Curable composition and reaction product

Abstract

To provide a curable composition which can be patterned by light irradiation.SOLUTION: The curable composition contains: a photobase generator; a base proliferator; at least one polymer selected from the group consisting of a polyimide, a polybenzoxazole, and a polyphenylene ether; and a polyfunctional epoxy compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to curable compositions and reaction products. [Background technology]

[0002] Photopolymerizable materials, which are polymerized by irradiation with light, are widely used in practical applications because the polymerization reaction can be precisely controlled with relatively simple operations, and they occupy an important position in, for example, the fields of electronic materials and printing materials. As photopolymerizable materials, for example, radical polymerization type resin compositions containing a photoinitiator that generates radical species upon exposure and a radically polymerizable monomer or oligomer, and acid catalyst type resin compositions containing a photoacid generator that generates acid upon exposure and a monomer or oligomer that polymerizes by the action of acid, have been actively studied.

[0003] On the other hand, photopolymerizable materials also include base-catalyzed materials containing a photobase generator that generates a base upon exposure and a monomer or oligomer that polymerizes under the action of a base. Known photobase generators include, for example, ionic photobase generators that correspond to salts of carboxylic acids with strong bases such as guanidine (see, for example, Non-Patent Document 1). In such ionic photobase generators, a decarboxylation reaction occurs at the carboxy group upon exposure, liberating the strong base that formed a salt with the carboxy group, thereby generating a base.

[0004] In response to this, non-ionic photobase generators have also been investigated. Known examples of non-ionic photobase generators include carbamates having a nitrobenzyl skeleton, which undergo a decarboxylation reaction upon exposure to light, liberating a primary amine or a secondary amine to generate a base (see, for example, Non-Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Non-Patent Document 1] K.Arimitsu,R.Endo,Chem.Mater.2013,25,4461-4463. [Non-patent document 2] JFCameron,JMJFrechet,J.Am.Chem.Soc.1991,113,4303. Summary of the Invention [Problem to be solved by the invention]

[0006] In order to reduce the amount of transmission loss that occurs when radio waves transmitted for communication are converted into energy such as heat in a dielectric, it is desirable to use a material with low dielectric properties, such as a low dielectric constant and a low dielectric loss tangent. Examples of resins that have excellent heat resistance and low dielectric properties include resins such as polyimide. However, polyimide is difficult to process, and in order to perform patterning by light irradiation, it is necessary to introduce a photoreactive group such as an ethylenically unsaturated double bond into the polyimide. The present inventors have investigated a curable composition that allows patterning by light irradiation without introducing a photoreactive group such as an ethylenically unsaturated double bond into the polyimide.

[0007] An object of the present invention is to provide a curable composition that can be patterned by irradiation with light, and a reaction product obtained by reacting this photoreactive composition. [Means for solving the problem]

[0008] Specific means for solving the above problems are as follows. <1> a photobase generator; a base multiplier; at least one polymer selected from the group consisting of polyimide, polybenzoxazole, and polyphenylene ether; A curable composition comprising a polyfunctional epoxy compound. <2> The photobase generator is at least one selected from the group consisting of carbamates having a nitrobenzyl skeleton, compounds having a coumaric acid amide skeleton, and ionic base generators which are salts of a base and a carboxylic acid. <1> The curable composition according to claim 1. <3> The base amplifier is a compound that decomposes under the action of a base to generate a base containing an aminopyridine skeleton. <1> or <2> The curable composition according to claim 1. <4> The base amplifier is a compound that decomposes under the action of a base to generate 4-methylaminopyridine. <1> ~ <3> 10. The curable composition according to claim 9, wherein the curable composition is a curable composition having a molecular weight of 100 or more. <5> Multifunctional epoxy compounds include 1,3,5-tris(3-oxiranylpropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione <1> ~ <4> 10. The curable composition according to claim 9, wherein the curable composition is a curable composition having a molecular weight of 100 or more. <6> The polymer includes a polyimide containing a structural unit represented by the following general formula (A): <1> ~ <5> 10. The curable composition according to claim 9, wherein the curable composition is a curable composition having a molecular weight of 100 or more.

[0009] [ka]

[0010] In the general formula (A), R represents a tetravalent organic group, and R' represents a divalent organic group. <7> <1> ~ <6> 10. A reaction product obtained by reacting the curable composition according to any one of the above items. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a curable composition that can be patterned by irradiation with light, and a reaction product obtained by reacting this photoreactive composition. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a graph showing the relationship between the exposure dose and the film remaining rate in a coating film formed using curable composition 1. [Figure 2]1 is a graph showing the relationship between heating time and the residual rate of epoxy groups in a coating film formed using curable composition 1 before and after light irradiation. [Figure 3] 1 is a graph showing the results of measurement by a Fourier transform infrared spectrophotometer (FT-IR) of a coating film before and after development (reaction product 3), a polyimide (PHI) alone, and a polyfunctional epoxy compound alone. DETAILED DESCRIPTION OF THE INVENTION

[0013] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the numerical ranges described in stages in the present disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range. The upper or lower limit of a numerical range described in the present disclosure may be replaced by a value shown in the examples. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.

[0014] [Curable composition] The curable composition of the present disclosure is a composition comprising a photobase generator, a base amplifier, at least one polymer selected from the group consisting of polyimide, polybenzoxazole, and polyphenylene ether, and a multifunctional epoxy compound.

[0015] When the curable composition of the present disclosure is irradiated with light, a base is generated from the photobase generator, and the generated base acts on the base multiplier to generate more base. The base generated from the photobase generator or the base amplifier acts on the polyfunctional epoxy compound, causing the reaction to proceed, and the polyfunctional epoxy compound reacts to form a crosslinked structure. In this case, the polyimide, polybenzoxazole, or polyphenylene ether polymer has poor reactivity and, for example, becomes entangled in the crosslinked structure. Therefore, in the light-irradiated region of the curable composition, the crosslinking reaction proceeds to form a crosslinked structure in which polyimide is entangled, while in the light-unirradiated region, the crosslinking reaction is inhibited and the curable composition is removed by development, thereby enabling patterning by light irradiation.

