TW202126704A - Resin composition, cured product and siloxane modified (meth) acrylic resin for providing a curable resin composition that can provide a cured product having a relatively low dielectric constant - Google Patents

Abstract

The present invention provides a curable resin composition that can provide a cured product having a relatively low dielectric constant, a cured product of the resin composition, a method for producing a patterned cured film using a specific resin composition as the resin composition, and a siloxane modified (meth) acrylic resin suitably used as a component of the resin composition. In the present invention, a siloxane modified (meth) acrylic resin is incorporated into a resin composition as a curable component. The siloxane modified (meth) acrylic resin is a reaction product of a (meth) acrylic resin having an alicyclic epoxy group and an epoxy group-containing cyclic siloxane compound having a specific structure.

Description

Resin composition, cured product, and silicone modified (meth)acrylic resin

The present invention relates to a curable resin composition containing a silicone-modified (meth)acrylic resin (A1) with a specific structure, a cured product of the resin composition, and a method for producing a cured product using the above-mentioned resin composition, A specific photosensitive composition is used as a method for producing a patterned cured film of the above-mentioned resin composition, and a silicone-modified (meth)acrylic resin suitably used as a component of the above-mentioned resin composition.

As an unsaturated carboxylic acid ester compound with alicyclic epoxy group, (meth)acrylate with alicyclic epoxy group is a compound commonly used in the fields of coating agents, inks, adhesives, sealants, etc. . In particular, polymers and cured products obtained from (meth)acrylates containing alicyclic structures and epoxy groups have excellent weather resistance and are suitable for outdoor use. The reason is that the polymer and the cured product are usually regulated by the ring-opening reactivity of the epoxy group present in the alicyclic structure, the reactivity of the radical polymerizable double bond in the (meth)acrylate structure, etc. performance.

At present, as unsaturated carboxylic acid esters having epoxy groups in the molecule, for example, glycidyl methacrylate, 1-methyl-1,2-epoxyethyl methacrylate, etc., containing terminal epoxy groups are known. (Meth)acrylates; (meth)acrylates having alicyclic epoxy groups such as 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, etc. In addition, Patent Document 1 discloses a β-hydroxy acrylate compound having an epoxy group in the molecule.

In addition, Patent Document 2 discloses an ^{unsaturated carboxylic acid ester containing 3,4-epoxytricyclo[5.2.1.0 2,6} ]decane skeleton, which is to provide a resin composition having the following properties: When used as a radiation-sensitive resin, it can form a high-performance film with excellent solvent solubility, transparency, heat resistance, etching resistance, flatness and developability, and high storage stability. [Prior Technical Documents] [Patent Documents]

[Patent Document 1] Japanese Patent Laid-Open No. 61-263968 [Patent Document 2] International Publication No. 2006-059564

[The problem to be solved by the invention]

For films such as insulators in display panels for various image display devices, it is desirable that the relative dielectric constant be low. However, the cured product of the curable composition described in Patent Document 1 and Patent Document 2 has a high relative dielectric constant. Therefore, it is difficult to apply the curable composition described in Patent Document 1 and Patent Document 2 as a material for manufacturing a film constituting a display panel.

In view of the above-mentioned problems of the prior art, the purpose of the present invention is to provide a curable resin composition that provides a cured product with a relatively low dielectric constant, a cured product of the resin composition, and a specific resin composition used as the above-mentioned resin composition. A method for producing a patterned cured film, and a silicone-modified (meth)acrylic resin suitably used as a component of the above-mentioned resin composition. [Technical means to solve the problem]

The inventors discovered that the reaction product of a (meth)acrylic resin with an alicyclic epoxy group and a cyclic siloxane compound containing an epoxy group with a specific structure, that is, silicone is modified ( The meth)acrylic resin is blended into the resin composition as a curable component to solve the above-mentioned problems, and the present invention has been completed. More specifically, the present invention provides the following.

(式(a-I)中，R^a01 及R^a02 表示含有環氧基之一價基或烷基，x1表示3以上之整數，x1個R^a01 及x1個R^a02 中之至少兩個為含有環氧基之一價基)The first aspect of the present invention is a resin composition containing a silicone-modified (meth)acrylic resin (A1), and the silicone-modified (meth)acrylic resin (A1) contains a resin derived from The (meth)acrylic resin (AI), which is the structural unit of the (meth)acrylate of the cyclic epoxy group, and the epoxy-containing cyclic siloxane compound (A-) represented by the following formula (aI) II) The reactant. [化1]

(In formula (aI), ^Ra01 and ^Ra02 represent monovalent groups or alkyl groups containing epoxy groups, x1 represents an integer of 3 or more, and at least two of ^{x1 Ra01} and x1 ^{Ra02 contain epoxy} (Basic one valence basis)

The second aspect of the present invention is a cured product formed by curing the resin composition of the first aspect by heating and/or exposure.

The third aspect of the present invention is a method for producing a cured product, which heats and/or exposes the resin composition of the first aspect.

The fourth aspect of the present invention is a method for manufacturing a patterned cured film, which includes: The resin composition of the first aspect is a resin containing a (meth)acrylic resin (A1), a photopolymerizable monomer (B), and a photopolymerization initiator (C) containing a structural unit having an alkali-soluble group The composition is coated on the substrate to form a coating film; For the coated film, the position is selectively exposed; Use an alkaline developer to develop the exposed coating film to pattern the coating film; and The patterned coating film is heated.

(式(a-I)中，R^a01 及R^a02 表示含有環氧基之一價基或烷基，x1表示3以上之整數，x1個R^a01 及x1個R^a02 中之至少兩個為含有環氧基之一價基) [發明之效果]The fifth aspect of the present invention is a silicone-modified (meth)acrylic resin, which is a (meth)acrylic resin containing structural units derived from a (meth)acrylate having an alicyclic epoxy group (AI), reactant with epoxy-containing cyclic siloxane compound (A-II) represented by the following formula (aI). [化2]

(In formula (aI), ^Ra01 and ^Ra02 represent monovalent groups or alkyl groups containing epoxy groups, x1 represents an integer of 3 or more, and at least two of ^{x1 Ra01} and x1 ^{Ra02 contain epoxy} One-valent basis) [Effects of the invention]

According to the present invention, it is possible to provide a curable resin composition that provides a cured product with a low relative dielectric constant, a cured product of the resin composition, and a patterned cured film using a specific resin composition as the resin composition. The production method and the silicone-modified (meth)acrylic resin suitably used as a component of the above-mentioned resin composition.

(式(a-I)中，R^a01 及R^a02 表示含有環氧基之一價基或烷基，x1表示3以上之整數，x1個R^a01 及x1個R^a02 中之至少兩個為含有環氧基之一價基)≪Resin composition≫ The resin composition contains silicone modified (meth)acrylic resin (A1). Silicone modified (meth)acrylic resin (A1) is a (meth)acrylic resin (AI) containing structural units derived from (meth)acrylates with alicyclic epoxy groups, and the following formula (aI) The reactant of the epoxy-containing cyclic siloxane compound (A-II). [化3]

(In formula (aI), ^Ra01 and ^Ra02 represent monovalent groups or alkyl groups containing epoxy groups, x1 represents an integer of 3 or more, and at least two of ^{x1 Ra01} and x1 ^{Ra02 contain epoxy} (Basic one valence basis)

In the specification of this application and the scope of the patent application, "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid. In the specification of this application and the scope of the patent application, "(meth)acrylate" refers to both acrylate and methacrylate. In the specification of this application and the scope of the patent application, "(meth)acryloyl" refers to both acryloyl and methacryloyl.

Since the above-mentioned resin composition contains the above-mentioned silicone modified (meth)acrylic resin (A1) as an epoxy compound, the compound represented by formula (1), it can be cured by the related reaction of the epoxy group. The method of hardening the resin composition is not particularly limited. The resin composition to which the thermosensitive hardening agent is added can be hardened by heating. In addition, the resin composition to which the photosensitive curing agent is added can be cured by exposure.

The resin composition may contain a photopolymerizable compound and a photopolymerization initiator. The resin composition containing the above-mentioned silicone modified (meth)acrylic resin (A1) as an epoxy compound, a photopolymerizable compound and a photopolymerization initiator can be exposed only by exposure or by a combination of exposure and heating And hardened.

Hereinafter, preferred aspects of the silicone-modified (meth)acrylic resin (A1) and the resin composition will be described. In addition, the resin composition is not limited to the composition described later, as long as it contains a silicone-modified (meth)acrylic resin (A1).

<Siloxane modified (meth)acrylic resin (A1)> As mentioned above, the silicone modified (meth)acrylic resin (A1) is a (meth)acrylic resin (AI) containing structural units derived from (meth)acrylates with alicyclic epoxy groups, Reactant with the above-mentioned epoxy-containing cyclic siloxane compound (A-II). By including the silicone-modified (meth)acrylic resin (A1) in the resin composition, the resin composition can provide a cured product with a relatively low dielectric constant. Hereinafter, the production method of (meth)acrylic resin (AI), epoxy-containing cyclic silicone compound (A-II), and silicone modified (meth)acrylic resin (A1) will be explained .

[(Meth) acrylic resin (A-I)] The (meth)acrylic resin (A-I) is a (meth)acrylic resin containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group. The (meth)acrylic resin (AI) can be a homopolymer of (meth)acrylate with alicyclic epoxy group, or it can be a (meth)acrylate with alicyclic epoxy group and other monomers. Body copolymer.

((Meth)acrylate with alicyclic epoxy group) The alicyclic group constituting the (meth)acrylate having an alicyclic epoxy group may be a monocyclic ring or a polycyclic ring. In terms of the ease of obtaining a cured product with a low dielectric constant, it is preferable that the alicyclic group is a polycyclic alicyclic group, and the (meth)acrylate having an alicyclic epoxy group has a polycyclic alkane skeleton. As a monocyclic alicyclic group, cyclopentyl, cyclohexyl, etc. are mentioned. In addition, as the polycyclic alicyclic group, there can be exemplified nordoxy, isooxy, tricyclononyl, tricyclodecyl, tetracyclododecyl, and the like.

As a specific example of the (meth)acrylate which has an alicyclic epoxy group, the compound shown by following formula (a-4-1a)-(a-4-1o) is mentioned, for example. Among these, in order to keep the developability in an appropriate range, the compounds represented by the following formulas (a-4-1a) to (a-4-1e) are preferred, and the following formulas (a-4- 1a) ~ (a-4-1c) the compounds shown.

[化4]

[化5]

[化6]

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent saturated aliphatic hydrocarbon group with 1 to 6 ^{carbon atoms, R a22} represents a divalent hydrocarbon group with 1 to 10 carbon atoms, and t represents 0 or more Integers below 10. R ^{a21 is} preferably a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene base. As R ^a22 , for example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH are preferred. ₂ -Ph-CH _2- (Ph represents phenylene).

(式(1)中，環A表示與環B縮合之包含五員或六員脂環之環，環B表示與環A及C縮合且含有於環B內交聯之交聯基之脂環，環C表示與環B縮合之包含五員或六員脂環之環，R¹ 表示(甲基)丙烯醯基，R² 表示烷基、烷醯基、芳醯基、或三烴基矽烷基，環A、環B及環C可具有取代基，亦可不具有取代基)・The compound represented by formula (1), as a (meth)acrylate having an alicyclic epoxy group, is easy to form a cured product with a low relative permittivity, as shown in the following formula (1) The compound is also preferred. Hereinafter, the compound represented by formula (1) will be described. [化7]

(In formula (1), ring A represents a five-member or six-member alicyclic ring condensed with ring B, and ring B represents an alicyclic ring condensed with rings A and C and containing a crosslinking group crosslinked in ring B , Ring C represents a five-member or six-member alicyclic ring condensed with ring B, R ¹ represents a (meth)acryloyl group, R ² represents an alkyl, alkane, aryl, or trihydrocarbylsilyl group , Ring A, Ring B and Ring C may or may not have substituents)

In the formula (1), the ring A is a five-member or six-member alicyclic ring condensed with the ring B. Ring B is an alicyclic ring which is condensed with rings A and C and contains a crosslinking group crosslinked in ring B. Ring C is a five-member or six-member alicyclic ring condensed with ring B. Rings A, B, and C may or may not have substituents.

The ring A may contain the same cross-linking group as the ring B that will cross-link in the ring A, or it may not contain the cross-linking group. In terms of easy synthesis of the compound represented by formula (1), the ring A is preferably a six-membered alicyclic ring. Ring C may contain the same cross-linking group as ring B that will cross-link in ring C, or may not contain the cross-linking group. In terms of easy synthesis of the compound represented by formula (1), the ring C is preferably a five-membered alicyclic ring. From the viewpoint of the selectivity of the epoxy ring-opening reaction during production, a five-membered alicyclic ring is preferred.

Ring B can contribute to heat resistance by having a crosslinking group that can crosslink in ring B. As the ring B, an alicyclic ring containing five members or more and eight members or less of the above-mentioned crosslinking group can be exemplified. The ring B is preferably a six-membered or seven-membered alicyclic ring containing the above-mentioned cross-linking group, and more preferably a six-membered ring containing the above-mentioned cross-linking group.

Examples of the above-mentioned cross-linking group capable of cross-linking in the ring B include a divalent group having 1 to 5 carbon atoms. The number of carbon atoms of the crosslinking group is more preferably 1 or more and 3 or less, and still more preferably 1 or 2. As the above-mentioned crosslinking group, an alkylene group, an ether bond (-O-), a thioether bond (-S-), a carbonyl group (-CO-) or a divalent group composed of at least two of these are preferred , More preferably an alkylene, ether bond, thioether bond or a divalent group formed by a combination of at least two of these, particularly preferably an alkylene, ether bond or thioether bond, and most preferably an alkylene.

As said alkylene group, the C1-C5 alkylene group which may have a substituent is mentioned. The number of carbon atoms of the alkylene group is more preferably 1 or more and 3 or less, and still more preferably 1 or 2. Specific examples of the alkylene group include methylene, ethylene group, propylene group, butylene group, pentylene group, etc., preferably methylene, ethylene group or propylene group, and more preferably Methylene or ethylene.

Examples of the substituents that the above-mentioned alkylene group may have, and the substituents that the rings A, B, and C may have, include a halogen atom or a hydrocarbon group. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. As the hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms may be mentioned. As a preferable example of a hydrocarbon group, an alkyl group etc. can be mentioned. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms may be mentioned. Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, n-hexyl, N-heptyl, n-octyl, n-nonyl, and n-decyl, etc. Among these alkyl groups, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and the first alkyl group having 1 to 4 carbon atoms are preferred. Tributyl. The alkyl group may have a substituent. When the alkyl group has a substituent, the substituent may, for example, be a halogen atom or the like.

(式(2)中，L表示上述交聯基，上述交聯基為伸烷基、醚鍵、硫醚鍵、酮基或該等之至少兩個組合而成之二價基，R³ 及R⁴ 分別獨立表示氫原子、鹵素原子或烴基，*表示與環A之鍵結鍵，**表示與環C之鍵結鍵)The ring B is preferably a ring represented by the following formula (2). [化8]

(In formula (2), L represents the above-mentioned cross-linking group, and the above-mentioned cross-linking group is an alkylene group, an ether bond, a thioether bond, a ketone group, or a divalent group formed by a combination of at least two of these, R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group, * represents a bond with ring A, ** represents a bond with ring C)

Specific examples and preferred examples of the above-mentioned crosslinking group related to L are as described above. Specific examples and preferred examples of halogen atoms and hydrocarbon groups as R ³ and R ⁴ include those described above as "substituents that may be possessed by the above-mentioned alkylene group, and substituents that may be possessed by rings A, B and C" Specific examples and preferred examples of the halogen atom or hydrocarbon group. As R ³ and R ⁴ , a hydrogen atom, a halogen atom or an alkyl group is preferable, and a hydrogen atom is more preferable.

In the formula (1), R ² is an alkyl group, an alkane group, an aryl group, or a trihydrocarbylsilyl group.

The alkyl group as R ² may be linear or branched, and is preferably linear. The number of carbon atoms of the alkyl group as R ² is preferably 1 or more and 10 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or 2. Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, n-hexyl, N-heptyl, n-octyl, n-nonyl, and n-decyl, etc. Among these alkyl groups, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and the first alkyl group having 1 to 4 carbon atoms are preferred. The tributyl group is more preferably a methyl group and an ethyl group, and still more preferably a methyl group.

The alkanoyl group as R ² may be linear or branched, and is preferably linear. The number of carbon atoms of the alkanoyl group as R ² is preferably 2 or more and 10 or less, more preferably 2 or more and 4 or less, and still more preferably 2. Specific examples of the alkanoyl group include acetyl, propanoyl, butanoyl, pentanyl, hexyl, heptanoyl, octanoyl, nonanoyl, and decanoyl. Among these alkyl groups, acetyl group and propyl group are preferred, and acetyl group is more preferred.

Regarding the aryl group as R ² , a benzyl group, a naphthyl group and the like can be mentioned.

The trihydrocarbyl silyl group as R ² is a group in which 3 hydrocarbyl groups are bonded to a silicon atom. The three hydrocarbyl groups in the trihydrocarbylsilyl group may be the same or different. When the compound represented by formula (1) is produced, it is easy to synthesize or obtain a silane compound for introducing a trihydrocarbylsilyl group, it is preferable that the three hydrocarbyl groups in the trihydrocarbylsilyl group are the same.

In the trihydrocarbyl silyl group, the hydrocarbon group to be bonded to the silicon atom may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. In the trihydrocarbylsilyl group, when the hydrocarbyl group to be bonded to the silicon atom is an aliphatic hydrocarbyl group, the aliphatic hydrocarbyl group may contain one or more unsaturated bonds. In the trihydrocarbylsilyl group, when the hydrocarbyl group to be bonded to the silicon atom is an aliphatic hydrocarbyl group, the structure of the aliphatic hydrocarbyl group may be linear, branched, cyclic, or It is a combination of these structures.

