 Polymer inhibitors type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 migration inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - Quality - - - - - - - - - - - type - - - - - - - - - - - Quality - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 evaluate Adhesion to copper substrate A A A A A B C A A B C Drug resistance C B B C B B C A C C C

[0336] [Table 5] Example Example Example Example Example Example Example Example Example Example Example 44 45 46 47 48 49 50 51 52 53 54 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 7 Resin 8 Mw 30000 10000 5000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 25 45 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 - M-1 - M-1 Quality 6 6 6 6 6 6 6 - 6 - 6 polymerization initiator or Photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-3 I-1 I-4 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2 1.1 2 1.1 Alkali generating agent type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - Quality - - - - - - - - - - - Polymer inhibitors type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 migration inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - E-3 - E-3 - Quality - - - - - - - 1 - 1 - type - - - - - - - - - - - Quality - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone TMAH aqueous solution Cyclopentanone TMAH aqueous solution Cyclopentanone Development conditions burden burden burden burden burden burden burden just burden just burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 evaluate Adhesion to copper substrate A A B A A A A C A C A Drug resistance B C C C C C C C C C C

[0337] [Table 6] Example Example Example Example Example Example Example Example Example Example Example 55 56 57 58 59 60 61 62 63 64 65 composition resin type Resin 9 resin 10 resin 11 resin 12 Resin 1 / Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 / 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 17 / 17 35 35 35 35 35 35 monomer type - - M-1 - M-1 DPHA M-1 M-1 M-1 M-1 M-1 Quality - - 6 - 6 6 6 6 6 6 6 polymerization initiator or Photoacid generator type I-3 I-4 I-1 I-4 I-1 I-1 I-1 I-1 I-2 I-5 I-1 / I-2 Quality 2 2 1.1 2 1.1 1.1 0.5 3 2 2 0.6 / 0.6 Alkali generating agent type A-1 A-1 A-1 A-1 A-1 A-3 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - Quality - - - - - - - - - - - Polymer inhibitors type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B4 B-1 B-1 B-1 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 migration inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type E-3 E-3 E-3 Quality 1 1 1 type Quality solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 405 365 Exposure conditions M M M M M M M M M D M Developer TMAH aqueous solution TMAH aqueous solution Cyclopentanone TMAH aqueous solution Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions just just burden just burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 evaluate Adhesion to copper substrate C C A C A B A B A A A Drug resistance C C B C C B C B C C C

[0338] [Table 7] Example Example Example Example Example Example Example Example Example Example Example 66 67 68 69 70 71 72 73 74 75 76 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 polymerization initiator or Photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generating agent type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - Quality - - - - - - - - - - - Polymer inhibitors type B-1 B-1 B-2 B-3 B-4 B-1 / B-2 B-1 B-1 B-1 B-1 B-1 Quality 0.05 0.5 0.1 0.1 0.1 0.05 / 0.05 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-2 C-3 C-1 / C-2 Quality 1 1 1 1 1 1 0.5 3 1 1 0.5 / 0.5 migration inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - Quality - - - - - - - - - - - type - - - - - - - - - - - Quality - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 evaluate Adhesion to copper substrate A A A A A A A A A A A Drug resistance C C C C C C C C C C C

[0339] [Table 8] Example Example Example Example Example Example Example Example Example Example Example 77 78 79 80 81 82 83 84 85 86 87 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 polymerization initiator or Photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generating agent type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - Quality - - - - - - - - - - - Polymer inhibitors type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 migration inhibitors type D-2 D-3 D-4 D-1 D-1 D-1 D-1 D-1 D-1 D-1 - Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 - additive type - - - E-4 E-5 E-6 E-7 - - - - Quality - - - 2 2 2 0.1 - - - - type - - - - - - - - - - - Quality - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL NMP GBL ratio 40 40 40 40 40 40 40 30 10 20 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO EL DMSO ratio 10 10 10 10 10 10 10 20 40 35 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 evaluate Adhesion to copper substrate A A A A A A A A A A A Drug resistance C C C B B B C C C C C