[0016] The curable composition can be used, for example, as a photosensitive material, a semiconductor sealing material, an adhesive, etc. The curable composition may be a negative curable composition.

[0017] (Photobase Generator) The curable composition of the present disclosure contains a photobase generator. The photobase generator includes a compound that generates a base upon irradiation with light.

[0018] The photobase generator is preferably at least one selected from the group consisting of carbamates having a nitrobenzyl skeleton, compounds having a coumaric acid amide skeleton, and ionic base generators which are salts of a base and a carboxylic acid.

[0019] Examples of carbamates having a nitrobenzyl skeleton include compounds having a structure represented by the following general formula (3): Carbamates having a nitrobenzyl skeleton are compounds that undergo a decarboxylation reaction upon irradiation with light, generating a base.

[0020] [ka]

[0021] In general formula (3), R a , R b , R c and R dare each independently a hydrogen atom or a monovalent substituent, and R e is a monovalent substituent containing a nitrogen atom attached to the carbonyl carbon.

[0022] R a , R b , R c and R d Examples of the monovalent substituent in the above formula include an alkyl group, an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylthio group, an arylthio group, a cyano group (-CN), a halogen atom, a nitro group, a haloalkyl group (halogenated alkyl group), a hydroxyl group (-OH), a mercapto group (-SH), an amino group, an aromatic hydrocarbon group, and an aromatic heterocyclic group.

[0023] R a and R d is preferably a hydrogen atom, and R b and R c is preferably an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or an n-butoxy group.

[0024] The photobase generator may contain a structure represented by general formula (1)-12, (1)-13, (1)-14, or (2)-1. For example, in the structure represented by general formula (3) in a carbamate having a nitrobenzyl skeleton, R e may be a structure represented by general formula (1)-12, (1)-13, (1)-14 or (2)-1.

[0025] [ka]

[0026] [ka]

[0027] In general formula (1)-12 to general formula (1)-14, R 22 , R 23 , R 24 , R 32 , R 33 , R 41 , R 42 , R 43 and R 44 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R 21 and R 31 R each independently represents a hydrocarbon group which may have a substituent, and * represents the bonding position at which it bonds to the carbonyl carbon in general formula (3) to form a single bond. 21 ~R 24 At least two of may be bonded to each other to form a ring structure, R 31 ~R 33 At least two of may be bonded to each other to form a ring structure, R 41 ~R 44 At least two of these may be bonded to each other to form a ring structure.

[0028] R 21 ~R 24 , R 31 ~R 33 , and R 41 ~R 44 The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group (aryl group), may be an aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with an aromatic hydrocarbon group, or may be a polycyclic hydrocarbon group in which a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group are condensed.

[0029] The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group.

[0030] The linear or branched alkyl group preferably has 1 to 20 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 1-methylbutyl group, an n-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, an n-heptyl group, Examples of such alkyl groups include 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups.

[0031] The cyclic alkyl group preferably has 3 to 20 carbon atoms, and examples of the alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, and tricyclodecyl groups. Examples of the cyclic alkyl group include those in which one or more hydrogen atoms are substituted with a linear, branched, or cyclic alkyl group. Examples of the linear, branched, and cyclic alkyl group that substitutes a hydrogen atom include those exemplified above for the alkyl group.

[0032] The unsaturated aliphatic hydrocarbon group may be linear, branched, or cyclic, and if cyclic, may be monocyclic or polycyclic. The unsaturated aliphatic hydrocarbon group preferably has 2 to 20 carbon atoms. Examples of the unsaturated aliphatic hydrocarbon group include groups in which one or more single bonds (CC) between carbon atoms in the alkyl group are replaced with unsaturated double bonds (C=C) or triple bonds (C≡C). The unsaturated aliphatic hydrocarbon group may have one or more unsaturated bonds. When the number of unsaturated bonds is two or more, the unsaturated bonds may be double bonds only, triple bonds only, or a mixture of double and triple bonds. In the unsaturated aliphatic hydrocarbon group, the position of the unsaturated bond is not particularly limited.

[0033] Preferred examples of the unsaturated aliphatic hydrocarbon group include linear or branched alkenyl and alkynyl groups, which correspond to groups having one unsaturated bond, and cyclic cycloalkenyl and cycloalkynyl groups. Examples of the alkenyl group include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), and a cyclohexenyl group.

[0034] The aryl group may be either monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms. Examples of such aryl groups include phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p-tolyl, and xylyl (dimethylphenyl) groups, and also include aryl groups in which one or more hydrogen atoms are further substituted with such aryl groups, the alkyl groups, or the like. The aryl groups having such substituents preferably have 6 to 20 carbon atoms, including the carbon atoms of the substituents.

[0035] In general formula (1)-12, R 21 , R 22 , R 23 and R 24When two or more of the hydrocarbon groups are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring together with the nitrogen atom to which these hydrocarbon groups are bonded and the carbon atom bonded to this nitrogen atom (the same carbon atom to which all three nitrogen atoms are bonded). Here, "two or more hydrocarbon groups are bonded to each other" means, for example, 21 ~R 24 In the case where only two, three or all (four) of the above are hydrocarbon groups, and only two or three of the hydrocarbon groups are bonded to each other, or in the case where R 21 ~R 24 All of the above (four types) are hydrocarbon groups, and there are cases where all of these hydrocarbon groups are bonded to each other.