In the trihydrocarbylsilyl group, the number of carbon atoms of the hydrocarbyl group to be bonded to the silicon atom is preferably 1 or more in terms of the molecular weight and epoxy equivalent of the compound represented by formula (1) not becoming too large 10 or less, more preferably 1 or more and 6 or less, and still more preferably 1 or more and 4 or less.

As the hydrocarbon group in the trihydrocarbylsilyl group, for example, an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group are preferable.

Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, n-hexyl, N-heptyl, n-octyl, n-nonyl, and n-decyl, etc. Among these alkyl groups, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and the first alkyl group having 1 to 4 carbon atoms are preferred. Tributyl.

Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

As a specific example of an aryl group, a phenyl group, a naphth-1-yl group, and a naphth-2-yl group can be mentioned.

As specific examples of the aralkyl group, a benzyl group and a phenethyl group may be mentioned.

As preferred specific examples of the trihydrocarbylsilyl group described above, there may be mentioned: trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group , Triisobutylsilyl group, tri-second butylsilyl group, tri-tertiary butylsilyl group, ethyl dimethyl silyl group, n-propyl dimethyl silyl group, isopropyl dimethyl silyl group Group, n-butyldimethylsilyl group, isobutyldimethylsilyl group, second butyldimethylsilyl group, and tertiary butyldimethylsilyl group.

(式(3)及式(4)中，環B表示含有會於環B內交聯之上述交聯基之脂環，R¹ 表示(甲基)丙烯醯基，R² 表示烷基、烷醯基、芳醯基、或三烴基矽烷基，R¹¹ 表示單鍵或-CHR¹⁵ -所示之二價基，於R¹¹ 為單鍵之情形時，R¹² 及R¹³ 、或R¹³ 及R¹⁴ 相互鍵結而形成環氧乙烷環(環氧基)，於R¹¹ 為-CHR¹⁵ -所示之二價基之情形時，R¹² 及R¹³ 、R¹³ 及R¹⁴ 、或R¹⁴ 及R¹⁵ 相互鍵結而形成環氧乙烷環，R¹² ～R¹⁵ 中之未形成環氧乙烷環之基表示氫原子)The compound represented by the above formula (1) is preferably a compound represented by the following formula (3) or (4). [化9]

(In formulas (3) and (4), ring B represents an alicyclic ring containing the above-mentioned crosslinking group that will crosslink within ring B, R ¹ represents a (meth)acryloyl group, and R ² represents an alkyl group or an alkane group. R ¹¹ represents a single bond or a ^{divalent group represented by -CHR 15} -. When R ¹¹ is a single bond, R ¹² and R ¹³ , or R ¹³ and R ^{14 is} bonded to each other to form an oxirane ring (epoxy group). When R ¹¹ is a divalent group represented by ^{-CHR 15 -, R 12} and R ¹³ , R ¹³ and R ¹⁴ , or R ¹⁴ and R ¹⁵ are bonded to each other to form an oxirane ring, and the group in R ¹² to R ¹⁵ that does not form an oxirane ring represents a hydrogen atom)

In formulas (3) and (4), specific examples and preferred examples of ring B include the same alicyclic rings as the specific examples and preferred examples of ring B in formula (1). Preferably, ring B is a ring represented by formula (2).

R ^{11 is} preferably a ^{divalent group represented by -CHR 15} -, more preferably R ¹¹ is a divalent group represented by ^{-CHR 15 -, R 12} and R ¹³ , R ¹³ and R ¹⁴ , or R ¹⁴ And R ¹⁵ are bonded to each other to form an oxirane ring, and ^{the groups in R 12} to R ¹⁵ that do not form an oxirane ring represent a hydrogen atom.

(式(M1)中，環A表示與環B縮合之包含五員或六員脂環之環，環B表示與環A及C縮合且含有於環B內交聯之交聯基之脂環，環C表示與環B縮合之包含五員或六員脂環之環，環A、環B及環C可具有取代基，亦可不具有取代基) [化11]

(式(M2)中，環A、環B及環C與式(M1)中之該等相同，R¹ 表示(甲基)丙烯醯基)The method for producing the compound represented by formula (1) is not particularly limited. As a preferable manufacturing method, a method including the following steps can be exemplified: reacting the compound represented by the following formula (M1) with (meth)acrylic acid to produce the compound represented by the following formula (M2); and The hydroxyl group of the compound represented by the formula (M2) is alkylated, alkylated, arylated, or trihydrocarbyl silylated. [化10]

(In formula (M1), ring A represents a five-member or six-member alicyclic ring condensed with ring B, and ring B represents an alicyclic ring condensed with rings A and C and containing a crosslinking group within ring B , Ring C means a five-membered or six-membered alicyclic ring condensed with ring B. Ring A, ring B and ring C may or may not have substituents) [化11]

(In formula (M2), ring A, ring B and ring C are the same as those in formula (M1), and R ¹ represents (meth)acryloyl)

The reaction between the compound represented by formula (M1) and (meth)acrylic acid can be carried out under either acidic conditions or alkaline conditions, and is preferably carried out under alkaline conditions. Under alkaline conditions, it can be set in an inert solvent and under alkaline conditions, or it can be set under alkaline conditions using a basic solvent (for example, pyridine, etc.). Specifically, for example, the reaction can be carried out under basic conditions using alkylamines such as triethylamine and the like. In addition, the above-mentioned reaction between the compound represented by formula (M1) and (meth)acrylic acid can also be carried out in the presence of a phase transfer catalyst such as a quaternary ammonium halide such as benzyltriethylammonium chloride.

The reaction temperature is preferably about -50°C or higher and lower than the boiling point of the solvent, and more preferably room temperature or higher and 100°C or lower.

In addition, the ratio (molar ratio) of the compound represented by the formula (M1) to (meth)acrylic acid is not particularly limited, but is preferably 80/20 to 20/80, more preferably 70/30 to 30/ 70. As the total concentration of the compound represented by formula (M1) and (meth)acrylic acid in the reaction solution, it can usually be 0.001 mol/L or more and 6 mol/L or less, preferably 0.005 mol/L or more and 4 mol/L Hereinafter, it is more preferably 0.01 mol/L or more and 3 mol/L or less.

The usage amount of the quaternary ammonium salt is preferably in the range of 0.001 mol times to 5 mol times, and more preferably in the range of 0.005 mol times to 1 mol times, relative to the compound represented by formula (M1). More preferably, it is the range of 0.01 mol times or more and 0.1 mol times or less.

A solvent can also be used in the above reaction. Various solvents can be used. For example, one or more selected from the group consisting of nitrile solvents such as acetonitrile; hydrocarbon solvents such as benzene, toluene, and xylene; glycol-based solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether can be used. Solvents, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane and other ether-based solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, ring Ketone solvents such as pentanone and cyclohexanone; alcohol solvents such as ethanol, isopropanol, and butanol.

The method of alkylating, alkoxylating, arylating, or trihydrocarbyl silylating the hydroxyl group of the compound represented by the formula (M2) is not particularly limited.

As the alkylation method, a method of reacting an alkylating agent such as halogenated alkane, dialkyl sulfate, dialkyl carbonate, and the like with a compound represented by formula (M2) in the presence of a base can be mentioned. Examples of alkylating agents include methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propane bromide, propane iodide, dimethyl sulfate, dimethyl carbonate, diethyl sulfate, and diethyl carbonate. . Examples of the base include sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, lithium methoxide, and the like. The solvent used in the alkylation method is not particularly limited as long as it is a solvent that does not react with the compound represented by the formula (M2) and the alkylating agent. From the alkylation reaction using the hydroxyl group of the above-mentioned alkylating agent Appropriate selection among commonly used solvents. The reaction temperature and reaction time can be appropriately selected from the range generally used in the alkylation reaction using the above-mentioned alkylating agent.

As a method of alkylation, a method of reacting a fatty acid halide or fatty acid anhydride corresponding to an alkano group with a compound represented by the formula (M2) can be exemplified. As a fatty acid halogen, for example, acetyl chloride, acetyl bromide, propyl chloride, propyl bromide, etc. may be mentioned. As fatty acid anhydride, acetic anhydride, propionic anhydride, butyric anhydride, etc. are mentioned, for example. When using fatty halides, it is better to capture the by-product hydrogen halide due to the reaction between hydroxyl and fatty halides in the presence of alkalis such as pyridine, triethylamine, sodium hydroxide, and potassium hydroxide The alkylation is carried out below. In the case of using fatty acid anhydride, it is preferable to carry out alkylation in the presence of a catalyst such as N,N-dimethyl-4-aminopyridine. The solvent used in the alkylation method is not particularly limited as long as it does not react with the compound represented by the formula (M2) and the fatty acid halide or fatty acid anhydride. Appropriate selection of solvents commonly used in the alkylation reaction of hydroxyl group. The reaction temperature and reaction time can be appropriately selected from the range generally used in the alkylation reaction using fatty acid halogen or fatty acid anhydride.

As a method of arylation, a method of reacting an aromatic carboxylic acid halide corresponding to an aryl group with a compound represented by the formula (M2) can be exemplified. As the aromatic carboxylic acid halogen, for example, benzyl chloride, benzyl bromide, α-naphthyl chloride, α-naphthyl bromide, β-naphthyl chloride, and β-naphthyl bromide Wait. The reaction of the aromatic carboxylic acid halide with the compound represented by the formula (M2) can proceed in the same manner as the reaction of the aliphatic carboxylic acid halide with the compound represented by the formula (M2). The solvent used in the arylation method is not particularly limited as long as it does not react with the compound represented by the formula (M2) and the aromatic carboxylic acid halide. It can be selected from among the hydroxyl groups of the aromatic carboxylic acid halide. Appropriate selection of solvents commonly used in the arylation reaction. The reaction temperature and the reaction time can be appropriately selected from the range generally used in the arylation reaction using an aromatic carboxylic acid.

As a method of trihydrocarbyl silylation, a method of reacting a compound represented by formula (M2) with a silylation agent corresponding to the type of trihydrocarbyl silyl group can be exemplified. As the silylation agent, for example, trihydrocarbyl monohalosilanes such as trihydrocarbyl monochlorosilane and trihydrocarbyl monobromosilane; trihydrocarbyl monoalkoxy silanes such as trihydrocarbyl monomethoxysilane and trihydrocarbyl monoethoxy silane; Silane.

As preferred examples of trihydrocarbyl monohalosilanes, examples include: trimethyl monochlorosilane, triethyl monochlorosilane, tri-n-propyl monochlorosilane, triisopropyl monochlorosilane, tri-n-butyl monochlorosilane Chlorosilane, triisobutyl monochlorosilane, tri-second butyl monochlorosilane, tri-tertiary butyl monochlorosilane, ethyl dimethyl monochlorosilane, n-propyl dimethyl monochlorosilane, Isopropyl dimethyl monochlorosilane, n-butyl dimethyl monochlorosilane, isobutyl dimethyl monochlorosilane, second butyl dimethyl monochlorosilane, and tertiary butyl dimethyl mono Trialkyl monochlorosilanes such as chlorosilanes; Trimethyl monobromosilane, triethyl monobromosilane, tri-n-propyl monobromosilane, triisopropyl monobromosilane, tri-n-butyl monobromosilane, triisobutyl monobromosilane, tri-second Butyl monobromosilane, tri-tertiary butyl monobromosilane, ethyl dimethyl monobromosilane, n-propyl dimethyl monobromosilane, isopropyl dimethyl monobromosilane, n-butyl dimethyl Trialkyl monobromosilanes such as methyl monobromosilane, isobutyldimethylmonobromosilane, sec-butyldimethylmonobromosilane, and tert-butyldimethylmonobromosilane; Trimethylmonomethoxysilane, triethylmonomethoxysilane, tri-n-propylmonomethoxysilane, triisopropylmonomethoxysilane, tri-n-butylmonomethoxysilane, triisopropyl Butyl monomethoxysilane, tri-second butyl monomethoxysilane, tri-tertiary butyl monomethoxysilane, ethyl dimethyl monomethoxy silane, n-propyl dimethyl mono Methoxysilane, isopropyldimethylmonomethoxysilane, n-butyldimethylmonomethoxysilane, isobutyldimethylmonomethoxysilane, sec-butyldimethylmonomethyl Trialkyl monomethoxysilane such as oxysilane, and tert-butyldimethylmonomethoxysilane; Trimethylmonoethoxysilane, triethylmonoethoxysilane, tri-n-propylmonoethoxysilane, triisopropylmonoethoxysilane, tri-n-butylmonoethoxysilane, triiso Butyl monoethoxy silane, tri-second butyl monoethoxy silane, tri-tertiary butyl monoethoxy silane, ethyl dimethyl monoethoxy silane, n-propyl dimethyl mono Ethoxysilane, isopropyldimethylmonoethoxysilane, n-butyldimethylmonoethoxysilane, isobutyldimethylmonoethoxysilane, second-butyldimethylmonoethyl Trialkyl monoethoxysilanes such as oxysilane and tert-butyldimethylmonoethoxysilane.

The amount of the silylating agent used in the reaction between the compound represented by formula (M2) and the silylating agent is preferably equal to or more than the molar number of the compound represented by formula (M2), more preferably 1.2 times Molar or more, more preferably 1.5 times mol or more, and particularly preferably 2.0 times mol or more. The upper limit of the amount of silylation agent used is not special. In terms of cost, relative to the number of moles of the compound represented by formula (M2), it is preferably 5.0 times mol or less, and more preferably 3.0 times mol. the following.

The reaction between the compound represented by the formula (M2) and the silylation agent is usually carried out in an organic solvent. As the organic solvent, an organic solvent that does not have a functional group such as a hydroxyl group, a carboxyl group, or an amine group that can react with the silylation agent is used. Specific examples of organic solvents include halogenated alkanes such as carbon tetrachloride, chloroform, dichloromethane, bromopropane, bromobutane, bromopentane, bromohexane, methyl iodide, ethyl iodide, and propane iodide. ; Acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone and other ketones; pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, Hydrocarbons such as cyclohexane, petroleum ether, benzyne, kerosene, toluene, xylene, 1,3,5-trimethylbenzene, and benzene.

The temperature at the time of the reaction between the compound represented by the formula (M2) and the silylation agent is not particularly limited as long as the silylation reaction proceeds well. The reaction temperature is preferably -20°C or higher and 100°C or lower, more preferably -10°C or higher and 80°C or lower, and still more preferably 0°C or higher and 50°C or lower.

The reaction time is not particularly limited as long as the silylation reaction proceeds well. The reaction time is, for example, 5 minutes or more and 12 hours or less, preferably 10 minutes or more and 6 hours or less.

When the silylation agent is a trihydrocarbyl monohalosilane, hydrogen halide is by-produced during the silylation reaction. To capture the by-product hydrogen halide, bases such as triethylamine, pyridine, and N,N-dimethyl-4-aminopyridine can be added to the reaction solution.

The compound represented by the formula (1) produced in the manner described above is preferably recovered from the reaction solution according to the usual practice, and after purification as necessary, it is used as a component of the resin composition or the following (meth)acrylic resin ( A1) raw materials.

(Other monomers) As mentioned above, the (meth)acrylic resin (A1) can be a monomer other than (meth)acrylate with alicyclic epoxy group and (meth)acrylate with alicyclic epoxy group的copolymer. From the viewpoint of the curability of the resin composition, the content of the structural unit derived from the (meth)acrylate having an alicyclic epoxy group in the (meth)acrylic resin (A1) is preferably 50% by mass Above, it is more preferably 60% by mass or more, and still more preferably 70% by mass or more. The upper limit of the content of the structural unit derived from the (meth)acrylate having an alicyclic epoxy group in the (meth)acrylic resin (A1) is not particularly limited, and it can be 95% by mass or less, or 90% by mass. % Or less, may be 80% by mass or less.

Examples of other monomers include unsaturated carboxylic acids, (meth)acrylates without epoxy groups, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, benzene Ethylenes, and maleimines, etc. These compounds can be used alone or in combination of two or more kinds. In terms of the storage stability of the resin composition and the chemical resistance of the cured product formed using the resin composition to alkalis and the like, the (meth)acrylic resin (A1) is preferably free of unsaturation origin. The unit of carboxylic acid. On the other hand, when the resin composition is a negative photosensitive composition that can be developed with an alkaline developer, it is preferable that the (meth)acrylic resin (A1) contains a structural unit having an alkali-soluble group. It does not specifically limit as an alkali-soluble group, A carboxyl group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc. are mentioned. In terms of the stability of the resin composition over time, the alkali-soluble group is preferably a carboxyl group. That is, it is preferable that the (meth)acrylic resin (A1) contains a unit derived from an unsaturated carboxylic acid.

Examples of unsaturated carboxylic acids include: (meth)acrylic acid; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid, methylmaleic acid, Methyl fumaric acid, itaconic acid, anhydrides of these dicarboxylic acids. Among them, (meth)acrylic acid is preferred.

When the (meth)acrylic resin (A1) contains a structural unit derived from an unsaturated carboxylic acid, the content of the structural unit derived from an unsaturated carboxylic acid in the (meth)acrylic resin (A1) is preferably 3 Mass% or more and 50 mass% or less, more preferably 5 mass% or more and 40 mass% or less, and still more preferably 10 mass% or more and 30 mass% or less.

Examples of (meth)acrylates that do not have an epoxy group include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, pentyl (meth)acrylate Straight-chain or branched alkyl (meth)acrylate such as esters, tertiary octyl (meth)acrylate, etc.; chloroethyl (meth)acrylate, 2,2-dimethyl (meth)acrylate Hydroxypropyl ester, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; with alicyclic skeleton The base of (meth)acrylate. Among the (meth)acrylates that do not have an epoxy group, the (meth)acrylates that have an alicyclic skeleton-containing group are preferred.

In the (meth)acrylate having a group containing an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. In addition, as the polycyclic alicyclic group, there may be exemplified nordoxy, isooxy, tricyclononyl, tricyclodecyl, tetracyclododecyl, and the like.