[0340] [Table 9] Example Example Example Example Example Example Example Example Example Example Example 88 89 90 91 92 93 94 95 96 97 98 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 polymerization initiator or Photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generating agent type A-4 A-20 A-1 A-4 A-20 A-1 A-1 A-4 A-4 A-4 A-4 Quality 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - Quality - - - - - - - - - - - Polymer inhibitors type B-1 B-1 - - - B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 - - - 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 - - - C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 - - - 1 1 1 1 1 1 migration inhibitors type - - - - - D-1 D-1 D-1 D-1 D-1 D-1 Quality - - - - - 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - Quality - - - - - - - - - - - type - - - - - - - - - - - Quality - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 process Film thickness (μm) 20 20 20 20 20 30 10 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 200 180 160 IR Hardening time (minutes) 180 180 180 180 180 180 180 120 120 120 180 evaluate Adhesion to copper substrate A A A A A A A A B C A Drug resistance A A C A A C B A B C A

[0341] The details of each component recorded in the table are as follows.

[0342] 〔Resin〕・Resin 1~Resin 12: Resin 1~Resin 12 obtained by the above synthesis example

[0343] 〔Monomers (polymeric compounds)〕 • M-1: Compounds with the following structures, where the subscript in parentheses indicates the number of repetitions. • DPHA: Dipentaerythritol hexaacrylate [Chemical Formula 44]

[0344] 〔Polymerization initiator or photoacid generator〕 •I-1~I-5: Compounds with the following structures [Chemical Formula 45]

[0345] 〔Base-generating agents〕 ・A-1~A-34: Compounds with the following structures. A-1~A-34 are all compounds belonging to the specific base-generating agents mentioned above. ・AX-1~AX-3: Compounds with the following structures. AX-1~AX-3 are all compounds not belonging to the specific base-generating agents mentioned above. ・AR-1: Compound AR-1 with the following structure is a compound not belonging to the specific base-generating agents mentioned above. [Chemical Formula 46][Chemical Formula 47][Chemical Formula 48]

[0346] 〔Polymerization Inhibitor〕・B-1~B-4: Compounds with the following structures [Chemical Formula 49]

[0347] 〔Silane Coupling Agent (Metal Adhesion Modifier)〕 •C-1~C-3: Compounds with the following structures, where Et represents the ethyl group. [Chemical Formula 50]

[0348] 〔Migration Inhibitor〕 ・D-1~D-4: Compounds with the following structures [Chemical Formula 51]

[0349] 〔Additive〕・E-1~E-7: Compounds with the following structures [Chemical Formula 52]

[0350] [Solvents] • NMP: N-methyl-2-pyrrolidone • EL: ethyl lactate • DMSO: dimethyl sulfoxide • GBL: γ-butyrolactone

[0351] <Evaluation> 〔Evaluation of Adhesion to Copper Substrate〕 By spin coating, the resin composition or comparative composition prepared in each embodiment and comparative example was applied in a layered manner onto a copper substrate to form a resin composition layer or comparative composition layer. The copper substrate with the obtained resin composition layer or comparative composition layer was dried on a heating plate at 100°C for 5 minutes, thereby forming a resin composition layer or comparative composition layer with uniform film thickness as recorded in the "Film Thickness (μm)" column of the table on the copper substrate. In the examples where "Development Conditions" is marked "Negative" in the table, a photomask with a non-masked portion forming a square shape of 100 μm was used. In the examples where "Development Conditions" is marked "Positive" in the table, a photomask with a masked portion forming a square shape of 100 μm was used. The resin composition layer or comparison composition layer on the copper substrate was exposed using light at the exposure wavelength (nm) specified in the table's "Exposure Wavelength (nm)" column, with an exposure energy of 500 mJ / cm². In the example where "Exposure Conditions" is marked "M", a stepper was used as the light source for exposure. In the example where "Exposure" is marked "D", a direct exposure apparatus (ADTEC DE-6UH III) was used as the light source, and direct laser imaging exposure was performed within a 100 μm square area without a photomask. Afterwards, development was performed for 60 seconds using the developer specified in the table, resulting in a resin layer with a square shape of 100 μm. The "TMAH aqueous solution" listed in the table refers to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. In examples where a value is listed in the "Curing Temperature" column, a heating plate was used, and the exposed resin composition layer was heated at a rate of 10°C / min under a nitrogen atmosphere until the temperature listed in the "Curing Temperature (°C)" column was reached, and then maintained for the time specified in the "Curing Time (min)" column. In examples where "Curing Temperature (°C)" is listed as "IR", an infrared lamp heating device (ADVANCE RIKO, Inc., RTP-6) was used, and the resin film obtained in each embodiment was heated at a rate of 10°C / min under a nitrogen atmosphere until 230°C was reached, and then maintained for the time specified in the "Curing Time (min)" column. Shear force was measured on a 100μm square resin layer on a copper substrate using an adhesion tester (XYZTEC, CondorSigma) at 25°C and 65% relative humidity (RH), and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Adhesion to Copper Substrate" column of the table. Generally, the greater the shear force, the better the metal adhesion (copper adhesion) of the hardened film. -Evaluation Criteria- A: Shear force exceeds 30gf. B: Shear force exceeds 25gf but is below 30gf.C: Shear force exceeding 20gf but below 25gf. D: Shear force below 20gf. Also, 1gf is 0.00980665N.