[0036] When two or more hydrocarbon groups are bonded to each other, the position of the carbon atom to which they are bonded (bonding position) is not particularly limited. For example, when the hydrocarbon groups to be bonded are linear or branched, the bonding position may be a terminal carbon atom of the hydrocarbon group, or a so-called root carbon atom directly bonded to the nitrogen atom shown in general formula (1)-12 of the hydrocarbon group, or a carbon atom intermediate between the terminal and root. On the other hand, when the hydrocarbon groups to be bonded are cyclic or have both a chain structure and a cyclic structure, the bonding position may be a root carbon atom or any other carbon atom.

[0037] R 21 , R 22 , R 23 and R 24 When two of the hydrocarbon groups are bonded to each other, the ring formed thereby may be either monocyclic or polycyclic.

[0038] In general formula (1)-13, R 31 , R 32 and R 33When two or more of the hydrocarbon groups are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring together with the nitrogen atom or carbon atom to which these hydrocarbon groups are bonded and the carbon atom bonded to this nitrogen atom or the nitrogen atom bonded to the carbon atom. Here, "two or more hydrocarbon groups are bonded to each other" means that, as described above, R 21 ~R 24 This means that the hydrocarbon groups of either R 31 ~R 33 In the case where only two or all (three) of the above are hydrocarbon groups and only two of the hydrocarbon groups are bonded to each other, or in the case where R 31 ~R 33 All of these (three types) are hydrocarbon groups, and all of these hydrocarbon groups may bond to each other. The way in which the hydrocarbon groups bond to each other also varies depending on the R 21 ~R 24 The same is true for the case.

[0039] In general formula (1)-14, R 41 , R 42 , R 43 and R 44 When two or more of the hydrocarbon groups are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring together with the nitrogen atom to which these hydrocarbon groups are bonded and the carbon atom bonded to this nitrogen atom (the same carbon atom to which all three nitrogen atoms are bonded). Here, "two or more hydrocarbon groups are bonded to each other" means that, as described above, 21 ~R 24 This means that the hydrocarbon groups of either R 41 ~R 44 In the case where only two, three or all (four) of the above are hydrocarbon groups, and only two or three of the hydrocarbon groups are bonded to each other, or in the case where R 41 ~R 44 All of these (four types) are hydrocarbon groups, and all of these hydrocarbon groups may bond to each other. The way in which the hydrocarbon groups bond to each other also varies depending on the R 21 ~R 24 This is the same as in the case of

[0040] Among the structures represented by the general formula (1-13), R 32 is a hydrocarbon group, and R 31 and R 33 are preferably hydrocarbon groups bonded to each other, and R 32 is a methyl group, and R 31 and R 33 More preferably, they are bonded to each other to form an ethylene group.

[0041] Among the structures represented by the general formula (1-14), R 41 ~R 44 are preferably all hydrocarbon groups, and R 41 ~R 44 are more preferably all methyl groups.

[0042] In general formula (2)-1, R5 and R6 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, R7 represents a divalent linking group, and two * represent bonding positions which bond to the carbonyl carbon in general formula (3) to form a single bond. At least two of R5 to R7 may bond to each other to form a ring structure. Examples of the divalent linking group include divalent hydrocarbon groups, more specifically, divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, etc. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

[0043] The structure represented by general formula (2)-1 is preferably a structure represented by the following general formula (2)-2.

[0044] [ka]

[0045] In general formula (2)-2, R8 represents a divalent linking group, and the two * represent bonding positions where they bond to the carbonyl carbon in general formula (3) to form single bonds. Examples of the divalent linking group include divalent hydrocarbon groups, more specifically, divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, etc. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

[0046] R in general formula (3) e is a compound having a structure represented by general formula (2)-1, R in general formula (3) e Examples of the compound having the structure represented by general formula (2)-2 include the following compounds (3)-1 and (3)-2.

[0047] [ka]

[0048] [ka]

[0049] In each of the compound (3)-1 and the compound (3)-2, the two nitrobenzyl skeletons contained therein may be the same or different.

[0050] The compound having a coumaric acid amide skeleton can be exemplified by a compound having a structure represented by the following general formula (4): j is released, forming a cyclic compound, while HR j This generates an amine compound represented by the formula:

[0051] [ka]

[0052] In general formula (3), R f , R g , R h and R i are each independently a hydrogen atom or a monovalent substituent, and R jis a monovalent substituent containing a nitrogen atom attached to the carbonyl carbon.

[0053] The compound having a coumaric acid amide skeleton is preferably a compound that generates, upon irradiation with light, a base in which a hydrogen atom is bonded to a nitrogen atom bonded to a carbonyl carbon, and coumarin or a coumarin derivative.

[0054] In general formula (4), R f , R g , R h and R i R each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylthio group, an arylthio group, a cyano group (-CN), a halogen atom, a nitro group, a haloalkyl group (halogenated alkyl group), a hydroxyl group (-OH), a mercapto group (-SH), an amino group, an aromatic hydrocarbon group, or an aromatic heterocyclic group. f ~R i At least two of these may be bonded to each other to form a ring structure.

[0055] R j may be a structure represented by general formula (1)-12, (1)-13, (1)-14, (2)-1 or (2)-2.

[0056] Examples of ionic base generators that are salts of a base and a carboxylic acid include conventionally known ionic base generators, such as the ionic base generator corresponding to a salt of a strong base such as guanidine with an aromatic component-containing carboxylic acid described in "K. Arimitsu, R. Endo, Chem. Mater. 2013, 25, 4461-4463," ionic base generators such as carboxylates formed from carboxylic acids and bases described in JP-A-2011-80032, and ionic photobase generators such as salts of aromatic component-containing carboxylic acids with tertiary amines described in JP-A-2017 / 122744.