As the (meth)acrylate having an alicyclic skeleton-containing group, for example, compounds represented by the following formulas (a1-1) to (a1-8) can be mentioned. Among these, compounds represented by the following formulas (a1-3) to (a1-8) are preferred, and compounds represented by the following formulas (a1-3) or (a1-4) are more preferred.

[化12]

[化13]

In the above formula, R ^A1 represents a hydrogen atom or a methyl group, R ^A2 represents a single bond or a divalent saturated aliphatic hydrocarbon group with 1 to 6 carbon atoms, and R ^A3 represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. . R ^{A2 is} preferably a single bond, linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, Hexamethylene. As R ^A3 , methyl and ethyl are preferred.

When the (meth)acrylic resin (A1) contains a structural unit derived from a (meth)acrylate having an alicyclic skeleton-containing group, the (meth)acrylic resin (A1) is derived from an alicyclic The content of the structural unit of the (meth)acrylate based on the formula skeleton is preferably 3% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and still more preferably 7% by mass or more and 20% by mass %the following.

Examples of (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N, N-dialkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl- N-methyl(meth)acrylamide and the like.

Examples of allyl compounds include: allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate Allyl esters such as propyl ester, allyl acetate, and allyl lactate; allyloxyethanol, etc.

Examples of vinyl ethers include: hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl Vinyl ether, 1-methyl-2,2-dimethyl propyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylamino ethyl ethylene Aliphatic vinyl ethers such as ether, diethylamino ethyl vinyl ether, butylamino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, Vinyl aryl ethers such as vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether.

Examples of vinyl esters include: vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate , Vinyl dichloroacetate, methoxy vinyl acetate, butoxy vinyl acetate, phenyl vinyl acetate, acetyl vinyl acetate, vinyl lactate, β-phenyl butyrate vinyl ester, vinyl benzoate , Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.

Examples of styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl Styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy methyl styrene, acetoxy methyl benzene Alkylstyrenes such as ethylene; Alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, etc. Styrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4- Halogenated styrenes such as fluoro-3-trifluoromethylstyrene, etc. As far as the relative dielectric constant of the cured product of the resin composition is low, the smaller the amount of the styrene-derived structural unit in the (meth)acrylic resin (A1), the better, and the more preferred is (A The base) acrylic resin (A1) does not contain structural units derived from styrene.

Examples of maleimines include N-methyl maleimines, N-ethyl maleimines, and N-propyl maleimines , N-isopropyl maleimide, N-butyl maleimide, N-pentyl maleimide, N-hexyl maleimide, etc. N-substituted maleimide by an alkyl group with 1 to 10 carbon atoms; N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-ring Heptyl maleimide and other maleimides N-substituted by alicyclic groups with 3 to 20 carbon atoms; N-phenylmaleimide, N-α -Naphthyl maleimide, N-β-naphthyl maleimide, etc. N-aryl maleimide N-substituted by aryl groups with 6 to 20 carbon atoms Amine; N-benzyl maleimide, N-phenethyl maleimide, etc. N-aralkyl cis-butane substituted with aralkyl groups with 7 to 20 carbon atoms Endiimines.

The weight average molecular weight of the (meth)acrylic resin (A1) is not particularly limited within a range that does not interfere with the purpose of the present invention. The weight average molecular weight in terms of polystyrene is preferably 3,000 or more and 30,000 or less, and more preferably Above 5,000 and below 15,000.

[Epoxy group-containing cyclic siloxane compound (A-II)] As the epoxy group-containing cyclic siloxane compound (A-II), a compound represented by the following formula (aI) is used. [化14]

In the formula (aI), R ^a01 and R ^a02 represent an epoxy group-containing monovalent group or an alkyl group. Wherein the formula (aI) of the compound represented by the number of x1 x1 and R ^a01 R ^a02 in one of at least two divalent groups containing one epoxy group. Moreover, x1 in formula (aI) represents an integer of 3 or more. ^{Furthermore, Ra01} and ^Ra02 in the compound represented by the formula (b1-III) may be the same or different. In addition, a plurality of ^Ra01 may be the same or different. A plurality of ^Ra02 may also be the same or different. Examples of the above-mentioned alkyl group include linear or branched alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, and isopropyl. The number of carbon atoms of the alkyl group is preferably 1 or more and 6 or less, particularly preferably 1 or more and 3 or less.

In formula (aI), x1 represents an integer of 3 or more. Among them, it has excellent reactivity with (meth)acrylic resin (AI) and obtains silicone-modified (meth)acrylic resin (A1) with excellent curability. In terms of ), it is preferably an integer of 3 or more and 6 or less.

The compound represented by formula (aI) has 2 or more epoxy groups in the molecule, which has excellent reactivity with (meth)acrylic resin (AI) and obtains silicone with excellent curability In terms of the modified (meth)acrylic resin (A1), 2 or more and 6 or less are preferable, and 2 or more and 5 or less are more preferable.

(上述式(a-Ia)及式(a-Ib)中，D¹ 及D² 分別獨立地表示伸烷基，ms表示0以上2以下之整數)As the above-mentioned epoxy-containing monovalent group, an alicyclic epoxy group and a ^{glycidyl ether group represented by -D A} -OR ^{a03 are} preferable, an alicyclic epoxy group is more preferable, and an alicyclic epoxy group is more preferable. An alicyclic epoxy group represented by the following formula (a-Ia) or the following formula (a-Ib). D ^A represents alkylene, R ^a03 represents a glycidyl group. Regarding the alkylene group as the above D ^A , for example, methylene, methylmethylene, dimethylmethylene, dimethylmethylene, trimethylene, etc., have carbon atoms of 1 or more and 18 or less. Linear or branched alkylene, etc. [化15]

(In the above formula (a-Ia) and formula (a-Ib), D ¹ and D ² each independently represent an alkylene group, and ms represents an integer of 0 to 2)

As the compound represented by the formula (a-I), more specifically, a cyclic siloxane having two or more glycidyl groups in the molecule represented by the following formula, and the like can be exemplified. In addition, as the compound represented by formula (aI), for example, trade names "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738", and " "X-40-2740" (the above is made by Shin-Etsu Chemical Co., Ltd.) and other commercially available products.

[化16]

[化17]

<Manufacturing method of silicone modified (meth)acrylic resin (A1)> Silicone modified (meth)acrylic resin (A1) is a (meth)acrylic resin (AI) containing structural units derived from (meth)acrylates with alicyclic epoxy groups, and the above-mentioned ring-containing The reactant of the cyclic siloxane compound (A-II) of the oxy group.

When manufacturing silicone modified (meth)acrylic resin (A1), the amount of epoxy-containing cyclic silicone compound (A-II) to be reacted with (meth)acrylic resin (AI) and There is no particular limitation. Regarding the amount of the epoxy group-containing cyclic silicone compound (A-II) to be reacted with the (meth)acrylic resin (AI), for example, relative to 100 parts by mass of the (meth)acrylic resin (AI), It is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, and still more preferably 1 part by mass or more and 15 parts by mass or less.

The reaction is typically carried out in the presence of an organic solvent. As the organic solvent, for example, it can be appropriately selected from the organic solvents described below as components of the resin composition. The amount of the organic solvent used is, for example, 100 parts by mass, preferably 50 parts by mass relative to the total of the mass of the (meth)acrylic resin (AI) and the mass of the epoxy-containing cyclic silicone compound (A-II) Above 5000 parts by mass or less, more preferably 100 parts by mass or more and 3000 parts by mass or less, and still more preferably 150 parts by mass or more and 2000 parts by mass or less.

Regarding the reaction temperature and reaction time, the reaction is not particularly limited unless the reaction reaches a desired level. From the viewpoint of enabling the desired reaction to proceed well, the reaction temperature is preferably 0°C or higher and 150°C or lower, more preferably 10°C or higher and 120°C or lower, and still more preferably 20°C or higher and 100°C or lower. The reaction time is preferably 5 minutes or more and 12 hours or less, more preferably 10 minutes or more and 6 hours or less.

Regarding the reaction between the (meth)acrylic resin (A-I) and the epoxy-containing cyclic silicone compound (A-II), in order to promote the reaction, it can be carried out in the presence of a catalyst. Preferred examples of the above catalyst include imidazole compounds, secondary amine compounds, tertiary amine compounds, organic phosphine compounds, and tetraphenyl boron salts, more preferably imidazole compounds and tertiary amine compounds. Specific examples of imidazole compounds include 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, benzo Imidazole and so on. Specific examples of tertiary amine compounds include: 1,8-diazabicyclo[5.4.0]-7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, Dimethylethanolamine, tris(dimethylaminomethyl)phenol, etc. As a specific example of a secondary amine compound, diethylamine, dipropylamine, dibutylamine, etc. can be mentioned. As a specific example of an organic phosphine compound, tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, diphenyl phosphine, phenyl phosphine, etc. can be mentioned. Specific examples of the tetraphenyl boron salt include: tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, and N-methylpyrolinium tetraphenylborate. Borate, etc.

The amount of the catalyst used is not particularly limited, and it is 100 parts by mass of the total of the mass of the (meth)acrylic resin (AI) and the mass of the epoxy-containing cyclic silicone compound (A-II) 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.2 parts by mass or more and 10 parts by mass or less, and still more preferably 0.5 parts by mass or more and 5 parts by mass or less.

For example, when the (meth)acrylic resin (AI) has a carboxyl group and an epoxycyclohexyl group, and the epoxy group-containing cyclic silicone compound (A-II) has an epoxycyclohexyl group, it is ( The reaction between the meth)acrylic resin (AI) and the epoxy-containing cyclic silicone compound (A-II) produces the following reaction. The reaction in which the moisture in the following reactions participates can be produced by the trace moisture in the reaction device, organic solvent, etc., which is added and brought into the reaction system. [化18]

The silicone-modified (meth)acrylic resin (A1) prepared according to the above method is directly used in the form of a reaction liquid or used in the preparation of a resin composition in a state of being isolated from the reaction liquid according to the convention.

[Preferred aspect of resin composition] Hereinafter, with regard to preferable aspects of the resin composition, the first resin composition and the second resin composition will be described. In addition, the resin composition containing the silicone modified (meth)acrylic resin (A1) is not limited to the first resin composition and the second resin composition described below.

(First resin composition) The first resin composition is a resin composition containing a silicone modified (meth)acrylic resin (A1) and a curing agent.

The first resin composition contains a silicone modified (meth)acrylic resin (A1) as an epoxy compound. The first resin composition contains a curing agent for curing the silicone-modified (meth)acrylic resin (A1), which is an epoxy compound. The curing agent may be a photosensitive curing agent, a heat-sensitive curing agent, or a combination of the two.

The first resin composition may contain epoxy compounds and/or oxetane compounds that are not silicone-modified (meth)acrylic resin (A1). The types of epoxy compounds and/or oxetane compounds that can be used together with the silicone-modified (meth)acrylic resin (A1) are not particularly limited as long as they do not hinder the purpose of the present invention.

As far as the relative dielectric constant of the cured product is low, the total mass of the silicone-modified (meth)acrylic resin (A1) in the first resin composition is relative to the mass of the epoxy compound and the oxygen The ratio of the total mass of the cyclobutane compound is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass .

The curing agent is not particularly limited as long as it is a compound previously used as a curing agent for epoxy compounds or oxetane compounds. Hereinafter, the preferred hardener will be described.

・Onium salt (D1) The onium salt (D1) can be used together with epoxy compounds or oxetane compounds, etc., to promote the hardening of epoxy compounds or oxetane compounds, etc. under the action of light or heat. The onium salt may, for example, be a diazonium salt, an ammonium salt, an iodonium salt, a sulfonium salt, a phosphonium salt, an oxonium salt, and the like. Among them, in terms of ease of obtaining and good hardening, sulphur salt and sulphur salt are preferred.

Hereinafter, preferred examples of the onium salt (D1) will be described. As a preferable example of the onium salt (D1), a sulfonium salt represented by the following formula (D-I) (hereinafter, also referred to as "a sulfonium salt (Q)") can be mentioned.

(式(D-I)中，R^D1 及R^D2 獨立地表示可經鹵素原子取代之烷基或下述式(D-II)所示之基，R^D1 及R^D2 可相互鍵結而與式中之硫原子一起形成環，R^D3 表示下述式(D-III)所示之基或下述式(D-IV)所示之基，A^D1 表示S、O、或Se，X^- 表示一價之陰離子，其中，R^D1 及R^D2 不同時為可經鹵素原子取代之烷基)[化19]

(In the formula (DI), R ^D1 and R ^D2 independently represent an alkyl group that can be substituted by a halogen atom or a group represented by the following formula (D-II). R ^D1 and R ^D2 can be bonded to each other to form The sulfur atoms together form a ring, R ^D3 represents a group represented by the following formula (D-III) or a group represented by the following formula (D-IV), A ^D1 represents S, O, or Se, and X ^- represents one Anion of valence, in which R ^D1 and R ^{D2 are} not at the same time an alkyl group which can be substituted by a halogen atom)

(式(D-II)中，環Z^D1 表示芳香族烴環，R^D4 表示可經鹵素原子取代之烷基、羥基、烷氧基、烷基羰基、烷氧基羰基、醯氧基、烷硫基、噻吩基、噻吩基羰基、呋喃基、呋喃基羰基、硒吩基、硒吩基羰基、雜環式脂肪族烴基、烷基亞磺醯基、烷基磺醯基、羥基(聚)伸烷氧基、可經取代之胺基、氰基、硝基、或鹵素原子，m1表示0以上之整數)[化20]

(In formula (D-II), ring Z ^D1 represents an aromatic hydrocarbon ring, and R ^D4 represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkane group which can be substituted by a halogen atom. Thio, thienyl, thienyl carbonyl, furyl, furyl carbonyl, selenyl, selenyl carbonyl, heterocyclic aliphatic hydrocarbon group, alkyl sulfinyl, alkyl sulfonyl, hydroxyl (poly) Alkylene group, substituted amine group, cyano group, nitro group, or halogen atom, m1 represents an integer of 0 or more)

(式(D-III)中，R^D5 表示可經如下基取代之伸烷基或下述式(D-V)所示之基，上述取代基即：羥基、烷氧基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、芳硫基羰基、醯氧基、芳硫基、烷硫基、芳基、雜環式烴基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可經取代之胺基、氰基、硝基或鹵素原子，R^D6 表示可經如下基取代之烷基或下述式(D-VI)所示之基，上述取代基即：羥基、烷氧基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、芳硫基羰基、醯氧基、芳硫基、烷硫基、芳基、雜環式烴基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可經取代之胺基、氰基、硝基、或鹵素原子，A^D2 表示單鍵、S、O、亞磺醯基、或羰基，n1表示0或1)[化21]

(In formula (D-III), R ^D5 represents an alkylene group which may be substituted by the following group or a group represented by the following formula (DV), the above-mentioned substituents are: hydroxy, alkoxy, alkylcarbonyl, aryl Carbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, alkylsulfinyl, aryl Sulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy (poly) alkoxy, substituted amine, cyano, nitro or halogen atom, R ^D6 means that it can be substituted by the following groups The alkyl group or the group represented by the following formula (D-VI), the above-mentioned substituents are: hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl , Acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfinyl, arylsulfinyl , Hydroxy (poly) alkoxy, substituted amine, cyano, nitro, or halogen atom, A ^D2 represents a single bond, S, O, sulfinyl, or carbonyl, n1 represents 0 or 1 )

(式(D-IV)中，R^D7 及R^D8 獨立地表示可經如下基取代之伸烷基或下述式(D-V)所示之基，上述取代基即：羥基、烷氧基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、芳硫基羰基、醯氧基、芳硫基、烷硫基、芳基、雜環式烴基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可經取代之胺基、氰基、硝基、或鹵素原子，R^D9 及R^D10 獨立地表示可經鹵素原子取代之烷基或上述式(D-II)所示之基，R^D9 及R^D10 可相互鍵結而與式中之硫原子一起形成環，A^D3 表示單鍵、S、O、亞磺醯基、或羰基，X^- 如上所述，n2表示0或1，其中，R^D9 及R^D10 不同時為可經鹵素原子取代之烷基)[化22]

(In formula (D-IV), R ^D7 and R ^D8 independently represent an alkylene group which may be substituted by the following group or a group represented by the following formula (DV). The above-mentioned substituents are: hydroxy, alkoxy, alkane Alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, alkylsulfinyl Amino groups, arylsulfinyl groups, alkylsulfinyl groups, arylsulfinyl groups, hydroxy (poly) alkoxy groups, optionally substituted amine groups, cyano groups, nitro groups, or halogen atoms, R ^D9 And R ^D10 independently represent an alkyl group that can be substituted by a halogen atom or the group represented by the above formula (D-II), R ^D9 and R ^D10 can be bonded to each other to form a ring with the sulfur atom in the formula, and A ^D3 represents Single bond, S, O, sulfinyl, or carbonyl, X ^- as described above, n2 represents 0 or 1, wherein R ^D9 and R ^{D10 are} not at the same time an alkyl group that can be substituted by a halogen atom)

(式(D-V)中，環Z^D2 表示芳香族烴環，R^D11 表示可經鹵素原子取代之烷基、羥基、烷氧基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、芳硫基羰基、醯氧基、芳硫基、烷硫基、芳基、雜環式烴基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可經取代之胺基、氰基、硝基、或鹵素原子，m2表示0以上之整數) [化24]

(式(D-VI)中，環Z^D3 表示芳香族烴環，R^D12 表示可經鹵素原子取代之烷基、羥基、烷氧基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、芳硫基羰基、醯氧基、芳硫基、烷硫基、噻吩基羰基、呋喃基羰基、硒吩基羰基、芳基、雜環式烴基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可經取代之胺基、氰基、硝基、或鹵素原子，m3表示0以上之整數)[化23]

(In formula (DV), ring Z ^D2 represents an aromatic hydrocarbon ring, and R ^D11 represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group which can be substituted by a halogen atom. Carbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl , Arylsulfonyl, hydroxy(poly)alkyleneoxy, substituted amine, cyano, nitro, or halogen atom, m2 represents an integer of 0 or more) [化24]

(In formula (D-VI), ring Z ^D3 represents an aromatic hydrocarbon ring, and R ^D12 represents an alkyl group, hydroxyl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aromatic Oxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, thienylcarbonyl, furylcarbonyl, selenylcarbonyl, aryl, heterocyclic hydrocarbon, aryloxy, alkylsulfinyl Amino groups, arylsulfinyl groups, alkylsulfinyl groups, arylsulfinyl groups, hydroxy (poly) alkoxy groups, optionally substituted amine groups, cyano groups, nitro groups, or halogen atoms, m3 represents Integer above 0)

(Amber salt (Q)) The following describes amber salt (Q). The sulfonium salt (Q) is characterized in that, in the benzene ring in the above formula (DI), a methyl group is bonded to a carbon atom that is ortho to the carbon atom ^{to which A D1 is bonded.} Since the sulfonium salt (Q) has a methyl group at the above-mentioned position, compared with the previous sulfonium salt, the sensitivity to active energy rays such as ultraviolet rays is higher.