[0352] [Evaluation of Chemical Resistance] The resin composition or comparative composition prepared in each example or comparative example was coated onto a silicon wafer by spin coating. The silicon wafer was dried at 100°C for 5 minutes on a hot plate, forming a resin composition layer of uniform thickness as described in the "Film Thickness (μm)" column of the table on the silicon wafer. In the example where the development conditions are described as "negative" and the exposure conditions as "M", the resin composition layer on the silicon wafer was exposed using a stepper. The entire surface of the photosensitive film was exposed using light of the wavelength described in the "Exposure Wavelength (nm)" column of the table without using a photomask. The exposure amount was set to 500 mJ / cm². In the example where the development conditions are described as "negative" and the exposure conditions as "D", exposure was performed using a direct exposure apparatus (ADTEC DE-6UH III). The entire surface of the photosensitive film was exposed using light of the wavelength described in the "Exposure Wavelength (nm)" column of the table. The exposure was set to 500 mJ / cm². In examples where the development conditions were marked "positive," no exposure was performed. In examples where a value was recorded in the "Curing Temperature (°C)" column, a heating plate was used, and the resin film (resin composition layer) obtained in each embodiment or comparative example was heated at a rate of 10°C / min under a nitrogen atmosphere until the temperature recorded in the "Curing Temperature (°C)" column was reached. This temperature was then maintained for the time recorded in the "Curing Time (min)" column, thereby forming a cured film. In examples where the "Curing Temperature (°C)" column was marked "IR," an infrared lamp heating device (ADVANCE RIKO, Inc. RTP-6) was used, and the resin film obtained in each embodiment was heated at a rate of 10°C / min under a nitrogen atmosphere until the temperature reached 230°C. This temperature was then maintained for the time recorded in the "Curing Time (min)" column, thereby forming a cured film. The obtained cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated. Chemical: A mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution in a 90:10 ratio. Evaluation conditions: The above-mentioned hardened film was immersed in the above-mentioned chemical mixture at 75°C for 15 minutes. The film thickness before and after immersion was compared to calculate the dissolution rate (nm / min). The obtained dissolution rate values ​​were evaluated according to the following evaluation criteria, and the evaluation results were recorded in the "Chemical Resistance Evaluation" column. It can be said that the slower the dissolution rate, the better the chemical resistance. -Evaluation Criteria- A: Dissolution rate less than 250 nm / min. B: Dissolution rate ≥ 250 nm / min but less than 500 nm / min. C: Dissolution rate ≥ 500 nm / min but less than 750 nm / min. D: Dissolution rate ≥ 750 nm / min.

[0353] As can be seen from the above results, the cured product formed from the resin composition of the present invention exhibits excellent adhesion to metal. The comparative composition of Comparative Example 1 did not contain a specific alkali-generating agent. Regarding such comparative compositions, it is known that the cured product obtained has poor adhesion to metal.