[0057] The photobase generator contained in the curable composition of the present disclosure may be one type only, or two or more types, and when two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0058] In the curable composition of the present disclosure, the content of the photobase generator may be 1 mol% to 20 mol%, 2 mol% to 15 mol%, or 3 mol% to 10 mol%, relative to the epoxy groups contained in the polyfunctional epoxy compound. When the content of the photobase generator is 1 mol% or more, the base generated from the photobase generator acts sufficiently on the base multiplier, accelerating the generation of the base. Furthermore, when the content of the photobase generator is 20 mol% or less, excessive use of the photobase generator is suppressed.

[0059] (base multiplier) The hardenable compositions of the present disclosure include a base multiplier. A base amplifying agent is a compound that decomposes under the action of a base in the system to generate new base molecules. Such a self-catalytic reaction that generates new bases through a base-induced decomposition reaction is called a base amplifying reaction. It is desirable for the base amplifying agent to decompose under the action of a base in the system, to release new base molecules during the decomposition process, and to be stable in the absence of a base. By including a photobase generator and a base amplifying agent in the curable composition, bases are generated in a chain reaction in the composition when energy such as light is applied.

[0060] Examples of base amplifiers include compounds having a carbamate structure in the molecule. In the case of compounds having a carbamate structure, an aliphatic amine is generated as a base. The base amplifier may also be a compound that generates a polyfunctional amine. Compounds that generate a polyfunctional amine are suitable as components of curable compositions. Specific examples of base amplifiers include compounds described in paragraphs 0010 to 0032 of JP 2000-330270 A and paragraphs 0116 to 0146 of JP 2006-20539 A. For details about base multipliers, please refer to "New Trends in Photofunctional Polymer Materials - Latest Technology and Its Prospects" (edited by Ichimura Kunihiro, CMC Publishing, 2008).

[0061] Suitable examples of the base multiplier include compounds represented by the following general formula (1):

[0062] [ka]

[0063] In the formula, R1 and R2 are hydrogen, a substituent, or an electron-withdrawing group, at least one of which is an electron-withdrawing group, R3 and R4 are hydrogen or a substituent, and Z represents a group represented by the following general formula (1)-11, general formula (1)-12, general formula (1)-13, general formula (1)-14, or general formula (1)-15.

[0064] [ka]

[0065] [ka]

[0066] In the general formula (1)-11, the general formula (1)-12, the general formula (1)-13, the general formula (1)-14, or the general formula (1)-15, R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , R 31 , R 32 , R 33 , R 41 , R 42 , R 43 , R 44 , R 51 and R 52 R each independently represents a hydrogen atom or a hydrocarbon group. 11 , R 12 and R13 When two or more of the groups are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring, and R 21 , R 22 , R 23 and R 24 When two or more of the groups are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring, and R 31 , R 32 and R 33 When two or more of the groups are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring, and R 41 , R 42 , R 43 and R 44 When two or more of the above are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring. * represents a bond to the carbon atom of the carbonyl group. n is an integer of 0 to 4.

[0067] Examples of the electron-withdrawing group in R1 and R2 include a fluorenyl group, an organic sulfoxide group, a cyano group, a nitro group, an ester group, a carbonyl group, an amide group, and a pyridyl group.

[0068] The base amplifier may contain a compound that decomposes under the action of a base to generate a base containing an aminopyridine skeleton, or may contain a compound that decomposes under the action of a base to generate 4-methylaminopyridine (hereinafter also referred to as a specific compound).

[0069] The specific compound is a compound represented by general formula (1) in which Z is the following general formula (1)-15A.

[0070] [ka]

[0071] In general formula (1)-15A, R 51 and R 52 each independently represents a hydrogen atom or a hydrocarbon group.

[0072] The curable composition of the present disclosure may contain only one type of base amplifier, or two or more types, and when two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0073] In the curable composition of the present disclosure, the content of the base amplifier may be 0.5 mol % to 10 mol %, 1 mol % to 5 mol %, or 1.5 mol % to 3 mol %, relative to the epoxy groups contained in the polyfunctional epoxy compound. When the content of the base amplifier is 0.5 mol % or more, the base generated from the base amplifier acts on the polyfunctional epoxy compound, facilitating the reaction to proceed sufficiently. Furthermore, when the content of the base amplifier is 10 mol % or less, preferably 3 mol % or less, the storage stability of the curable composition in a dark place is excellent.

[0074] (polymer) The curable composition of the present disclosure comprises at least one polymer selected from the group consisting of polyimides, polybenzoxazoles, and polyphenylene ethers. The polymer contained in the curable composition may contain only one type of polymer, may contain two or more types of the same type of polymer, or may contain different types of polymers.

[0075] The polymer may include a polyimide containing a structural unit represented by the following general formula (A):

[0076] [ka]

[0077] In general formula (A), R represents a tetravalent organic group, and R' represents a divalent organic group. The polyimide may have a plurality of structural units represented by general formula (A), and R and R' in the plurality of structural units may be the same or different.

[0078] The tetravalent organic group for R preferably has 4 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group in R may contain an aromatic ring.

[0079] Specific examples of the tetravalent organic group represented by R include groups represented by the following formulae (B-1) to (B-5).

[0080] [ka]

[0081] In formulas (B-1) to (B-5), * represents a bond bonded to the carbon atom of the carbonyl group. x is an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), or a group combining two or more of these.

[0082] The divalent organic group for R' preferably has 4 to 30 carbon atoms, more preferably 6 to 25 carbon atoms, and even more preferably 12 to 18 carbon atoms. The divalent organic group in R' may contain an aromatic ring.

[0083] Specific examples of the divalent organic group represented by R' include groups represented by the following formulae (C-1) and (C-2).