In the above formula (DI), it is preferable that both R ^D1 and R ^D2 are groups represented by the above formula (D-II). R ^D1 and R ^D2 may be the same or different from each other. In the above formula (DI), when R ^D1 and R ^D2 are bonded to each other to form a ring together with the sulfur atom in the formula, the number of atoms constituting the formed ring is preferably 3 or more including the sulfur atom. Hereinafter, it is more preferably 5 or more and 7 or less. The formed ring may be a polycyclic ring, and is preferably a polycyclic ring formed by the condensation of a monocyclic ring having 5 or more and 7 or less ring constituent atoms. In the above formula (DI), it is preferable that both R ^D1 and R ^D2 are phenyl groups. In the above formula (DI), R ^{D3 is} preferably a group represented by the above formula (D-III). In the above formula (DI), A ^{D1 is} preferably S or O, more preferably S.

In the above formula (D-II), R ^{D4 is} preferably an alkyl group, a hydroxyl group, an alkylcarbonyl group, a thienylcarbonyl group, a furylcarbonyl group, a selenophenylcarbonyl group, an amine group which may be substituted by a halogen atom, or The nitro group is more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted with a halogen atom. In the above formula (D-II), m1 can be selected according to ^{the type of ring Z D1} , for example, it can be an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, and more preferably an integer of 0 or more and 2 or less.

In the above formula (D-III), R ^{D5 is} preferably an alkylene group; an alkylene group which may be substituted by a hydroxyl group, an optionally substituted amine group or a nitro group; or a group represented by the above formula (DV); more preferably It is the base shown in the above formula (DV). In the above formula (D-III), R ^{D6 is} preferably an alkyl group; an alkyl group which may be substituted by a hydroxyl group, an optionally substituted amine group or a nitro group; or a group represented by the above formula (D-VI); more preferably It is the base represented by the above formula (D-VI). In the above formula (D-III), A ^{D2 is} preferably S or O, more preferably S. In the above formula (D-III), n1 is preferably zero.

In the above formula (D-IV), R ^D7 and R ^{D8 are} independently preferably an alkylene group; an alkylene group that may be substituted by a hydroxyl group, an optionally substituted amine group or a nitro group; or the above formula (DV) The base; more preferably the base shown in the above formula (DV). R ^D7 and R ^D8 may be the same or different from each other. In the above formula (D-IV), it is preferable that both R ^D9 and R ^D10 are groups represented by the above formula (D-II). R ^D9 and R ^D10 may be the same or different from each other. In the above formula (D-IV), when R ^D9 and R ^D10 are bonded to each other to form a ring together with the sulfur atom in the formula, the number of atoms constituting the formed ring is preferably 3 including the sulfur atom Above 10 or less, more preferably 5 or more and 7 or less. The formed ring may be a polycyclic ring, and is preferably a polycyclic ring formed by the condensation of a monocyclic ring having 5 or more and 7 or less ring constituent atoms. In the above formula (D-IV), A ^{D3 is} preferably S or O, more preferably S. In the above formula (D-IV), n2 is preferably zero.

In the above formula (DV), R ^{D11 is} preferably an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an amino group which may be substituted, or a nitro group, and more preferably an alkyl group which may be substituted by a halogen atom. In the above formula (DV), m2 can be selected according to ^{the type of ring Z D2} , for example, it can be an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, and more preferably an integer of 0 or more and 2 or less.

In the above formula (D-VI), R ^{D12 is} preferably an alkyl group, a hydroxyl group, an alkylcarbonyl group, a thienylcarbonyl group, a furylcarbonyl group, a selenylcarbonyl group, an amine group which may be substituted by a halogen atom, or The nitro group is more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted with a halogen atom. In the above formula (D-VI), m3 can be selected according to ^{the type of ring Z D3} . For example, it can be an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, and more preferably an integer of 0 or more and 2 or less.

In the above formula (DI), X ^- is a monovalent anion. As X ^-, can be preferably exemplified by a monovalent anion as many atoms, more preferably _{^{MY a -, (Rf) b}} PF 6-b -, R x1 c BY 4-c -, R x1 c GaY 4-c _{^{-, R x2 SO 3 -,}} (R x2 SO 2) 3 C -, or _{^{(R x2 SO 2) 2 N}} - anion of FIG. In addition, X ^- may be a halogen anion, and examples thereof include fluoride ion, chloride ion, bromide ion, and iodide ion.

M represents a phosphorus atom, a boron atom, or an antimony atom. Y represents a halogen atom (preferably a fluorine atom).

Rf represents an alkyl group in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms (preferably an alkyl group having 1 to 8 carbon atoms). Examples of the alkyl group to be substituted by fluorine to become Rf include straight chain alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, etc.), branched chain alkyl groups (isopropyl, Isobutyl, second butyl, tertiary butyl, etc.) and cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), etc. The ratio at which hydrogen atoms of the alkyl groups are substituted with fluorine atoms in Rf is preferably 80 mol% or more based on the number of moles of hydrogen atoms originally possessed by the alkyl group, and more preferably 90% or more, and more preferably Is 100%. If the substitution ratio of the fluorine atom is in these preferable ranges, the light sensitivity of the sulfonium salt (Q) becomes better. Plus as the Rf, ^{_{include: CF 3 -, CF 3 CF}} 2 -, (CF 3) 2 CF -, CF 3 CF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 -, (CF 3) ^{_{2 CFCF 2 -, CF 3 CF}} 2 (CF 3) CF - and (CF _{3) 3} C ^-. The b pieces of Rf are independent of each other, and therefore may be the same or different from each other.

P represents a phosphorus atom, and F represents a fluorine atom.

R ^x1 represents a phenyl group in which a part of a hydrogen atom is substituted by at least one element or an electron withdrawing group. As an example of such one element, a halogen atom is included, and a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned. As the electron withdrawing group, a trifluoromethyl group, a nitro group, a cyano group, etc. may be mentioned. Among these, a phenyl group in which at least one hydrogen atom is substituted by a fluorine atom or a trifluoromethyl group is preferred. The c pieces of R ^x1 are independent of each other, and therefore may be the same or different from each other.

B represents a boron atom, and Ga represents a gallium atom.

R ^x2 represents an alkyl group with 1 to 20 carbon atoms, a fluoroalkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms. The alkyl group and the fluoroalkyl group may be linear or branched. Either chain or cyclic, the alkyl group, fluoroalkyl group, or aryl group may be unsubstituted or may have a substituent. As said substituent, a hydroxyl group, an amino group which may be substituted, a nitro group, etc. are mentioned, for example. As the amino group which may be substituted, for example, the groups exemplified in the following description related to the above-mentioned formulas (D-II) to (D-VI) can be exemplified. In addition, ^{the carbon chain in the alkyl group, fluoroalkyl group, or aryl group represented by R x2} may have a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom. In particular ^{, the carbon chain in the alkyl group or fluoroalkyl group represented by R x2} may have a divalent functional group (for example, an ether bond, a carbonyl bond, an ester bond, an amino bond, an amide bond, an imine bond, a sulfonyl group Bond, sulfonamide bond, sulfonamide bond, urethane bond, etc.). When ^{the alkyl group, fluoroalkyl group or aryl group represented by R x2} has the above-mentioned substituents, heteroatoms or functional groups, the number of the above-mentioned substituents, heteroatoms or functional groups may be one or two More than one.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom. a represents an integer of 4 or more and 6 or less. b is preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, and particularly preferably 2 or 3. c is preferably an integer of 1 or more and 4 or less, more preferably 4.

As MY _a ^- of the anion represented may, for example ₆ SbF ^-, PF ₆ ^- anion shown in the ^- or BF _4.

As _{(Rf) b PF 6-b} - of the anion represented, _{include: (CF 3 CF 2) 2} PF 4 -, (CF 3 CF 2) 3 PF 3 -, ((CF 3) 2 CF) 2 ^{_{PF 4 -, ((CF 3}} ) 2 CF) 3 PF 3 -, (CF 3 CF 2 CF 2) 2 PF 4 -, (CF 3 CF 2 CF 2) 3 PF 3 -, ((CF 3) 2 CFCF ^{_{2) 2 PF 4 -, (}} (CF 3) 2 CFCF 2) 3 PF 3 -, (CF 3 CF 2 CF 2 CF 2) 2 PF 4 - or _{(CF 3 CF 2 CF 2 CF} 2) 3 PF 3 - Anions etc. shown. Of these, preferred are _{(CF 3 CF 2) 3 PF} 3 -, (CF 3 CF 2 CF 2) 3 PF 3 -, ((CF 3) 2 CF) 3 PF 3 -, ((CF 3) 2 ^{_{CF) 4 2 PF -, (}} (CF 3) 2 CFCF 2) 3 PF 3 - , or _{((CF 3) 2 CFCF 2} ) 2 PF 4 - anion of FIG.

As R ^x1 _c BY _4-c ^- the anion represented, preferably _{^{R x1 c BY 4-c -}} ( wherein, R ^x1 represents at least a portion of the hydrogen atoms substituted by a halogen atom or the electron withdrawing group phenyl, Y represents a halogen atom, c denotes an integer of 1 or more of the following 4), for example, _{include: (C 6 F 5) 4} B -, ((CF 3) 2 C 6 H 3) 4 B -, (CF 3 C 6 H 4 _{^{) 4 B -, (C 6}} F 5) 2 BF 2 -, C 6 F 5 BF 3 - or _{(2) 4 B C 6 H} 3 F - anion of FIG. Among these, the anion represented by _{(C 6} F ₅ ) ₄ B ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^{-is preferred.}

As R ^x1 _c GaY _4-c ^- the anion represented, _{include: (C 6 F 5) 4} Ga -, ((CF 3) 2 C 6 H 3) 4 Ga -, (CF 3 C 6 H 4 _{^{) 4 Ga -, (C 6}} F 5) 2 GaF 2 -, C 6 F 5 GaF 3 - or _{(C 6 H 3 F 2)} 4 Ga - anion of FIG. Among them, the anion represented by _{(C 6} F ₅ ) ₄ Ga ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^{-is preferred.}

Examples of the anion represented by R ^x2 SO ₃ ^- include: trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, pentafluorobenzenesulfonate anion, P-toluenesulfonate anion, benzenesulfonate anion, camphorsulfonate anion, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion and butanesulfonate anion, etc. Among these, preferred are trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion or p-toluenesulfonate anion.

As the ^{_{(2 R x2 SO) 3 C}} - anion represented, the include _{(CF 3 SO 2) 3 C} -, (C 2 F 5 SO 2) 3 C -, (C 3 F 7 SO 2) 3 C ^-Or (C ₄ F ₉ SO ₂ ) ₃ C ^- as an anion, etc.

As the ^{_{(2 R x2 SO) 2 N}} - as shown in the anion, include _{(CF 3 SO 2) 2 N} -, (C 2 F 5 SO 2) 2 N -, (C 3 F 7 SO 2) 2 N ^-Or (C ₄ F ₉ SO ₂ ) ₂ N ^- as an anion, etc.

As much as a monovalent anion atoms, except ^{_{MY a -, (Rf) b}} PF 6-b -, R x1 c BY 4-c -, R x1 c GaY 4-c -, R x2 SO 3 -, (R x2 SO _{2) 3} C ^- or ^{_{(2) 2 N R x2 SO}} - anion other than the illustrated, can be performed using halogen acid ion (ClO ₄ ^-, BrO ₄ ^-, etc.), a halogen acid ion (FSO ₃ ^-, ClSO ₃ ^-, etc.), sulfate ion ^{_{(CH 3 SO 4 -, CF}} 3 SO 4 -, HSO 4 - , etc.), carbonate ions ^{_{(HCO 3 -, CH 3 CO}} 3 - , etc.), aluminum ion (AlCl ₄ ^-, AlF ₄ ^-, etc.), hexafluoro bismuth ions (BiF ₆ ^-), carboxylate ion ^{_{(CH 3 COO -, CF 3}} COO -, C 6 H 5 COO -, CH 3 C 6 H 4 COO -, C 6 F ^{_{5 COO -, CF 3 C 6}} H 4 COO - , etc.), an aryl borate ion _{(B (C 6 H 5)} 4 -, CH 3 CH 2 CH 2 CH 2 B (C 6 H 5) 3 - , etc.) , thiocyanate ion (SCN ^-) and nitrate ion (NO ₃ ^-) and the like.

Such X ^- in terms of performance to the cationic polymerized, preferably _{^{MY a -, (Rf) b}} PF 6-b -, R x1 c BY 4-c -, R x1 c GaY 4-c - and _{^{(R x2 SO 2) 3 C}} - anion represented, the better is _{^{SbF 6 -, PF 6 -,}} (CF 3 CF 2) 3 PF 3 -, (C 6 F 5) 4 B -, ((CF 3 _{) 2 C 6 H 3) 4} B -, (C 6 F 5) 4 Ga -, ((CF 3) 2 C 6 H 3) 4 Ga - and _{(CF 3 SO 2) 3 C} -, and further preferably _{^{R x1 c BY 4-c -}} .

In the above formulas (D-II), (DV), and (D-VI), the aromatic hydrocarbon ring may, for example, be a benzene ring or a condensed polycyclic aromatic hydrocarbon ring. As the condensed polycyclic aromatic hydrocarbon ring, for example, a condensed bicyclic to tetracyclic aromatic hydrocarbon ring such as a condensed bicyclic hydrocarbon ring or a condensed tricyclic aromatic hydrocarbon ring is preferable. As condensed bicyclic hydrocarbon rings, e.g. naphthalene ring is preferably a C _{8 ~ 20} condensed bicyclic hydrocarbon rings, more preferably C _{10 ~ 16} condensed bicyclic hydrocarbon ring. As the condensed tricyclic aromatic hydrocarbon ring, for example, an anthracene ring, a phenanthrene ring, etc. are preferable. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

In the above formulas (D-I) to (D-VI), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the above formulas (DI) to (D-VI), examples of the alkyl group include straight chain alkyl groups having 1 to 18 carbon atoms, branched chain alkyl groups having 3 to 18 carbon atoms, and carbon atoms A cycloalkyl group having a number of 3 or more and 18 or less, etc. Especially in the above formulas (DI), (D-II), and (D-IV) to (D-VI), the so-called alkyl group substituted with a halogen atom refers to an alkyl group and an alkyl group substituted with a halogen atom. The alkyl group substituted with a halogen atom may, for example, be a group in which at least one hydrogen atom of the aforementioned linear alkyl group, branched chain alkyl group, or cycloalkyl group is substituted with a halogen atom. Preferred examples of straight-chain alkyl include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl Alkyl, n-hexadecyl, and n-octadecyl, etc. Preferred specific examples of branched alkyl groups include isopropyl, isobutyl, second butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, isohexyl, and Isooctadecyl and the like. Preferred specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-decylcyclohexyl, and the like. Preferred specific examples of the alkyl group substituted with a halogen atom include monofluoromethyl, difluoromethyl, and trifluoromethyl. Among the alkyl groups that may be substituted by halogen atoms, R ^D1 , R ^D2 , R ^D9 , or R ^{D10 is} particularly preferably a trifluoromethyl group, and R ^D4 , R ^D6 , R ^D11 , or R ^{D12 is} particularly preferably A base.

In the above formulas (D-II) to (D-VI), the alkoxy group may, for example, be a linear or branched alkoxy group having 1 to 18 carbon atoms. Examples of preferred alkoxy groups include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, and tertiary butoxy Group, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy, etc.

In the above formulas (D-II) to (D-VI), examples of the alkyl group in the alkylcarbonyl group include the above-mentioned linear alkyl groups having 1 to 18 carbon atoms, and branched groups having 3 to 18 carbon atoms. Alkyl group or cycloalkyl group having 3 to 18 carbon atoms. The alkylcarbonyl group may, for example, be a linear, branched or cyclic alkylcarbonyl group having 2 to 18 carbon atoms. Preferred specific examples of the alkylcarbonyl group include: acetyl, propionyl, butanoyl, 2-methylpropanoyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, Decanoyl, dodecanoic, octadecanoic, cyclopentanyl, and cyclohexyl and the like.

In the above formulas (D-III) to (D-VI), the arylcarbonyl group may, for example, be an arylcarbonyl group having 7 or more and 11 or less carbon atoms. Preferred specific examples of the arylcarbonyl group include benzyl and naphthyl.

In the above formulas (D-II) to (D-VI), the alkoxycarbonyl group may, for example, be a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms. Preferred specific examples of the alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, butyl Oxycarbonyl, tertiary butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl, etc.

In the above formulas (D-III) to (D-VI), the aryloxycarbonyl group may, for example, be an aryloxycarbonyl group having 7 to 11 carbon atoms. Preferable specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a naphthoxycarbonyl group.

In the above formulas (D-III) to (D-VI), the arylthiocarbonyl group may, for example, be an arylthiocarbonyl group having 7 or more and 11 carbon atoms. Preferable specific examples of the arylthiocarbonyl group include phenylthiocarbonyl, naphthyloxythiocarbonyl, and the like.