[0354] <Example 101> The resin composition used in Example 5 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 5 minutes, a photosensitive film with a thickness of 20 μm was formed. Exposure was then performed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-space pattern and a linewidth of 10 μm). After the exposure, development was performed with cyclohexanone for 2 minutes, followed by rinsing with PGMEA for 30 seconds to obtain the layer pattern. Next, the temperature was increased at a rate of 10°C / min under nitrogen atmosphere to reach 230°C, and then maintained at 230°C for 180 minutes to form an interlayer insulating film for the rewiring layer. This interlayer insulating film for the rewiring layer exhibits excellent insulation properties. Furthermore, the use of interlayer insulating films in these rewiring layers to manufacture semiconductor devices has confirmed normal operation.

Claims

1. A resin composition comprising: a resin; and a base generating agent, wherein the base generating agent is a compound represented by the following formula (1-1), wherein in formula (1-1), L1 is an n+m valence linking group of one of the structures shown in the following chemical formula 19, R1 independently represents a monovalent dimethylpiperidine ring or a monovalent dimethyl porphyrin ring, R2 represents a hydrocarbon group that may have substituents, R1 can be linked to each other to form a ring structure, m represents 1 or 2, and n represents 1 or 2: [Chemical Formula 19] In the above structure of L1, * represents the bonding site of a carbonyl group directly bonded to the nitrogen atom of R2 in formula (1-1), and # represents the bonding site of a carbonyl group directly bonded to the nitrogen atom of R1 in formula (1-1).

2. The resin composition as claimed in claim 1, wherein the aforementioned L1 in formula (1-1) comprises at least one aromatic ring structure.

3. The resin composition as described in claim 1, wherein the bonding sites of the aforementioned L1 in formula (1-1) and the m+n carbonyl groups in formula (1-1) are all carbon atoms.

4. The resin composition as described in any one of claims 1 to 3, wherein the dimethylpiperidine ring and the dimethyl porphyrin ring represented by R1 in formula (1-1) are cis-forms.

5. A resin composition as described in any one of claims 1 to 3, wherein the resin is selected from at least one resin selected from the group consisting of cyclized resins and their precursors.

6. A resin composition as described in any one of claims 1 to 3, wherein the resin comprises at least one group selected from the group consisting of a group having an ethylene unsaturated bond, an epoxy group, an oxobutyl group, an aldehyde group, and a ketone group.

7. The resin composition as described in any one of claims 1 to 3, further comprising a photopolymerization initiator.

8. The resin composition as described in any one of claims 1 to 3, further comprising a polymeric compound.

9. The resin composition as described in any one of claims 1 to 3, further comprising an organometallic complex.

10. A resin composition as described in any one of claims 1 to 3, comprising a cyclized resin or a precursor thereof as the aforementioned resin and used to form an interlayer insulating film for a rewiring layer.

11. A cured material formed by curing the resin composition described in any one of claims 1 to 10.

12. A laminate comprising two or more layers made of the hardened material described in claim 11, wherein a metal layer is included between the layers made of the hardened material.

13. A method for manufacturing a hardened material, comprising a film forming step of applying a resin composition described in any one of claims 1 to 10 to form a film on a substrate.

14. A method for manufacturing a hardened material as described in claim 13, comprising: The exposure step involves selectively exposing the aforementioned film; The developing step involves using a developing solution to develop the aforementioned film to form a pattern.

15. A method for manufacturing a hardened material as described in claim 13, comprising a heating step of heating the aforementioned film at 50 to 450°C.

16. A method for manufacturing a laminate, comprising a method for manufacturing a hardened material as described in any one of claims 13 to 15.

17. A method for manufacturing a semiconductor device, comprising a method for manufacturing the hardened material as described in any one of claims 13 to 15.

18. A method for manufacturing a semiconductor device, comprising the method for manufacturing a multilayer as described in claim 16.

19. A semiconductor device comprising the hardened material described in claim 11.

20. A semiconductor device comprising the stack as described in claim 12.