[0084] [ka]

[0085] In formula (C-1) and formula (C-2), R y1 , R y2 and R y3 each independently represents a hydroxy group, an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom; R zrepresents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-OC(=O)-), or a group combining two or more of these, and each n independently represents an integer of 0 to 4.

[0086] Polybenzoxazole is a polymer containing a benzoxazole structure in its structural unit. The polybenzoxazole preferably contains a compound having a structural unit represented by the following general formula (PB01).

[0087] [ka]

[0088] Polyphenylene ether is a polymer containing a phenylene ether structure in its structural unit. The polyphenylene ether preferably contains a compound having a structural unit represented by the following general formula (PPE1).

[0089] [ka]

[0090] In the general formula (PPE1), R y4 represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group or a halogen atom; and n represents an integer of 0 to 4.

[0091] (Multifunctional epoxy compound) The curable composition of the present disclosure includes a multifunctional epoxy compound. The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups.

[0092] Examples of polyfunctional epoxy compounds include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, carboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin Examples of suitable polyfunctional epoxy compounds include 1,3,5-tris(3-oxiranylpropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,13-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, and 1,3,5-tris(3-oxiranylpropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0093] (Other ingredients) The curable composition of the present disclosure may further contain other components in addition to the photobase generator, the base amplifier, the polymer, and the polyfunctional epoxy compound. The other components are not particularly limited as long as they do not impair the effects of the present invention, and can be selected arbitrarily depending on the purpose. The curable composition may contain only one type of other component, or two or more types. When two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0094] Examples of the other components include reactive compounds other than polyfunctional epoxy compounds (other reactive compounds), sensitizers, fillers, pigments, solvents, and the like.

[0095] <Other reactive compounds> The curable compositions of the present disclosure may contain other reactive compounds. Other reactive compounds include compounds having a functional group that is converted into a reactive group by the action of a base (sometimes referred to as "base-reactive compound (9-2a)" in the present disclosure), and compounds having a group that reacts by the action of a base (sometimes referred to as "base-reactive compound (9-2b)" in the present disclosure). The base-reactive compound (9-2b) differs from the base-reactive compound (9-2a) in that the reactive group is not a functional group that is converted into a reactive group by the action of a base.

[0096] Examples of reactions that proceed in the base-reactive compound include addition polymerization and condensation polymerization (polycondensation polymerization).

[0097] The base-reactive compound may be, for example, any of a monomer, an oligomer, and a polymer, and may be any of a low molecular weight compound and a high molecular weight compound.

[0098] As the base-reactive compound, known compounds can be used, for example, the base-reactive compounds described in JP-A-2011-80032, although this is just one example.

[0099] Examples of the base-reactive compound (9-2a) include compounds that are decomposed by the action of a base and have a functional group converted into a reactive group. Examples of such base-reactive compounds (9-2a) include compounds having a carbonate skeleton (-OC(=O)-O-), photosensitive polyimides, etc.

[0100] Examples of the base-reactive compound (9-2b) include silicone resins, alkoxysilane compounds, (meth)acrylate compounds, and monofunctional epoxy compounds. In the present disclosure, the term "(meth)acrylate" is a concept that encompasses both "acrylate" and "methacrylate."

[0101] The other reactive compounds may be used alone or in combination of two or more kinds, and when two or more kinds are used, the combination and ratio thereof can be set arbitrarily.

[0102] <Sensitizer> The curable compositions of the present disclosure may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include benzophenone, naphthoquinone, anthraquinone, xanthene, thioxanthene, xanthone, thioxanthone, anthracene, phenanthrene, phenanthroline, pyrene, pentacene, and derivatives thereof. The sensitizer may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof can be set arbitrarily. The content of the sensitizer in the curable composition is not particularly limited and may be adjusted appropriately.

[0103] <Filling material> The curable composition of the present disclosure may contain a filler. By including a filler, it is possible to adjust properties such as the viscosity of the curable composition itself and the strength of the curable composition after reaction (the reaction product described below). The filler may be any known filler without any particular limitation. For example, the filler may be fibrous, plate-like, or granular, and the shape, size, and material thereof may all be appropriately selected depending on the purpose. The curable composition may contain only one type of filler, or two or more types. When two or more types are contained, the combination and ratio of the fillers can be set arbitrarily. The content of the filler in the curable composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0104] <Pigments> The curable composition of the present disclosure may contain a pigment. By including a pigment, for example, light transmittance and the like can be adjusted. The pigment contained in the curable composition may be any known pigment, such as white, blue, red, yellow, or green pigment, and is not particularly limited. The curable composition may contain one kind of pigment or two or more kinds of pigments, and when two or more kinds of pigments are contained, the combination and ratio thereof can be set arbitrarily. The content of the pigment in the curable composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0105] <Solvent> The curable composition of the present disclosure may contain a solvent. By containing a solvent, handling properties are improved. The solvent is not particularly limited and may be appropriately selected in consideration of the solubility, stability, etc. of the curable composition and the photobase generator. The solvent is not particularly limited, and examples thereof include halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; aliphatic hydrocarbons such as hexane, heptane, and octane; carboxylic acid esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), and 1,2-dimethoxyethane (dimethylcellosolve); ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, and cyclopentanone; nitriles such as acetonitrile; and amides such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide.

[0106] The curable composition may contain one or more solvents, and when two or more solvents are contained, the combination and ratio thereof can be set arbitrarily.

[0107] In the curable composition, the content of the solvent is preferably 3 to 20 times by mass, more preferably 4 to 15 times by mass, and even more preferably 5 to 10 times by mass, relative to the content of the polyfunctional epoxy compound. When the content of the solvent is within such a range, the handleability of the curable composition is further improved.