In the above formulas (D-II) to (D-VI), examples of the anooxy group include linear or branched oxyoxy groups having 2 to 19 carbon atoms. Preferred specific examples of the acetoxy group include: acetoxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, and isobutylcarbonyloxy group. , Second butylcarbonyloxy, tertiary butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, and octadecylcarbonyloxy, etc.

In the above formulas (D-III) to (D-VI), the arylthio group may, for example, be an arylthio group having 6 or more and 20 or less carbon atoms. Preferred specific examples of the arylthio group include: phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3 -Chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4- Fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4 -[4-(phenylthio)benzyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]benzene Sulfuryl, 4-(phenylthio)phenylthio, 4-benzylphenylthio, 4-benzyl-2-chlorophenylthio, 4-benzyl-3-chlorophenylthio Group, 4-benzyl-3-methylthiophenylthio, 4-benzyl-2-methylthiophenylthio, 4-(4-methylthiobenzyl)phenylthio , 4-(2-Methylthiobenzyl)phenylthio, 4-(p-methylbenzyl)phenylthio, 4-(p-ethylbenzyl)phenylthio, 4- (P-isopropylbenzyl)phenylthio, 4-(p-tert-butylbenzyl)phenylthio, and the like.

In the above formulas (D-II) to (D-VI), the alkylthio group may, for example, be a linear or branched alkylthio group having 1 to 18 carbon atoms. Preferred specific examples of alkylthio include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, second butylthio, and third butylthio. Thiol, pentylthio, isopentylthio, neopentylthio, tertiary pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio, etc.

In the above formulas (D-III) to (D-VI), the aryl group may, for example, be an aryl group having 6 or more and 10 or less carbon atoms. Preferable specific examples of the aryl group include phenyl, tolyl, dimethylphenyl, naphthyl, and the like.

In the above formula (D-II), examples of the heterocyclic aliphatic group include a heterocyclic aliphatic group having 2 or more and 20 carbon atoms, preferably 4 or more and 20 or less, and the like. Preferred specific examples of the heterocyclic aliphatic group include: pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, piperidinyl, tetrahydropiperanyl, tetrahydrothiopyranyl, and linolinyl, etc. .

基、噻嗯基、啡㗁𠯤基、啡㗁噻基、𠳭烷基、異𠳭烷基、二苯并噻吩基、𠮿酮基、9-氧硫𠮿

基、及二苯并呋喃基等。In the above formulas (D-III) to (D-VI), the heterocyclic aromatic group may, for example, be a heterocyclic aromatic group having 4 or more and 20 or less carbon atoms. Preferred specific examples of the heterocyclic aromatic group include: thienyl, furyl, selenophene, piperanyl, pyrrolyl, azolyl, thiazolyl, pyridyl, pyrimidinyl, and pyridyl , Indolyl, benzofuranyl, benzothienyl, quinolinyl, isoquinolinyl, quinolinyl, quinazolinyl, carbazolyl, acridinyl, phenothionyl, phenanthrenyl , 𠮿

Group, thienyl group, phenanthrene group, phenanthrene group, thioalkyl group, isothioalkyl group, dibenzothienyl group, ketone group, 9-oxythio group

Group, and dibenzofuranyl, etc.

In the above formulas (D-III) to (D-VI), the aryloxy group may, for example, be an aryloxy group having 6 to 10 carbon atoms. Preferable specific examples of the aryloxy group include a phenoxy group and a naphthoxy group.

In the above formulas (D-II) to (D-VI), the alkylsulfinyl group may, for example, be a linear or branched sulfinyl group having 1 to 18 carbon atoms. Preferred specific examples of the alkylsulfinyl group include: methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, and butylsulfinyl Acetyl, isobutylsulfinyl, second butylsulfinyl, tertiary butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl Group, third pentyl sulfinyl group, octyl sulfinyl group, and isooctadecyl sulfinyl group, etc.

In the above formulas (D-III) to (D-VI), the arylsulfinyl group may, for example, be an arylsulfinyl group having 6 to 10 carbon atoms. Preferable specific examples of the arylsulfinyl group include phenylsulfinyl group, tolylsulfinyl group, naphthylsulfinyl group, and the like.

In the above formulas (D-II) to (D-VI), examples of the alkylsulfonyl group include linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms. Preferred specific examples of alkylsulfonyl groups include: methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutyl Sulfonyl, second butyl sulfonyl, tertiary butyl sulfonyl, pentyl sulfonyl, isoamyl sulfonyl, neopentyl sulfonyl, tertiary pentyl sulfonyl, octyl Sulfonyl, and octadecylsulfonyl, etc.

In the above formulas (D-III) to (D-VI), the arylsulfonyl group may, for example, be an arylsulfonyl group having 6 to 10 carbon atoms. Preferred specific examples of the arylsulfonyl group include phenylsulfonyl group, tolylsulfonyl (tosyl), naphthylsulfonyl group, and the like.

In the above formulas (D-II) to (D-VI), the hydroxyl (poly)alkoxyl group may, for example, be a hydroxyl(poly)alkoxyl group represented by HO(AO) _q -. In the above formula, AO independently represents ethoxylate and/or propoxylate, and q represents an integer of 1 or more and 5 or less.

In the above formulas (D-II) to (D-VI), the substituted amino group may, for example, be an amino group (-NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms. Preferred specific examples of the substituted amino group include: methylamino group, dimethylamino group, ethylamino group, methylethylamino group, diethylamino group, n-propylamino group , Methyl n-propyl amino, ethyl n-propyl amino, n-propyl amino, isopropyl amino, isopropyl methyl amino, isopropyl ethyl amino, diisopropyl amine Group, phenylamino group, diphenylamino group, methylphenylamino group, ethylphenylamino group, n-propylphenylamino group, isopropylphenylamino group, etc.

In the above formulas (D-III) and (D-IV), examples of the alkylene group include linear or branched alkylene groups having 1 to 18 carbon atoms. Preferred specific examples of alkylene include: methylene, 1,2-ethylene, 1,1-ethylene, propane-1,3-diyl, propane-1,2-diyl Base, propane-1,1-diyl, propane-2,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, Butane-1,1-diyl, butane-2,2-diyl, butane-2,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, Hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, 2-ethylhexane-1,6-diyl, nonane-1,9 -Diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane -1,14-diyl, pentadecane-1,15-diyl, and hexadecane-1,16-diyl, etc.

The following cations can be mentioned as specific examples of the cation part of the amenium salt (Q) represented by the above formula (DI). As a specific example of the anion part of the sulfonium salt (Q) represented by the above formula (DI), a conventionally known cation such as the cation exemplified in the description of ^{X-above can be exemplified.} The sulfonium salt (Q) represented by the above formula (DI) can be synthesized according to the above scheme, and by performing salt exchange as necessary, the cation part can be combined with the desired anion part, especially with R ^x1 _c BY _{4- c} ^- (wherein, R ^x1 represents a hydrogen atom is substituted with at least a portion of the electron-withdrawing group or a halogen atom, a phenyl group, Y represents a halogen atom, c denotes an integer of from 1 to 4) a combination of an anion FIG.

[化25]

Among the above-mentioned preferable group of cation parts, the cation part represented by the following formula is more preferable. [化26]

The content of the onium salt (D1) in the resin composition is not particularly limited as long as the curing of the resin composition proceeds well. In terms of easy curing of the resin composition, the content of the onium salt (D1) in the resin composition is typically based on the onium salt (D1) relative to the epoxy compound and/or oxetane compound. D1) 100 parts by mass of the material to be hardened, but 0.01 parts by mass or more and 50 parts by mass or more, preferably 0.01 parts by mass or more and 30 parts by mass or less, more preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.05 Part by mass or more and 15 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less.

・Epoxy compound or oxetane compound hardener (D2) The curing agent for epoxy compound or oxetane compound (D2) (hereinafter, also referred to as curing agent (D2)) is a curing agent other than the above-mentioned onium salt (D1), and can be appropriately selected from previously known curing agents . The hardener (D2) is used together with epoxy compounds or oxetane compounds to help harden by heating.

As the hardening agent (D2), for example, a phenol hardening agent, an acid anhydride hardening agent, a polyamine hardening agent, and a catalyst hardening agent may be mentioned. The usage amount of phenolic hardener and acid anhydride hardener is 100 parts by mass of the total amount of epoxy compound and oxetane compound in the resin composition, preferably 1 part by mass or more and 200 parts by mass or less, more preferably It is 50 parts by mass or more and 150 parts by mass or less, and more preferably 80 parts by mass or more and 120 parts by mass or less. The phenolic curing agent and the acid anhydride curing agent may be used alone, respectively, or two or more of them may be used in combination. The usage amount of the polyamine-based hardener is relative to 100 parts by mass of the total amount of the epoxy compound and the oxetane compound of the resin composition, preferably 0.1 part by mass or more and 50 parts by mass or less, more preferably 0.5 part by mass or more 30 parts by mass or less, particularly preferably 1 part by mass and 15 parts by mass. These polyamine-based hardeners may be used alone or in combination of two or more kinds. The usage amount of the catalyst-type hardener is relative to 100 parts by mass of the total amount of epoxy compound and oxetane compound of the resin composition, preferably 1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more 80 parts by mass or less, particularly preferably 1 part by mass or more and 50 parts by mass or less. These catalyst-type hardeners may be used alone or in combination of two or more kinds.

・A hardening agent (D3) that generates alkali components by heat As the hardener (D3) that generates an alkali component by heat, a compound previously used as a thermal alkali generator can be used without particular limitation. For example, 2-benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)-butan-1-one can be used as a hardener that generates an alkali component by heat. Furthermore, 2-benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)-butan-1-one will also produce a base under the action of light.

(式(d1)中，R^d1 、R^d2 及R^d3 分別獨立地表示氫原子、鹵素原子、羥基、巰基、硫基、矽烷基、矽烷醇基、硝基、亞硝基、膦基、磺酸根基、氧膦基、膦酸根基、或有機基)In addition, a compound that generates an imidazole compound represented by the following formula (d1) by heating (hereinafter, also referred to as a thermal imidazole generator) is also suitably used as a hardening agent. [化27]

(Formula (d1) of, R ^d1, R ^d2 and R ^d3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, thio, silicon alkyl, silicon alkoxide group, a nitro group, a nitroso group, a phosphino group, a sulfo (Acid radical, phosphinyl, phosphonate, or organic group)

As R ^d1, R ^{d2 and} R ^d3, and the organic group may include: alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl and the like. The organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. In addition, the organic group may be any of linear, branched, and cyclic. This organic group is usually monovalent, but in the case of forming a cyclic structure, etc., it may become an organic group having a valence of two or more.

R ^d1 and R ^d2 may allow these bonds to form a cyclic structure, and may further include heteroatom bonds. As a cyclic structure, a heterocycloalkyl group, a heteroaryl group, etc. are mentioned, and it may be a condensed ring.

R ^d1, R ^d2 and the key contained in the organic group of R ^d3 as long as effects of the present invention is not particularly limited, and may include an organic group containing a hetero atom bond of an oxygen atom, a nitrogen atom, silicon atom. Specific examples of bonds containing heteroatoms include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, imino bonds (-N= C(-R ^d0 )-, -C(=NR ^d0 )-: R ^d0 represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.

As R ^d1, R ^d2 and R ^d3 may have an organic group of the bond-containing hetero atoms, in view of heat resistance of the imidazole compound, it is preferably an ether bond, a thioether bond, a carbonyl bond, sulfur-carbonyl bond, an ester Bond, amide bond, urethane bond, imino bond (-N=C(-R ^d0 )-, -C(=NR ^d0 )-: R ^d0 represents a hydrogen atom or an organic group), carbonate Bond, sulfonyl bond, sulfinyl bond.

When in the R ^d1, R ^d2 and R ^d3 is an organic group other than the substituent of the hydrocarbon group of the case, R ^d1, R ^d2 and R ^d3 as long as the effects of the present invention, is not particularly limited. Specific examples of R ^d1, R ^d2 and R ^d3 of, include: a halogen atom, a hydroxyl, mercapto, thio, cyano, isocyano, isocyanato groups, isocyanato, thiocyanato, isocyanato sulfur Group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamethan group, carbothiocarbamate group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfinic group Acid group, sulfonate group, phosphine group, phosphinyl group, phosphonate group, alkyl ether group, alkenyl ether group, alkyl sulfide group, alkenyl sulfide group, aryl ether group, aryl sulfide group Wait. The hydrogen atom contained in the above substituent may be substituted by a hydrocarbon group. Moreover, the hydrocarbon group contained in the said substituent may be any of linear, branched, and cyclic.

R ^d1 , R ^d2 and R ^{d3 are} preferably hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, And a halogen atom, more preferably a hydrogen atom.

The thermal imidazole generator is not particularly limited as long as it is a compound that can generate the imidazole compound represented by the above formula (d1) by heating. Regarding the compound that produces amine under the action of heat (thermal base generator) previously formulated in various compositions, the skeleton derived from the amine produced upon heating is replaced with the one derived from the above-mentioned formula (d1) The skeleton of the imidazole compound is used to obtain a compound used as a thermal imidazole generator.

(式(d2)中，R^d1 、R^d2 及R^d3 分別獨立地表示氫原子、鹵素原子、羥基、巰基、硫基、矽烷基、矽烷醇基、硝基、亞硝基、磺酸根基、膦基、氧膦基、膦酸根基、或有機基。R^d4 及R^d5 分別獨立地表示氫原子、鹵素原子、羥基、巰基、硫基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺酸基、磺酸根基、膦基、氧膦基、膦酸基、膦酸根基、或有機基。R^d6 、R^d7 、R^d8 、R^d9 及R^d10 分別獨立地表示氫原子、鹵素原子、羥基、巰基、硫基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺酸基、磺酸根基、膦基、氧膦基、膦酸基、膦酸根基、胺基、銨基、或有機基。R^d6 、R^d7 、R^d8 、R^d9 及R^d10 可讓該等之兩個以上鍵結而形成環狀結構，亦可包含雜原子之鍵)As a preferable thermal imidazole generator, a compound represented by the following formula (d2) can be exemplified. [化28]

(In the formula ^{(d2), R d1, R} d2 and R ^d3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, thio, silicon alkyl, silicon alkanoyl, nitro, nitroso, sulfonate, Phosphine, phosphinyl, phosphonate, or organic group. R ^d4 and R ^d5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thio group, a silyl group, a silanol group, a nitro group, and a nitroso group , sulfinic acid group, a sulfonic acid group, a sulfonate, a phosphino group, a phosphinyl group, phosphonic acid, phosphonate, or an organic group ^{.R d6, R d7, R d8} , R d9 and R ^d10 are each independently Represents hydrogen atom, halogen atom, hydroxyl group, mercapto group, thio group, silyl group, silanol group, nitro group, nitroso group, sulfinic acid group, sulfonic acid group, sulfonate group, phosphine group, phosphinyl group, phosphonic acid group, a phosphonate, an amine, an ammonium group, or an organic group ^{.R d6, R d7, R d8} , R d9 and R ^d10 allows two or more of these bonds to form a cyclic structure may also include hetero Atomic bond)

In the illustrated, R ^d1, R ^d2 and R ^d3 of formula (d2) with respect to the formula ^(d1) R d1, R ^d2, and the same R ^d3.

In formula (d2), R ^d4 and R ^d5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thio group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinic acid group, and a sulfonic acid group. , Sulfonate group, phosphine group, phosphinyl group, phosphonate group, phosphonate group, or organic group.

As R ^d4 and R ^d5 in the organic group may be an organic group on R ^d1, R ^d2 and R ^d3 of exemplified. The organic group and R ^d1, R ^d2 and R ^d3 case the same manner as in the organic group may contain heteroatoms. In addition, the organic group may be any of linear, branched, and cyclic.

^{Among the} above, as R d4 and R ^d5 , each independently preferably is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, and a carbon atom of 4 to 13 or less. Cycloalkenyl groups, aryloxyalkyl groups with 7 to 16 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, cyano groups with 2 to 11 carbon atoms, and carbon atoms with hydroxyl groups Alkyl groups with 1 to 10, alkoxy groups with 1 to 10 carbon atoms, amide groups with 2 to 11 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, and 1 or more carbon atoms An acyl group with 10 or less, an ester group with 2 to 11 carbon atoms (-COOR ^d , -OCOR ^d : R ^d represents a hydrocarbon group), an aryl group with 6 to 20 carbon atoms, an electron-donating group, and/or An aryl group with 6 or more and 20 carbon atoms substituted with an electron withdrawing group, benzyl, cyano, and methylthio groups substituted with an electron donating group and/or an electron withdrawing group. More preferably ^{, both of Rd4} and ^Rd5 are hydrogen atoms, or ^Rd4 is a methyl group, and ^Rd5 is a hydrogen atom.

In formula (d2), ^Rd6 , ^Rd7 , ^Rd8 , ^Rd9, and ^Rd10 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thio group, a silyl group, a silanol group, a nitro group, and a nitroso group. , Sulfinic acid group, sulfonic acid group, sulfonate group, phosphine group, phosphinyl group, phosphonic acid group, phosphonate group, amine group, ammonium group, or organic group.

As ^{R d6, R d7, R d8} , R d9 and R ^d10 in the organic group include R ^d1, R ^{d2 and} R ^d3, and an organic group shown by the embodiment. The case where the organic radical R and R ^d1 and ^D2 in the same manner as the organic group may contain a key other than the hetero atom or a hydrocarbon substituent group. In addition, the organic group may be any of linear, branched, and cyclic.

R ^d6 , ^Rd7 , ^Rd8 , ^Rd9 and ^Rd10 can allow two or more of these to be bonded to form a cyclic structure, and may also include a heteroatom bond. As a cyclic structure, a heterocycloalkyl group, a heteroaryl group, etc. are mentioned, and it may be a condensed ring. For example, ^{R d6, R d7, R d8} , R d9 and R ^d10 allows two or more of these bonding, are bonded 5,977 ^{R d6, R d7, R d8} , R d9 atoms of the phenyl ring, and R ^d10 The formation of naphthalene, anthracene, phenanthrene, indene and other condensed rings.

Among the above, as ^Rd6 , ^Rd7 , ^Rd8 , ^Rd9 and ^Rd10 , each independently is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 4 to 13 carbon atoms , Cycloalkenyl groups with 4 to 13 carbon atoms, aryloxyalkyl groups with 7 to 16 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, and cyano groups with 2 to 11 carbon atoms Alkyl groups with hydroxy groups having 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, amide groups with 2 to 11 carbon atoms, and 1 to 10 carbon atoms Alkylthio groups, acyl groups with 1 to 10 carbon atoms, ester groups with 2 to 11 carbon atoms, aryl groups with 6 to 20 carbon atoms, substituted by electron donating groups and/or electron withdrawing groups Aryl groups with 6 to 20 carbon atoms, benzyl groups, cyano groups, methylthio groups, and nitro groups substituted with electron-donating groups and/or electron-withdrawing groups.

In addition, as ^Rd6 , ^Rd7 , ^Rd8 , ^Rd9, and ^Rd10 , it is also preferable to have the following situation: these two or more ^{bondings have a total of Rd6} , Rd7, ^Rd8 , ^Rd9, and ^Rd10 . The bonded benzene ring atoms form naphthalene, anthracene, phenanthrene, indene and other condensed rings.

(式(d3)中，R^d1 、R^d2 及R^d3 與式(d1)及(d2)同義。R^d4 ～R^d9 與式(d2)同義。R^d11 表示氫原子或有機基。R^d6 及R^d7 不為羥基。R^d6 、R^d7 、R^d8 及R^d9 可讓該等之兩個以上鍵結而形成環狀結構，亦可包含雜原子之鍵)Among the compounds represented by the above formula (d2), the compound represented by the following formula (d3) is preferred. [化29]

(In the formula ^{(d3), R d1, R} d2 and R ^d3 of formula (d1) and (d2) .R ^d4 ~ R ^d9 is synonymous with Formula (d2) synonymous .R ^d11 represents a hydrogen atom or an organic group and .R ^d6 R ^{d7 is} not a hydroxyl group. R ^d6 , R ^d7 , R ^d8 and R ^d9 can allow two or more of these to be bonded to form a cyclic structure, and may also include heteroatom bonds)

Since the compound represented by the formula (d3) has the substituent -OR ^d11 , it has excellent solubility in organic solvents.

In formula (d3), R ^d11 is a hydrogen atom or an organic group. In the case when R ^d11 is an organic group, the organic group as, include R ^d1, R ^{d2 and} R ^d3, and an organic group shown by the embodiment. The organic group may contain heteroatoms in the organic group. In addition, the organic group may be any of linear, branched, and cyclic. R ^{d11 is} preferably a hydrogen atom, an alkyl group or an alkoxyalkyl group having 1 to 12 carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Group, tertiary butyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, propoxymethyl, butoxymethyl.

Specific examples of compounds that are particularly preferred as thermal imidazole generators are shown below. [化30]

・Organic solvent (S) Typically, the resin composition may contain an organic solvent (S) for the purpose of adjusting coatability. As the organic solvent (S), for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene two Alcohol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly)alkylene Glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol mono Methyl ether acetate, propylene glycol monoethyl ether acetate and other (poly) alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene two Alcohol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionic acid methyl ester, 2-hydroxypropionic acid ethyl ester and other lactic acid Alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethoxy ethyl propionate, ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-acetic acid Methoxybutyl ester, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, Isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, Other esters such as methyl acetylacetate, ethyl acetylacetate, ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethyl Amides such as formamide and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more kinds.

The use amount of the organic solvent (S) can be appropriately determined according to the use of the resin composition. As an example of the usage amount of the organic solvent (S), the solid content concentration of the resin composition may be an amount in the range of 1% by mass to 50% by mass.

・Other ingredients The resin composition may optionally contain various additives other than the above-mentioned components. Specifically, examples thereof include dispersion aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, thermal polymerization inhibitors, defoamers, surfactants, and the like.

The resin composition may include an epoxy group-containing cyclic silicone compound (A-II) that does not react with the (meth)acrylic resin (A-I). In terms of easy formation of a cured product with a low relative permittivity, the resin composition preferably does not contain an epoxy group-containing cyclic siloxane compound. When the resin composition contains the epoxy-containing cyclic silicone compound (A-II), its content is preferably 40 mass relative to the mass of the resin composition excluding the mass of the organic solvent (S) % Or less, more preferably 10% by mass or less, and still more preferably 1% by mass or less.

(Second resin composition) The second resin composition contains the aforementioned silicone-modified (meth)acrylic resin (A1), a photopolymerizable monomer (B), and a photopolymerization initiator (C). Among them, the silicone modified (meth)acrylic resin (A1) contains a (meth)acrylic resin containing a structural unit having an alkali-soluble group as an alkali-soluble resin. It does not specifically limit as an alkali-soluble group, A carboxyl group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc. are mentioned. By containing the photopolymerizable monomer (B) and the photopolymerization initiator (C), the second resin composition is cured by exposure. On the other hand, the second resin composition in the unexposed state contains a silicone modified (meth)acrylic resin (A1) containing a structural unit having an alkali-soluble group, so it is soluble in an alkaline developer. Therefore, when the second resin composition is used, a negative mask can be used to pattern the cured film by photolithography. Since the second resin composition contains the epoxy-modified (meth)acrylic resin (A1), it can be cured by heating. The second resin composition may not contain the curing agent for epoxy compounds. The reason is that under the action of alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups of the silicone-modified (meth)acrylic resin, the curing reaction of the epoxy group proceeds.

Hereinafter, the essential or optional components that can be contained in the second resin composition will be described.

・Siloxane modified (meth)acrylic resin (A1) The silicone-modified (meth)acrylic resin (A1) containing the structural unit having an alkali-soluble group is as described above.

・Other resins The second resin composition may contain various alkali-soluble resins as resins other than the silicone-modified (meth)acrylic resin (A1). In terms of the relative dielectric constant of the cured product, the mass of the silicone-modified (meth)acrylic resin (A1) in the second resin composition is relative to that of the silicone-modified (meth)acrylic The ratio of the total mass of the resin (A1) to the mass of other resins is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more, especially Preferably, it is 100% by mass.

Hereinafter, an alkali-soluble resin, which is preferable as other resins, will be described.

As a preferable alkali-soluble resin, resin (a-1) having a Cardo structure (hereinafter, also referred to as "Cardo resin (a-1)") can be mentioned.

As the resin (a-1) having a Cardo structure, it can be used for a resin having a Cardo structure and a predetermined alkali solubility in its structure. The so-called Cardo structure refers to a structure in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting the first ring structure. Furthermore, the second cyclic structure and the third cyclic structure may be the same structure or different structures. As a representative example of the Cardo structure, a structure in which two aromatic rings (such as a benzene ring) are bonded to the 9-position carbon atom of the chrysanthemum ring can be exemplified.

It does not specifically limit as Cardo resin (a-1), A conventionally well-known resin can be used. Among them, the resin represented by the following formula (a-1) is preferred.

[化31]

In the formula (a-1), X ^{a represents a group} represented by the following formula (a-2). t1 represents an integer from 0 to 20.

[化32]

In the above formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, and R ^a3 each independently represents For linear or branched alkylene groups, t2 represents 0 or 1, and Wa represents ^{a group} represented by the following formula (a-3).

[化33]

In the formula (a-2), ^{Ra3 is} preferably an alkylene having 1 to 20 carbon atoms, more preferably an alkylene having 1 to 10 carbon atoms, and particularly preferably 1 or more carbon atoms The alkylene groups below 6 are most preferably ethane-1,2-diyl, propane-1,2-diyl, and propane-1,3-diyl.

^{The ring A 1} in the formula (a-3) represents an aliphatic ring that may be condensed with an aromatic ring and may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring. The aliphatic ring may, for example, be a monocycloalkane, a dicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, examples thereof include monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, nordecane, isodecane, tricyclodecane, and tetracyclododecane. The aromatic ring that can be condensed on the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferable.

As a preferable example of the divalent group represented by formula (a-3), the following groups can be mentioned. [化34]

Of formula (a-1) in the divalent radical X ^a system by providing that the Z ^a residue of tetracarboxylic dianhydride (a-2a) is reacted with a compound of the formula of the diphenols illustrated Cardo introduced into the resin (a -1) In. [化35]

In the formula (a-2a), ^Ra1 , ^Ra2 , ^Ra3 , and t2 are as described with respect to the formula (a-2). ^{Regarding the ring A 1} in the formula (a-2a), it is as described with respect to the formula (a-3).

The diphenol compound represented by the formula (a-2a) can be produced, for example, by the following method. First, the hydrogen atom in the phenolic hydroxyl group of the diphenol compound represented by the following formula (a-2b) is substituted with ^{the group represented by -R a3} -OH according to the convention as necessary, and then it is carried out using epichlorohydrin or the like Glycilylation is performed to obtain an epoxy compound represented by the following formula (a-2c). Next, by reacting the epoxy compound represented by the formula (a-2c) with acrylic acid or methacrylic acid, the diphenol compound represented by the formula (a-2a) is obtained. In formula (a-2b) and formula (a-2c), ^Ra1 , ^Ra3 , and t2 are as described with respect to formula (a-2). ^{Regarding the ring A 1} in the formula (a-2b) and the formula (a-2c), as described with respect to the formula (a-3). In addition, the manufacturing method of the diphenol compound represented by formula (a-2a) is not limited to the above-mentioned method. [化36]

As a preferable example of the diphenol compound represented by formula (a-2b), the following diphenol compounds can be mentioned. [化37]

In the above formula (a-1), ^Ra0 is a hydrogen atom or ^a group represented by -CO-Y a -COOH. Here, Y ^a represents the residue after removing the acid anhydride group (-CO-O-CO-) from the dicarboxylic anhydride. Examples of dicarboxylic anhydrides include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylene Methyltetrahydrophthalic anhydride, chlorbacteric acid anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.

In the formula ^(a-1), Z a represents a self-tetracarboxylic dianhydride after removal of two acid anhydride residue. Examples of tetracarboxylic dianhydride include: tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyl tetracarboxylic acid dianhydride Carboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, etc. Among them, pyromellitic dianhydride or biphenyl tetracarboxylic dianhydride is preferred, and pyromellitic dianhydride is preferred in terms of a wider development process range. In the above formula (a-1), t1 represents an integer of 0 or more and 20 or less.

(式(a-4)中，R^a4 、R^a5 及R^a6 分別獨立地表示選自由氫原子、碳原子數1以上10以下之烷基及氟原子所組成之群中之1種，t3表示0以上12以下之整數)[化38]

(In formula (a-4), R ^a4 , R ^a5 and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and t3 represents Integer from 0 to 12)

^{The alkyl group that can be selected as R a4} in the formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms of the alkyl group to this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and still more preferably 1 or more and 4 or less, particularly preferably 1 or more and 3 or less. When ^Ra4 is an alkyl group, the alkyl group may be linear or branched.

^{As R a4} in the formula (a-4), in terms of easily obtaining a Cardo resin having excellent heat resistance, each independently is more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ^{R a4} in the formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group. ^{Regarding the plural Ra4} in the formula (a-4), the same group is preferred in terms of easy preparation of high-purity tetracarboxylic dianhydride.

T3 in the formula (a-4) represents an integer of 0 to 12 or less. By setting the value of t3 to 12 or less, the purification of tetracarboxylic dianhydride can be facilitated. In terms of easy purification of tetracarboxylic dianhydride, the upper limit of t3 is preferably 5, more preferably 3. In terms of the chemical stability of tetracarboxylic dianhydride, the lower limit of t3 is preferably 1, and more preferably 2. In formula (a-4), t3 is particularly preferably 2 or 3.

The alkyl group with 1 to 10 carbon atoms that can be selected as ^Ra5 and ^Ra6 in the formula (a-4) is the same as the alkyl group with 1 to 10 carbon atoms that can be selected ^{as Ra4.} Regarding R ^a5 and R ^a6 , in terms of easy purification of tetracarboxylic dianhydride, a hydrogen atom or a carbon atom number of 1 or more and 10 or less (preferably 1 or more and 6 or less, more preferably 1 or more and 5 Hereinafter, the alkyl group of 1 or more and 4 or less is more preferable, and 1 or more and 3 or less) are more preferable, and a hydrogen atom or a methyl group is particularly preferable.

As the tetracarboxylic dianhydride represented by the formula (a-4), for example, norran-2-spiro-α-cyclopentanone-α'-spiro-2''-norman-5, 5``,6,6''-tetracarboxylic dianhydride '',6,6''-tetracarboxylic dianhydride''), methylnorman-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnormangan)- 5,5``,6,6''-Tetracarboxylic dianhydride, norrsan-2-spiro-α-cyclohexanone-α'-spiro-2''-normanthane-5,5'' ,6,6''-Tetracarboxylic dianhydride (alias is ``norman-2-spiro-2'-cyclohexanone-6'-spiro-2''-normanthane-5,5'', 6,6``-tetracarboxylic dianhydride''), methylnorman-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnormangan)-5,5 '',6,6''-Tetracarboxylic dianhydride, norman-2-spiro-α-cycloacetone-α'-spiro-2''-norman-5,5'',6,6 ''-Tetracarboxylic dianhydride, norcarboxane-2-spiro-α-cyclobutanone-α'-spiro-2''-norcarboxane-5,5'',6,6''-tetracarboxylic acid Acid dianhydride, norman-2-spiro-α-cycloheptanone-α'-spiro-2''-norman-5,5``,6,6''-tetracarboxylic dianhydride, norman 𦯉alkane-2-spiro-α-cyclooctanone-α'-spiro-2''-nor𦯉alkane-5,5'',6,6''-tetracarboxylic dianhydride, nor𦯉alkane-2- Spiro-α-cyclononanone-α'-spiro-2''-normanthane-5,5``,6,6''-tetracarboxylic dianhydride, normanthane-2-spiro-α-ring Decanone-α'-spiro-2``-norphine-5,5'',6,6''-tetracarboxylic dianhydride, norren-2-spiro-α-cycloundecone-α '-Spiro-2''-Norkane-5,5'',6,6''-Tetracarboxylic dianhydride, Normanne-2-spiro-α-cyclododecanone-α'-Spiro- 2``-Noralkane-5,5'',6,6''-tetracarboxylic dianhydride, noralkane-2-spiro-α-cyclotridecone-α'-spiro-2''- Noralkane-5,5``,6,6''-tetracarboxylic dianhydride, noralkane-2-spiro-α-cyclotetradecone-α'-spiro-2''-noralkane- 5,5``,6,6''-Tetracarboxylic dianhydride, norrsan-2-spiro-α-cyclopentadecone-α'-spiro-2''-normanthane-5,5' ',6,6''-Tetracarboxylic dianhydride, nor𦯉ane-2-spiro-α-(methylcyclopentanone)-α'-spiro-2''-nor𦯉ane-5,5'' ,6,6''-Tetracarboxylic dianhydride, norrethane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2''-norrethane-5,5'', 6,6''-tetracarboxylic dianhydride, etc.

The weight average molecular weight of the Cardo resin (a-1) is preferably 1,000 or more and 40,000 or less, more preferably 1,500 or more and 30,000 or less, and still more preferably 2,000 or more and 10,000 or less. By setting it in the above range, good developability can be obtained, and sufficient heat resistance and mechanical strength of the cured product can be obtained.

The novolak resin (a-2) is also preferable as an alkali-soluble resin used together with the (meth)acrylic resin (A1).

As the novolak resin (a-2), various novolak resins previously formulated in the photosensitive composition can be used. The novolak resin (a-2) is preferably a resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter, abbreviated as "phenols") and aldehydes under an acid catalyst.

Examples of phenols used in the production of novolak resin (a-2) include: phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2, 4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and other xylenols; o-ethylphenol, m-ethylphenol Ethyl phenols such as methyl phenol and p-ethyl phenol; 2-isopropyl phenol, 3-isopropyl phenol, 4-isopropyl phenol, o-butyl phenol, m-butyl phenol, p-butyl phenol, and Alkylphenols such as p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol and catechol , Hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol and other polyphenols; alkyl resorcinol, alkyl catechol, and alkyl hydroquinone Alkyl polyphenols (any alkyl group has 1 to 4 carbon atoms); α-naphthol; β-naphthol; hydroxybiphenyl; and bisphenol A, etc. These phenols may be used alone or in combination of two or more kinds.

Among these phenols, m-cresol and p-cresol are preferred, and the combined use of m-cresol and p-cresol is more preferred. In this case, by adjusting the blending ratio of the two, the heat resistance and other characteristics of the cured product formed using the resin composition can be adjusted. The blending ratio of m-cresol and p-cresol is not particularly limited, and the molar ratio of m-cresol/p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol in the ratio of this range, it is easy to obtain the resin composition which can form the hardened|cured material excellent in heat resistance.

In addition, a novolak resin produced by using m-cresol and 2,3,5-trimethylphenol in combination is also preferable. In the case of using the novolak resin, it is particularly easy to obtain a resin composition that can form a cured product that is difficult to flow excessively by heating during post-baking. The blending ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited. The molar ratio of m-cresol/2,3,5-trimethylphenol is preferably 70/30 or more 95/ 5 or less.

Examples of the aldehydes used when producing the novolak resin (a-2) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more kinds.

As the acid catalyst used in the production of novolac resin (a-2), for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and Organic acids such as p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more kinds.

Regarding the weight average molecular weight (Mw; hereafter, also referred to as "weight average molecular weight") in terms of polystyrene of the novolak resin (a-2), the cured product formed by using the photosensitive composition is relatively From the viewpoint of the resistance to flow, as the lower limit, it is preferably 2,000, more preferably 5,000, particularly preferably 10,000, further preferably 15,000, most preferably 20,000, and as the upper limit, preferably 50,000, more preferably 45,000, still more preferably 40,000, most preferably 35,000.