[0108] The curable composition can be obtained by blending a photobase generator, a base amplifier, the above-mentioned polymer, a polyfunctional epoxy compound, and other components as needed. After blending the components, the resulting composition may be used as a curable composition as is, or may be used as a curable composition after further performing a known purification procedure as needed.

[0109] When blending the components, all the components may be added and then mixed, or some of the components may be added sequentially while being mixed, or all the components may be added sequentially while being mixed. The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blades, a method of mixing using a mixer, or a method of mixing by adding ultrasound.

[0110] The temperature during blending is not particularly limited as long as the blended components do not deteriorate, and can be, for example, 3°C to 30°C. The blending time is not particularly limited as long as the blended components do not deteriorate, and can be, for example, 30 seconds to 1 hour. However, these compounding conditions are merely examples.

[0111] <Reaction products> The reaction product of the present disclosure is obtained by reacting the above-described curable composition. A method for producing the reaction product of the present disclosure will be described later in the method for producing the reaction product of the present disclosure. The shape of the reaction product of the present disclosure can be selected arbitrarily depending on the purpose, for example, in the form of a film or a line.

[0112] (Method for producing reaction product) The method for producing a reaction product of the present disclosure includes the steps of irradiating the curable composition with light to generate the base from the photobase generator, and generating a base from a base multiplier through the action of the base. Irradiating the curable composition containing the photobase generator with light generates a base from the photobase generator, and the generated base generates a base from the base multiplier through the action of the base. The action of the base causes a reaction of the polyfunctional epoxy compound, resulting in a reaction product. The reaction product may have a structure in which the polymer is entangled in a crosslinked structure formed by the reaction of the polyfunctional epoxy compound, or may have a structure in which at least a portion of the polymer is reacted with the polyfunctional epoxy compound, etc.

[0113] The curable composition may be applied to an object by a known method, and then optionally pre-baked (dried) to form a photoreactive composition layer, and the curable composition layer may be irradiated with light. For example, when a film-like reaction product is produced, the curable composition may be applied to a target object using a coating means such as a spin coater, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, a Mayer bar coater, or a kiss coater, or an applicator, or the like, or the target object may be immersed in the curable composition, thereby adhering the curable composition to the target object. For example, when producing a film-like or linear reaction product, the curable composition may be attached to a target object by using a printing method such as screen printing, flexographic printing, offset printing, inkjet printing, dispenser printing, jet dispenser printing, gravure printing, gravure offset printing, or pad printing.

[0114] The pre-baking may be carried out under conditions of, for example, 30° C. to 120° C. and 30 seconds to 10 minutes, and is not particularly limited.

[0115] The wavelength of the light irradiated onto the curable composition is not particularly limited and may be, for example, a wavelength in the ultraviolet to visible light range. The wavelength of the light irradiated onto the curable composition may be 10 nm or more, 200 nm or more, or 300 nm or more. Furthermore, the wavelength of the light irradiated onto the curable composition may be 600 nm or less, 500 nm or less, or 400 nm or less.

[0116] The illuminance of the light irradiated onto the curable composition is, for example, 1 mW / cm 2 ~100mW / cm 2 and preferably 5 mW / cm 2 ~80mW / cm 2 More preferably, it is 10 mW / cm 2 ~60mW / cm 2 It is more preferable that: The light irradiation dose applied to the curable composition is, for example, 100 mJ / cm 2 ~20,000mJ / cm 2and preferably 200 mJ / cm 2 ~15000mJ / cm 2 More preferably, it is 300 mJ / cm 2 ~12000mJ / cm 2 It is more preferable that: However, the light irradiation conditions given here are merely examples and are not limited to these.

[0117] The reaction product obtained by irradiating the curable composition with light may be further subjected to post-baking (heat treatment after light irradiation). The post-baking may be carried out under conditions of, for example, 50° C. to 180° C. and 20 minutes to 2 hours, and is not particularly limited.

[0118] The thickness of the reaction product may be appropriately set depending on the purpose and is not particularly limited. The thickness of the reaction product is, for example, preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm. To form a reaction product of such a thickness, for example, the thickness of the curable composition layer may be set to be equal to or greater than the thickness of the desired reaction product.

[0119] The curable composition may be irradiated with light through a photomask. After the light irradiation, the curable composition may be post-baked as needed, and then developed to remove the curable composition in the unexposed region, thereby producing a patterned reaction product. [Example]

[0120] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0121] <Production of Photobase Generator> First, a carbamate compound (NV-np) having a nitrobenzyl skeleton was produced as shown below. 4,5-Dimethoxy-2-nitrobenzyl alcohol (NV-OH, 2.8 g, 13 mmol), triethylamine (1.5 g, 15 mmol), and 40 mL of dry tetrahydrofuran were mixed in a recovery flask. 4-Nitrophenyl chloroformate (np-Cl, 3.0 g, 15 mmol) and 10 mL of dry tetrahydrofuran were mixed in a vial, and the mixture was transferred to the recovery flask and stirred at room temperature for 3 hours to carry out the reaction. After completion of the reaction, the reaction product was washed with 5% by mass hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated aqueous sodium chloride. The product was then recrystallized using toluene to obtain a carbamate compound (NV-np) with a nitrobenzyl skeleton as a yellow solid (yield: 2.7 g).

[0122] [ka]

[0123] Next, a carbamate compound having a nitrobenzyl skeleton (NV-np) was reacted with 4,4'-trimethylenebispiperidine (bp) to produce a photobase generator (NV-bp). NV-np (1.1 g, 2.9 mmol), 4,4'-trimethylenebispiperidine (bp, 0.25 g, 1.2 mmol), 4-dimethylaminopyridine (DMAP, 0.29 g, 2.4 mmol), and 50 mL of dry tetrahydrofuran were mixed in a recovery flask, and the mixture was refluxed at 70 °C for 3 hours. After completion of the reaction, the reaction product was washed with 5% by mass hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated aqueous sodium chloride. The washed reaction product was then purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane (3 / 2, volume ratio) as the mobile phase. Fractions containing the target product were collected and concentrated to obtain the target photobase generator (NV-bp) as a yellow solid (yield: 0.51 g, 26%). The obtained photobase generator (NV-bp) 1 The results of the H-NMR analysis are shown in Table 1.