As the novolak resin (a-2), at least two types of resins having different weight average molecular weights in terms of polystyrene can be used in combination. By combining resins with different weight average molecular weights, the developability of the photosensitive composition can be balanced with the heat resistance of the cured product formed using the photosensitive composition.

The modified epoxy resin (a-3) is also preferable as an alkali-soluble resin used together with the silicone modified (meth)acrylic resin (A1).

In terms of easy formation of hardened products that are difficult to deform by heating and have high water resistance, it can be contained in the reactant of epoxy compound (a-3a) and unsaturated group-containing carboxylic acid (a-3b) Additions of polybasic acid anhydrides (a-3c) are added. The adduct is also referred to as "modified epoxy resin (a-3)". Furthermore, in the specification and patent application scope of this application, the compound that meets the above definition and does not belong to the above-mentioned resin (a-1) with the Cardo structure is referred to as modified epoxy resin (a-3).

Hereinafter, the epoxy compound (a-3a), the unsaturated group-containing carboxylic acid (a-3b), and the polybasic acid anhydride (a-3c) will be described.

The epoxy compound (a-3a) is not particularly limited as long as it is a compound having an epoxy group. It may be an aromatic epoxy compound having an aromatic group or an aliphatic epoxy compound not containing an aromatic group. , Preferably an aromatic epoxy compound having an aromatic group. The epoxy compound (a-3a) may be a monofunctional epoxy compound or a multifunctional epoxy compound having two or more functions, and a multifunctional epoxy compound is preferred.

Specific examples of the epoxy compound (a-3a) include: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, naphthalene 2-functional epoxy resin such as type epoxy resin and biphenyl type epoxy resin; glycidyl ester type epoxy resin such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidylamino diphenylmethane , Triglycidyl p-aminophenol, tetraglycidyl metaxylylenediamine, and tetraglycidyl diaminomethyl cyclohexane and other glycidyl amine epoxy resins; triglycidyl isocyanurate Heterocyclic epoxy resins; phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2 ,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1,3-Bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy) )Phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol and other trifunctional epoxy resins; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl Four-functional epoxy resins such as benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidyloxy biphenyl.

Moreover, as an epoxy compound (a-3a), the epoxy compound which has a biphenyl skeleton is preferable. The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) in the main chain. The epoxy compound having a biphenyl skeleton is preferably a polyfunctional epoxy compound having two or more epoxy groups. By using an epoxy compound having a biphenyl skeleton, it is easy to obtain a resin composition that has an excellent balance between sensitivity and developability, and can form a cured product with excellent adhesion to the substrate.

(式(a-3a-1)中，R^a7 分別獨立為氫原子、碳原子數1以上12以下之烷基、鹵素原子、或可具有取代基之苯基，j為1以上4以下之整數)[化39]

(In formula (a-3a-1), R ^{a7 is} each independently a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, and j is an integer of 1 to 4 )

When ^Ra7 is an alkyl group with 1 to 12 carbon atoms, specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. , Second butyl, third butyl, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, the first Trioctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl.

When ^Ra7 is a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When ^Ra7 is a phenyl group which may have a substituent, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 or more and 5 or less, preferably 0 or 1. Examples of substituents include: alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, aliphatic acyl groups with 2 to 4 carbon atoms, halogen atoms, and cyano groups. Base, and nitro.

(式(a-3a-2)中，R^a7 及j與式(a-3a-1)相同，k為括號內之結構單元之平均重複數且為0以上10以下)The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited. For example, a ring represented by the following formula (a-3a-2) may be mentioned Oxygen compounds. [化40]

(In formula (a-3a-2), ^Ra7 and j are the same as formula (a-3a-1), k is the average repeating number of the structural unit in the brackets and is 0 or more and 10 or less)

(式(a-3a-3)中，k與式(a-3a-2)相同)Among the epoxy compounds represented by the formula (a-3a-2), the resin composition having an excellent balance between sensitivity and developability is particularly preferred in terms of easy to obtain a resin composition represented by the following formula (a-3a-3) Show the compound. [化41]

(In formula (a-3a-3), k is the same as formula (a-3a-2))

When preparing the modified epoxy compound (a-3), the epoxy compound (a-3a) is reacted with the unsaturated group-containing carboxylic acid (a-3b). The unsaturated group-containing carboxylic acid (a-3b) is preferably a monocarboxylic acid having a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, α-cyanocinnamic acid, cinnamic acid, and the like. Moreover, unsaturated group-containing carboxylic acid (a-3b) can be used individually or in combination of 2 or more types.

The epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) can be reacted by a known method. As a preferable reaction method, for example, the following method can be exemplified: tertiary amines such as triethylamine and benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethyl chloride Quaternary ammonium salts such as ammonium chloride, benzyltriethylammonium chloride, pyridine or triphenylphosphine, etc. are used as catalysts to make epoxy compounds ( a-3a) React with unsaturated group-containing carboxylic acid (a-3b) for several hours to several tens of hours.

Regarding the ratio of the two amounts used in the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b), the epoxy equivalent of the epoxy compound (a-3a) and the The ratio of the carboxylic acid equivalent of the saturated carboxylic acid (a-3b) is usually 1:0.5-1:2, more preferably 1:0.8-1:1.25, and particularly preferably 1:0.9-1: 1.1. If the ratio of the use amount of epoxy compound (a-3a) to the use amount of unsaturated group-containing carboxylic acid (a-3b) is 1:0.5 to 1:2 based on the above equivalent ratio, the crosslinking efficiency will be improved The tendency is better.

The polybasic acid anhydride (a-3c) is an anhydride of a carboxylic acid having two or more carboxyl groups. The polybasic acid anhydride (a-3c) is not particularly limited, and examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Dicarboxylic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexa Hydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride , 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, The compound represented by the formula (a-3c-1) and the compound represented by the following formula (a-3c-2) are described. Moreover, polybasic acid anhydride (a-3c) can be used individually or in combination of 2 or more types.

(式(a-3c-2)中，R^a8 表示碳原子數1以上10以下之可具有取代基之伸烷基)[化42]

(In the formula (a-3c-2), R ^a8 represents an alkylene group having 1 to 10 carbon atoms that may have a substituent)

The polybasic acid anhydride (a-3c) is preferably a compound having two or more benzene rings in terms of easily obtaining a resin composition having an excellent balance between sensitivity and developability. In addition, the polybasic acid anhydride (a-3c) more preferably contains at least one of the compound represented by the above formula (a-3c-1) and the compound represented by the above formula (a-3c-2).

The method of reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and then reacting with the polybasic acid anhydride (a-3c) can be appropriately selected from known methods. In addition, the ratio of the amount used is based on the ratio of the molar number of the OH group in the component after the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) are reacted with the polybasic acid anhydride (a-3c) The equivalent ratio of acid anhydride groups is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. By setting it as the said range, it becomes easy to obtain the resin composition with good developability.

The acid value of the modified epoxy resin (a-3), based on the solid content of the resin, is preferably 10 mgKOH/g or more and 150 mgKOH/g or less, more preferably 70 mgKOH/g or more and 110 mgKOH/g or less. By setting the acid value of the resin to 10 mgKOH/g or more, sufficient solubility for the developer can be obtained. In addition, by setting the acid value to 150 mgKOH/g or less, sufficient curability can be obtained, and Make the surface of the hardened material become better.

The weight average molecular weight of the modified epoxy resin (a-3) is preferably 1,000 or more and 40,000 or less, more preferably 2,000 or more and 30,000 or less. By making the weight average molecular weight 1000 or more, it is easy to form a cured product with excellent heat resistance and strength. In addition, by making the weight average molecular weight 40,000 or less, it is easy to obtain a resin composition showing sufficient solubility for the developer.

Moreover, (meth)acrylic resin (a-4) which is a resin other than (meth)acrylic resin (A1) can also be used as a component which comprises an alkali-soluble resin. When the (meth)acrylic resin (AI) that has not been modified with the epoxy-containing cyclic silicone compound (A-II) has alkali-soluble groups, the (meth)acrylic resin can also be used (AI) is used as (meth)acrylic resin (a-4). As the (meth)acrylic resin (a-4), a resin containing a structural unit derived from (meth)acrylic acid and/or a structural unit derived from other monomers such as (meth)acrylate can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. The (meth)acrylate is a compound represented by the following formula (a-4-1), and is not particularly limited as long as it does not interfere with the purpose of the present invention.

[化43]

In the above formula (a-4-1), ^Ra9 is a hydrogen atom or a methyl group, and ^Ra10 is a monovalent organic group. The organic group may include a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. In addition, the organic group may be any of linear, branched, and cyclic.

^{Substituents other than the hydrocarbon group in the organic group of Ra10} are not particularly limited as long as they do not impair the effects of the present invention. Examples include halogen atoms, hydroxyl groups, mercapto groups, thio groups, cyano groups, isocyano groups, and cyanic acid groups. Groups, isocyanato groups, thiocyanato groups, thioisocyanato groups, silyl groups, silanol groups, alkoxy groups, alkoxycarbonyl groups, carboxamides, carboxamides, nitro groups, nitroso groups, Carboxyl group, carboxylate group, acyl group, acyloxy group, sulfinic acid group, sulfonic acid group, sulfonate group, phosphine group, phosphinyl group, phosphonic acid group, phosphonate group, hydroxyimine group, alkyl ether Group, alkyl sulfide group, aryl ether group, aryl sulfide group, amine group (-NH ₂ , -NHR, -NRR': R and R'each independently represent a hydrocarbon group), etc. The hydrogen atom contained in the above substituent may be substituted by a hydrocarbon group. Moreover, the hydrocarbon group contained in the said substituent may be any of linear, branched, and cyclic.

In addition, the organic group as R ^a10 may have Bingxi Xi group, Bing Xixi methyl group, an epoxy group, an oxetanyl group of the reactive functional groups. Acrylic groups having unsaturated double bonds, such as acryloxy groups or methacryloxy groups, can be produced by, for example, making a (meth)acrylic resin (a-4) containing a structural unit having an epoxy group At least part of the epoxy group reacts with unsaturated carboxylic acid such as acrylic acid or methacrylic acid. After reacting at least a part of the epoxy group with the unsaturated carboxylic acid, the group generated by the reaction may be reacted with the polybasic acid anhydride.

Specific examples of polybasic acid anhydrides include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydro Phthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4 -Methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride Phthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, etc.

As a specific example, if a structural unit derived from glycidyl methacrylate is reacted with acrylic acid, a structural unit having a hydroxyl group shown in the following reaction formula is generated. By reacting the structural unit having a hydroxyl group with an anhydride of a polybasic acid such as tetrahydrophthalic acid, a structural unit having a carboxyl group and an unsaturated double bond that imparts alkali solubility to the resin is generated. [化44]

R ^{a10 is} preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. In addition, when these groups contain alkylene moieties, the alkylene moieties can be interrupted by ether bonds, thioether bonds, and ester bonds.

When the alkyl group is linear or branched, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Examples of preferable alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, isopentyl Base, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl, iso Decyl and others.

When the alkyl group is an alicyclic group or a group containing an alicyclic group, the preferred alicyclic group contained in the alkyl group includes monocyclic alicyclic groups such as cyclopentyl and cyclohexyl Formula group; adamantyl group, nor 𦯉 group, iso 𦯉 group, tricyclononyl, tricyclodecyl, and tetracyclododecyl and other polycyclic alicyclic groups.

As a specific example of the compound represented by the formula (a-4-1) when the compound represented by the formula (a-4-1) contains a chain-like group having an epoxy group as R ^{a10, there may be mentioned: (formula (a-4-1)} Base) glycidyl acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, etc. Base) epoxy alkyl acrylates.

In addition, the compound represented by the formula (a-4-1) may also be a (meth)acrylate containing an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. As a monocyclic alicyclic group, cyclopentyl, cyclohexyl, etc. are mentioned. In addition, as the polycyclic alicyclic group, there can be exemplified nordoxy, isooxy, tricyclononyl, tricyclodecyl, tetracyclododecyl, and the like.

As a specific example when the compound represented by the formula (a-4-1) is a (meth)acrylate containing an alicyclic epoxy group, for example, the following formulas (a-4-1a) to (a) -4-1o) The compound shown in. Among these, in order to bring the developability into an appropriate range, the compounds represented by the following formulas (a-4-1a) to (a-4-1e) are preferred, and the following formulas (a-4- 1a) ~ (a-4-1c) the compounds shown.

[化45]

[化46]

[化47]

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent saturated aliphatic hydrocarbon group with 1 to 6 ^{carbon atoms, R a22} represents a divalent hydrocarbon group with 1 to 10 carbon atoms, and t represents 0 or more Integers below 10. R ^{a21 is} preferably a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene base. As R ^a22 , for example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH are preferred. ₂ -Ph-CH _2- (Ph represents phenylene).

In addition, the (meth)acrylic resin (a-4) may be a copolymer obtained by further polymerizing monomers other than (meth)acrylate. Examples of monomers other than (meth)acrylates include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers can be used individually or in combination of 2 or more types. Preferable examples of these monomers are as described for (meth)acrylic resin (A1).

The amount of structural units derived from (meth)acrylic acid and the amount of structural units derived from other monomers in the (meth)acrylic resin (a-4) are not particularly limited within a range that does not interfere with the purpose of the present invention limited. The amount of the (meth)acrylic acid-derived structural unit in the (meth)acrylic resin (a-4) relative to the mass of the (meth)acrylic resin (a-4) is preferably 5% by mass or more and 50% by mass % Or less, more preferably 10% by mass or more and 30% by mass or less.

When the (meth)acrylic resin (a-4) contains structural units with unsaturated double bonds, the amount of structural units with unsaturated double bonds in the (meth)acrylic resin (a-4) is preferred It is 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and particularly preferably 1% by mass or more and 20% by mass or less. Since the (meth)acrylic resin (a-4) contains the structural unit having unsaturated double bonds in an amount within the above range, the acrylic resin can be introduced into the cross-linking reaction in the resist film to make it uniform. Effective for improving the heat resistance and mechanical properties of the cured film.

The weight average molecular weight of the (meth)acrylic resin (a-4) is preferably 2,000 or more and 50,000 or less, more preferably 3,000 or more and 30,000 or less. By setting it as the said range, there exists a tendency for the film-forming ability of a resin composition and the developability after exposure to balance easily to be obtained.

The total of the mass of the (meth)acrylic resin (A1) and the mass of other resins in the second resin composition is relative to the mass of the resin composition (the total solid content) excluding the mass of the organic solvent (S) described below, It is preferably 20% by mass or more and 85% by mass or less, and more preferably 25% by mass or more and 75% by mass or less. By setting it as the said range, the resin composition excellent in developability can be obtained easily.

・Photopolymerizable monomer (B) The second resin composition contains a photopolymerizable monomer (B). As the photopolymerizable monomer (B), the compound previously formulated in the photosensitive composition can be used without particular limitation.

As a monofunctional photopolymerizable monomer, for example, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (Meth)acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, N-methylol(meth)acrylamide (N-methylolmethacrylamide), N-(hydroxymethyl)methacrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride , Iconic acid, Iconic anhydride, Methylmaleic acid, Methylmaleic anhydride, Crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tertiary butylacrylic acid Aminosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino(meth)acrylic acid Ester, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, phthalic acid derivatives (Meth) acrylic acid half ester, etc. These monofunctional photopolymerizable monomers can be used alone or in combination of two or more kinds.

Examples of the multifunctional photopolymerizable monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate. (Meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate Base) acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2- Bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, (methyl) Acrylic acid 2-hydroxy-3-(meth)acryloxypropyl ester, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, ortho Diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie, toluene diisocyanate) ), the reactant of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylene bis(meth)acrylamide, (meth)propylene Multifunctional monomers such as the condensate of amide methylene ether, polyol and N-methylol (meth)acrylamide; tripropylene formal, etc. These polyfunctional photopolymerizable monomers can be used alone or in combination of two or more kinds.

Among these photopolymerizable monomers (B), in terms of the tendency to improve the adhesion of the resin composition to the substrate and the strength after curing of the resin composition, a polyfunctional photopolymerization of trifunctional or higher is preferred The polyfunctional monomer is more preferably a polyfunctional monomer with tetrafunctional or higher, and more preferably a polyfunctional photopolymerizable monomer with pentafunctional or higher.

The content of the photopolymerizable monomer (B) in the resin composition is preferably 1% by mass or more and 50% by mass relative to the mass of the resin composition (total solid content) other than the mass of the organic solvent (S) described below Below, it is more preferable that it is 5 mass% or more and 40 mass% or less. By setting it in the above range, there is a tendency to easily obtain a balance of sensitivity, developability, and resolution.

・Photopolymerization initiator (C) As the photopolymerization initiator, compounds used for the purpose of curing the photopolymerizable monomer having an unsaturated bond among the previously known photosensitive compositions can be used without particular limitation.