[0124] [ka]

[0125] [Table 1]

[0126] <Production of base multiplier> First, a compound (tBuFmoc-np) having a fluorene skeleton and a carbonate skeleton was produced as shown below. 2,7-Di(tert-butyl)-9H-fluorene-9-methanol (tBuFmoc-OH, 4 g, 13 mmol) and 20 mL of dry tetrahydrofuran were mixed in a recovery flask. 4-Nitrophenyl chloroformate (np-Cl, 2.6 g, 13 mmol) and dry tetrahydrofuran were mixed in an Erlenmeyer flask, and the mixture was added to the recovery flask. The recovery flask was then placed in an ice bath, and triethylamine (TEA, 1.32 g, 8.8 mmol) was added. The mixture was then stirred at room temperature for 40 hours to carry out the reaction. After completion of the reaction, the reaction product was washed with 5% by mass hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated aqueous sodium chloride. The washed reaction product was then purified by silica gel column chromatography using a hexane / toluene (1 / 1.2, volume ratio) mixed solvent as the mobile phase. The fractions containing the target product were collected and concentrated to obtain the target product, tBuFmoc-np (yield 2.08 g, 33%).

[0127] [ka]

[0128] Next, a compound having a fluorene skeleton and a carbonate skeleton (tBuFmoc-np) was reacted with 4-dimethylaminopyridine to prepare a base multiplier (tBuFmoc-4MApy). tBuFmoc-np (2.08 g, 6 mmol), 4-dimethylaminopyridine (0.5 g, 6 mmol), and 20 mL of dry dichloromethane were mixed in a recovery flask and stirred at room temperature for 24 hours. After completion of the reaction, the reaction mixture was washed with aqueous sodium bicarbonate and saturated aqueous sodium chloride. The washed reaction mixture was then purified by silica gel column chromatography using a mixed solvent of ethyl acetate and toluene (1 / 1.2, volume ratio) as the mobile phase. The fractions containing the target product were collected and concentrated to obtain the target base amplifier (tBuFmoc-4MApy) as a white powder (yield: 0.61 g, 31%). The obtained base amplifier (tBuFmoc-4MApy) 1 The results of the H-NMR analysis are shown in Table 2.

[0129] [ka]

[0130] [Table 2]

[0131] <Production of Polyimide> Next, 5,5'-sulfonylbis(isobenzofuran-1,3-dione) (DSDA) was reacted with 2,2'-diamino-4,4'-(propane-2,2-diyl)diphenol (AHPP) to prepare polyimide (PHI). AHPP (4.7 g, 19 mmol), DSDA (6.5 g, 19 mmol), 4-dimethylaminopyridine (DMAP, 0.022 g, 1 mol% relative to AHPP), and 69 mL of dry N-methylpyrrolidone were mixed in a recovery flask and stirred at room temperature for 20 hours to carry out the reaction. Subsequently, 12.6 mL of dry toluene was added to the recovery flask, and the mixture was refluxed at 180 °C for 6 hours. Filtration and reprecipitation were carried out using dry N-methylpyrrolidone as a good solvent and methanol as a poor solvent. The target polyimide (PHI) was obtained as a pale yellow powder solid (yield: 8.4 g, 74%). The obtained polyimide (PHI) 1 The results of the H-NMR analysis are shown in Table 3.

[0132] [ka]

[0133] [Table 3]

[0134] <Preparation of Curable Composition 1> Photobase generator 1 (NV-bp, 0.027 g, 5 mol% relative to the epoxy group), base amplifier (tBuFmoc-4MApy, 0.0065 g, 1.9 mol% relative to the epoxy group), polyimide (PHI, 0.10 g), multifunctional epoxy compound (TEPIC-VL, 1,3,5-tris(3-oxiranylpropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 0.10 g), and 500 μL of dimethylformamide (DMF) were added to a glass bottle and stirred to prepare curable composition 1.

[0135] <Production of reaction product 1> The curable composition 1 obtained above was spin-coated onto a silicon wafer at 2000 rpm for 30 seconds. Then, this coating film (photoreactive composition layer) was heated (pre-baked) at 60°C for 5 minutes. Thereafter, an LED lamp was used to illuminate only the right half of the coating film at an illuminance of 50 mW / cm. 2 , light irradiation dose 1000mJ / cm 2 The coating film was then irradiated with light having a wavelength of 365 nm. Thereafter, the irradiated coating film was heated at 90° C. for 30 minutes (post-baking). The post-baked coating film was developed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 60 seconds to produce reaction product 1. It was then rinsed with water. The silicon wafer was then air-dried. The presence or absence of a residual film in the exposed and unexposed areas was confirmed. Since a residual film was observed in the exposed areas, the residual film rate was calculated using the following formula, which was 48%. On the other hand, no residual film was observed in the unexposed areas, and the residual film rate was 0%. Residual film rate (%) = [(film thickness after development [μm]) / (film thickness before development [μm])] × 100

[0136] <Production of Reaction Product 2> The curable composition 1 obtained above was spin-coated onto a silicon wafer at 2000 rpm for 30 seconds. Then, this coating film (photoreactive composition layer) was heated (pre-baked) at 60°C for 5 minutes. Thereafter, an LED lamp was used to illuminate only the right half of the coating film at an illuminance of 50 mW / cm. 2 , light irradiation dose 1000mJ / cm 2 The coating film was then irradiated with light having a wavelength of 365 nm. Thereafter, the irradiated coating film was heated at 100° C. for 10 minutes (post-baking). The post-baked coating film was developed in the same manner as in <Production of Reaction Product 1> to produce Reaction Product 2, and the presence or absence of a residual film in the exposed and unexposed areas was confirmed. A residual film was confirmed in the exposed areas, but not in the unexposed areas.

[0137] <Production of Reaction Product 3> The curable composition 1 obtained above was spin-coated onto a silicon wafer at 2000 rpm for 30 seconds. Then, this coating film (photoreactive composition layer) was heated (pre-baked) at 60°C for 5 minutes. Thereafter, the coating film was exposed to an illuminance of 50 mW / cm using an LED lamp. 2 The coating was irradiated with light having a wavelength of 365 nm at a light irradiation dose shown in Figure 1. Thereafter, the coating film after light irradiation was heated (post-baked) at 90°C for 30 minutes. The post-baked coating film was developed in the same manner as in <Production of Reaction Product 1> to produce Reaction Product 3, and the residual film ratio was calculated based on the above formula. As shown in Figure 1, it was confirmed that the residual film ratio changes depending on the light irradiation dose, and a tendency for the residual film ratio to increase as the light irradiation dose increases was confirmed. For example, when the light irradiation dose was 1000 mJ / cm 2 When the film thickness was 100 μm, the remaining film ratio was 47%.

[0138] <Production of Reaction Products 4 and 5> The curable composition 1 obtained above was spin-coated onto a silicon wafer at 2000 rpm for 30 seconds. Then, this coating film (photoreactive composition layer) was heated (pre-baked) at 60°C for 5 minutes. Thereafter, the coating film was exposed to an illuminance of 50 mW / cm using an LED lamp. 2 , light irradiation dose 1000mJ / cm 2 The coating film was then irradiated with light at a wavelength of 365 nm. The unirradiated and irradiated coating films were then post-baked at 90°C for 120 minutes to produce reaction product 4 (unirradiated) and reaction product 5 (irradiated). After post-baking, the peak intensity (910 cm) derived from epoxy groups in the unirradiated and irradiated coating films was -1 ) was measured using a Fourier transform infrared spectrophotometer (FT-IR). As shown in Figure 2, it was confirmed that the epoxy residual rate changed depending on whether or not light was irradiated and the post-bake time. Specifically, after heating at 90°C for 120 minutes, the epoxy residual rate was 91% for reaction product 4 (unirradiated) and 82% for reaction product 5 (irradiated).

[0139] <Confirmation of the chemical structure of reaction product 3> For reaction product 3 produced in the same manner as in <Production of reaction product 3>, the peak intensity (1730 cm ) due to the C═O stretching vibration contained in the polyimide was measured. -1 ) and the peak intensity (1686 cm ) due to the C=O stretching vibration contained in the polyfunctional epoxy compound (TEPIC-VL). -1) was measured using a Fourier transform infrared spectrophotometer (FT-IR). Figure 3 shows the measurement results for the coating film before development ((1) in the figure) and after development (reaction product 3, (2) in the figure), as well as the measurement results for polyimide (PHI) alone ((3) in the figure) and the multifunctional epoxy compound alone ((4) in the figure). As shown in Figure 3, peaks due to the C=O stretching vibration in the polyimide and the C=O stretching vibration in the multifunctional epoxy compound were observed in both the coating film before and after development. These results indicated the presence of polyimide in the developed coating. Since polyimide has low reactivity with multifunctional epoxy compounds and was confirmed even after development, it is inferred that a structure (semi-IPN structure) is formed in which linear polymer polyimide is entangled in the crosslinked structure formed by the reaction of the multifunctional epoxy compound.

[0140] <Production of Patterned Reaction Product 6> The curable composition 1 obtained above was spin-coated onto a silicon wafer at 2000 rpm for 30 seconds. Then, this coating film (photoreactive composition layer) was heated (pre-baked) at 60°C for 5 minutes. After that, a photomask was placed on the coating film, and an LED lamp was used to heat the coating film at an illuminance of 50 mW / cm. 2 , light irradiation dose 1000mJ / cm 2 The coating film was then irradiated with light having a wavelength of 365 nm. Thereafter, the irradiated coating film was heated at 90° C. for 30 minutes (post-baking). The post-baked coating film was developed in the same manner as in <Production of Reaction Product 1> to produce a patterned reaction product 6. The patterned reaction product 6 was observed with an SEM, and a line / space pattern of 10 μm / 10 μm was confirmed.

Claims

1. a photobase generator; a base multiplier; at least one polymer selected from the group consisting of polyimide, polybenzoxazole, and polyphenylene ether; A curable composition comprising a polyfunctional epoxy compound.

2. 2. The curable composition according to claim 1, wherein the photobase generator is at least one selected from the group consisting of carbamates having a nitrobenzyl skeleton, compounds having a coumaric acid amide skeleton, and ionic base generators which are salts of a base and a carboxylic acid.

3. The curable composition according to claim 1 , wherein the base amplifier is a compound that decomposes under the action of a base to generate a base containing an aminopyridine skeleton.

4. 2. The curable composition according to claim 1, wherein the base amplifier is a compound that decomposes under the action of a base to generate 4-methylaminopyridine.

5. The curable composition of claim 1, wherein the polyfunctional epoxy compound comprises 1,3,5-tris(3-oxiranylpropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

6. The curable composition according to claim 1 , wherein the polymer comprises a polyimide containing a structural unit represented by the following general formula (A): 【Chemistry 1】 In formula (A), R represents a tetravalent organic group, and R' represents a divalent organic group.

7. A reaction product obtained by reacting the curable composition according to any one of claims 1 to 6.

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