、2-氯9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、1-氯-4-丙氧基9-氧硫𠮿

、硫𠮿

、2-氯硫𠮿

、2,4-二乙基硫𠮿

、2-甲基硫𠮿

、2-異丙基硫𠮿

、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌、偶氮雙異丁腈、過氧化苯甲醯、氫過氧化異丙苯、2-巰基苯并咪唑、2-巰基苯并㗁唑、2-巰基苯并噻唑、2-(鄰氯苯基)-4,5-二(間甲氧基苯基)咪唑二聚物、二苯甲酮、2-氯二苯甲酮、p,p'-雙二甲基胺基二苯甲酮、4,4'-雙二乙基胺基二苯甲酮、4,4'-二氯二苯甲酮、3,3-二甲基-4-甲氧基二苯甲酮、二苯基乙二酮、安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香正丁醚、安息香異丁醚、安息香丁醚、苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對第三丁基苯乙酮、對二甲基胺基苯乙酮、對第三丁基三氯苯乙酮、對第三丁基二氯苯乙酮、α,α-二氯-4-苯氧基苯乙酮、9-氧硫𠮿

、2-甲基9-氧硫𠮿

、2-異丙基9-氧硫𠮿

、二苯并環庚酮、4-二甲基胺基苯甲酸戊酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、對甲氧基三𠯤、2,4,6-三(三氯甲基)對稱三𠯤、2-甲基-4,6-雙(三氯甲基)對稱三𠯤、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)對稱三𠯤、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)對稱三𠯤、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)對稱三𠯤、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)對稱三𠯤、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)對稱三𠯤、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)對稱三𠯤、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)對稱三𠯤、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基對稱三𠯤、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基對稱三𠯤、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基對稱三𠯤、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基對稱三𠯤等。As the photopolymerization initiator (C), specifically, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4 -(2-Hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane Alkane-1-one, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌line propan-1-one, 2-benzyl-2-dimethylamino-1-(4-𠰌linephenyl)-butan-1-one, 4-benzyl-4'-methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate 2-ethylhexyl aminobenzoate, 2-isopentyl 4-dimethylaminobenzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1 -Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzyl benzoate, 2,4-diethyl 9-oxythio𠮿

, 2-chloro-9-oxysulfur 𠮿

, 2,4-Dimethyl 9-oxysulfur 𠮿

, 1-chloro-4-propoxy 9-oxysulfur 𠮿

Sulphur

, 2-Chlorosulfur𠮿

, 2,4-Diethylsulfide 𠮿

, 2-Methylsulfide

, 2-isopropyl sulfide 𠮿

, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzyl peroxide, isohydroperoxide Propylbenzene, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole dimerization Compounds, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4 '-Dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, diphenylethylenedione, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin positive Butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone , Trichloroacetophenone, p-tertiary butyl acetophenone, p-dimethylamino acetophenone, p-tertiary butyl trichloroacetophenone, p-tertiary butyl dichloroacetophenone, α, α-Dichloro-4-phenoxyacetophenone, 9-oxysulfur 𠮿

, 2-Methyl 9-oxysulfur 𠮿

, 2-isopropyl 9-oxysulfur 𠮿

, Dibenzocycloheptanone, pentyl 4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-( 9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytris, 2,4,6-tris(trichloromethyl) symmetrical tris, 2- Methyl-4,6-bis(trichloromethyl) symmetric tris, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl) symmetric Tris, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl) symmetric tris, 2-[2-(4-diethylamino-2- Methylphenyl)vinyl]-4,6-bis(trichloromethyl) symmetric tris, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis (Trichloromethyl) symmetric tris, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) symmetric tris, 2-(4-ethoxystyryl)- 4,6-bis(trichloromethyl) symmetrical tris, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl) symmetrical tris, 2,4-bis-tris Chloromethyl-6-(3-bromo-4-methoxy)phenyl symmetric tris, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl symmetric Tris, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl symmetric tris, 2,4-bis-trichloromethyl-6-( 2-Bromo-4-methoxy)styryl phenyl symmetric tri 𠯤 and so on.

These photopolymerization initiators (C) can be used alone or in combination of two or more kinds.

Moreover, in terms of the sensitivity of the resin composition, the photopolymerization initiator (C) is preferably an oxime ester compound. As the oxime ester compound, for example, an oxime ester compound represented by the following formula (c1) is preferred. [化48]

In the above formula (c1), R ^c11 represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted carbazolyl group. a is 0 or 1. R ^c12 represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted carbazolyl group. R ^c13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent.

When R ^c11 is an alkyl group having 1 or more and 10 carbon atoms which may have a substituent, the type of the substituent that the alkyl group has is not particularly limited within a range that does not interfere with the purpose of the present invention.

Examples of preferable substituents that an alkyl group having 1 to 10 carbon atoms may have include: alkoxy having 1 to 20 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, and carbon Cycloalkoxy groups with 3 to 10 atoms, saturated aliphatic acyl groups with 2 to 20 carbon atoms, alkoxycarbonyl groups with 2 to 20 carbon atoms, saturated aliphatic groups with 2 to 20 carbon atoms An oxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent group, a thiophenyl group which may have a substituent group, a benzyl group which may have a substituent group, a phenoxycarbonyl group which may have a substituent group, Benzyloxy group which may have substituents, phenylalkyl group which may have substituents and carbon atoms of 7 or more and 20 or less, naphthyl which may have substituents, naphthyloxy which may have substituents, and which may have substituents The naphthyl group, the naphthyloxycarbonyl group which may have a substituent, the naphthyloxycarbonyl group which may have a substituent, the naphthylalkyl group with 11 to 20 carbon atoms which may have a substituent, and which may have a substituent Heterocyclic groups, heterocyclic carbonyl groups that may have substituents, amine groups, amino groups substituted with 1 or 2 organic groups, linolin-1-yl, and piperidine-1-yl, halogen, nitro, And cyano, etc.

The alkyl group having 1 to 10 carbon atoms may be linear or branched. In this case, the number of carbon atoms of the alkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less.

When R ^c11 is a phenyl group which may have a substituent, the type of the substituent is not particularly limited within a range that does not hinder the purpose of the present invention. Preferable examples of the substituents that the phenyl group may have include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, and saturated aliphatic acyloxy groups. , Phenyl which may have substituents, phenoxy which may have substituents, benzyloxy which may have substituents, phenoxycarbonyl which may have substituents, benzyloxy which may have substituents, A substituted phenylalkyl group, a substituted naphthyl group, a substituted naphthyloxy group, a substituted naphthyloxy group, a substituted naphthyloxycarbonyl group, a substituted naphthyl group The naphthyloxy group, the naphthylalkyl group which may have substituents, the heterocyclic group which may have substituents, the amino group, the amino group substituted by one or two organic groups, the linolin-1-yl group, and Piper-1-yl, halogen, nitro, and cyano, etc. When R ^c11 is a phenyl group which may have a substituent, and the phenyl group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent of the phenyl group is an alkyl group, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, still more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 Below, the best value is 1. In addition, the alkyl group may be linear or branched. Specific examples when the substituent of the phenyl group is an alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Base, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, iso Nonyl, n-decyl, and isodecyl, etc. In addition, the alkyl group may include an ether bond (-O-) in the carbon chain. In this case, as the substituent of the phenyl group, for example, an alkoxyalkyl group and an alkoxyalkoxyalkyl group may be mentioned. When the substituent of the phenyl group is an alkoxyalkyl group, it is preferably a group represented by ^{-R c14} -OR ^c15. R ^c14 is an alkylene group having 1 to 10 carbon atoms, which may be linear or branched. R ^c15 is a linear or branched alkyl group having 1 to 10 carbon atoms. The ^{number of carbon atoms of R c14} is preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. The ^{number of carbon atoms of R c15} is preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. Examples of alkyl groups with ether bonds in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc.

When the substituent of the phenyl group is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. In addition, the alkoxy group may be linear or branched. Specific examples when the substituent of the phenyl group is an alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and Dibutoxy, tertiary butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, tertiary pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctoxy Group, second octyloxy group, third octyloxy group, n-nononyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. In addition, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include: methoxyethoxy, ethoxyethoxy, 2-methoxy-1-methylethoxy, and methoxyethoxy. Oxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, and methoxypropoxy, etc.

When the substituent of the phenyl group is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples when the substituent of the phenyl group is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Specific examples when the substituent of the phenyl group is a cycloalkoxy group include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy. Oxy etc.

When the substituent of the phenyl group is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. As specific examples when the substituent of the phenyl group is a saturated aliphatic acyl group, acetyl group, propyl group, n-butanyl group, 2-methylpropanyl group, n-pentanyl group, 2,2 -Dimethyl propanyl, n-hexyl, n-heptanyl, n-octyl, n-nonanyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl , N-fourteen-carbon acyl group, n-five-carbon acyl group, and n-hexadecyl acyl group and so on. Specific examples when the substituent of the phenyl group is a saturated aliphatic oxy group include: acetoxy group, propoxy group, n-butoxy group, 2-methylpropoxy group, n- Pentanoyloxy, 2,2-dimethylpropanoyloxy, n-hexyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecyloxy Oxooxy, n-dodecanoyloxy, n-tridecanooxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoxyoxy, etc.

When the substituent of the phenyl group is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. As specific examples when the substituent of the phenyl group is an alkoxycarbonyl group, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, Isobutoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexoxycarbonyl , N-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl , And isodecyloxycarbonyl, etc.

When the substituent of the phenyl group is a phenylalkyl group, the number of carbon atoms is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. When the substituent of the phenyl group is a naphthylalkyl group, the number of carbon atoms is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples when the substituent of the phenyl group is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when the substituent of the phenyl group is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-naphthylmethyl. (β-Naphthyl) ethyl. When the substituent of the phenyl group is a phenylalkyl group or a naphthylalkyl group, the substituent may further have a substituent on the phenyl group or the naphthyl group.

When the substituent of the phenyl group is a heterocyclic group, the heterocyclic group is a monocyclic ring containing more than one of five or six members of N, S, and O, or the monocyclic rings or the monocyclic ring Heterocyclic group condensed with benzene ring. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 at most. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, azole, isoazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine , Da 𠯤, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoindole Quinoline, quinazoline, quinoline, quinoline, and quinoline, etc. When the substituent of the phenyl group is a heterocyclic group, the heterocyclic group may further have a substituent.

When the substituent of the phenyl group is an amine group substituted with one or two organic groups, preferable examples of the organic group include: an alkyl group having 1 to 20 carbon atoms, and 3 carbon atoms. Cycloalkyl groups of more than 10 or less, saturated aliphatic acyl groups of 2 to 20 carbon atoms, saturated aliphatic oxy groups of 2 to 20 carbon atoms, phenyl groups that may have substituents, and those that may have substituents Benzyl group, optionally substituted phenylalkyl group with 7 or more carbon atoms and less than 20 carbon atoms, optionally substituted naphthyl group, optionally substituted naphthyl group, optionally substituted carbon atom number 11 Above 20 naphthyl alkyl, heterocyclic group, etc. As specific examples of these preferable organic groups, the same groups as those described above regarding the substituents of the phenyl group can be cited. Specific examples of the amino group substituted with one or two organic groups include: methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, Isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decyl Amino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentanylamino, n-hexylamino, n-heptanylamino , N-octanoylamino, n-decanoylamino, benzylamino, α-naphthylamino, β-naphthylamino, and N-acetyl-N-acetoxy Amino groups and so on.

Examples of the substituent when the phenyl, naphthyl, and heterocyclic group included in the substituent of the phenyl group further have a substituent include: an alkyl group having 1 to 6 carbon atoms, and 1 or more carbon atoms Alkoxy groups with 6 or less, saturated aliphatic acyl groups with 2 to 7 carbon atoms, alkoxycarbonyl groups with 2 to 7 carbon atoms, saturated aliphatic oxy groups with 2 to 7 carbon atoms, Monoalkylamino groups of alkyl groups with 1 to 6 carbon atoms, dialkylamino groups with alkyl groups with 1 to 6 carbon atoms, linolin-1-yl, piperidine-1-yl, halogen , Nitro, and cyano, etc. When the phenyl, naphthyl and heterocyclic groups included in the substituents of the phenyl group further have substituents, the number of the substituents is not limited within the range that does not interfere with the purpose of the present invention. Preferably, it is 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent of the phenyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Above, the ^{substituent when R c11} is a phenyl group which may have a substituent is explained, and among these substituents, an alkyl group or an alkoxyalkyl group is preferable.

When R ^c11 is a phenyl group which may have a substituent, the number of substituents and the bonding position of the substituents are not particularly limited within a range that does not interfere with the purpose of the present invention. When R ^c11 is a phenyl group that may have a substituent, the phenyl group that may have a substituent is preferably an o-tolyl group that may have a substituent in terms of excellent base generation efficiency.

When R ^c11 is a carbazolyl group which may have a substituent, the type of the substituent is not particularly limited within a range that does not hinder the purpose of the present invention. Examples of preferable substituents that the carbazolyl group may have on carbon atoms include: alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, and 3 or more carbon atoms. Cycloalkyl groups of 10 or less, cycloalkoxy groups of carbon atoms of 3 to 10, saturated aliphatic aliphatic groups of carbon atoms of 2 to 20, alkoxycarbonyl groups of 2 to 20 carbon atoms, number of carbon atoms 2 Saturated aliphatic acyloxy groups of more than 20 and less than 20, phenyl groups which may have substituents, phenoxy groups which may have substituents, phenylthio groups which may have substituents, phenylcarbonyl groups which may have substituents, and which may be substituted Benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted phenylalkyl group with 7 to 20 carbon atoms, optionally substituted The naphthyl group, the naphthyloxy group that may have a substituent, the naphthylcarbonyl group that may have a substituent, the naphthyloxycarbonyl group that may have a substituent, the naphthyloxycarbonyl group that may have a substituent, and the naphthyloxycarbonyl group that may have a substituent Oxy group, optionally substituted naphthylalkyl with 11 or more and 20 carbon atoms, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl group, amino group, with 1 or 2 organic Group substituted amine, linolin-1-yl, piperidine-1-yl, halogen, nitro, and cyano, etc.

When R ^c11 is a carbazolyl group that may have a substituent, examples of preferable substituents that the carbazolyl group may have on the nitrogen atom include: an alkyl group having 1 to 20 carbon atoms, carbon Cycloalkyl groups with 3 to 10 atoms, saturated aliphatic acyl groups with 2 to 20 carbon atoms, alkoxycarbonyl groups with 2 to 20 carbon atoms, optionally substituted phenyl groups, optionally substituted The benzyl group, the phenoxycarbonyl group which may have a substituent, the phenylalkyl group which may have a substituent and the carbon number of 7 or more and 20 or less, the naphthyl which may have a substituent, and the naphthyl which may have a substituent Group, optionally substituted naphthyloxycarbonyl, optionally substituted naphthylalkyl having 11 or more and 20 or less carbon atoms, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl group, etc. . Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

Regarding specific examples of the substituents that the carbazolyl group may have, the alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, saturated aliphatic acyl group, alkoxycarbonyl group, saturated aliphatic acyloxy group, may have Substituent phenylalkyl, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, and amine group substituted with one or two organic groups, and R ^c11 is optionally substituted The examples of the substituents of the phenyl group in the case of the phenyl group are the same.

In R ^c11 , examples of the substituent when the phenyl, naphthyl, and heterocyclic group contained in the substituent of the carbazolyl group further have a substituent include: an alkyl having 1 to 6 carbon atoms Group; Alkoxy with 1 to 6 carbon atoms; Saturated aliphatic acyl with 2 to 7 carbon atoms; Alkoxycarbonyl with 2 to 7 carbon atoms; Saturated with 2 to 7 carbon atoms Aliphatic phenyloxy; phenyl; naphthyl; benzyl; naphthyl; Benzoyl substituted with a group consisting of phenyl and phenyl; monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; dialkyl having an alkyl group having 1 to 6 carbon atoms Amino; 𠰌lin-1-yl; piper-1-yl; halogen; nitro; cyano. When the phenyl, naphthyl and heterocyclic groups included in the substituents of the carbazolyl group further have substituents, the number of the substituents is not limited within a range that does not interfere with the purpose of the present invention. Preferably it is 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclic group have plural substituents, the plural substituents may be the same or different.

R ^c12 is an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted phenyl group, or an optionally substituted carbazolyl group.

When R ^c12 is an optionally substituted alkyl group having 1 to 10 carbon atoms, the alkyl group may be linear or branched. In this case, the number of carbon atoms of the alkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less.

In R ^c12 , the substitution of the alkyl group or the phenyl group is not particularly limited as long as it does not interfere with the purpose of the present invention. Examples of preferable substituents that the alkyl group may have on carbon atoms include: alkoxy groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and 3 or more carbon atoms Cycloalkoxy groups of 10 or less, saturated aliphatic acyl groups of 2 to 20 carbon atoms, alkoxycarbonyl groups of 2 to 20 carbon atoms, saturated aliphatic oxy groups of 2 to 20 carbon atoms, Phenyl which may have substituents, phenoxy which may have substituents, thiophenyl which may have substituents, benzyl which may have substituents, phenoxycarbonyl which may have substituents, which may have substituents The benzyloxy group, the phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, the naphthyl group which may have a substituent, the naphthoxy group which may have a substituent, the naphthyloxy group which may have a substituent Group, optionally substituted naphthyloxycarbonyl, optionally substituted naphthyloxy, optionally substituted naphthylalkyl with 11 to 20 carbon atoms, optionally substituted heterocyclic group, Heterocyclic carbonyl group, amine group, amine group substituted by 1 or 2 organic groups, pyrolin-1-yl, piperidine-1-yl, halogen, nitro, and cyano group which may have substituents, etc. . As examples of preferable substituents that the phenyl group may have on carbon atoms, in addition to the groups exemplified above as preferable substituents that the alkyl group may have on carbon atoms, the number of carbon atoms may be from 1 to 20.之alkyl.

Regarding specific examples of substituents that an alkyl group or a phenyl group may have, there are alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, For phenylalkyl which may have substituents, naphthylalkyl which may have substituents, heterocyclic groups which may have substituents, and amine groups substituted with one or two organic groups, R ^c11 is optional In the case of a substituted phenyl group, the examples of the substituents of the phenyl group are the same.

In R ^c12 , examples of substituents when the phenyl, naphthyl, and heterocyclic groups contained in the substituents of the alkyl group or the phenyl group further have a substituent include: 1 to 6 carbon atoms Alkyl groups with 1 to 6 carbon atoms; saturated aliphatic aliphatic groups with 2 to 7 carbon atoms; alkoxycarbonyl with 2 to 7 carbon atoms; 2 to 7 carbon atoms The saturated aliphatic aliphatic oxy; phenyl; naphthyl; benzyl; naphthyl; Benzyl group substituted with a group consisting of a phenyl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; two of an alkyl group having 1 to 6 carbon atoms Alkylamino; 𠰌lin-1-yl; piper-1-yl; halogen; nitro; cyano. When the phenyl, naphthyl and heterocyclic groups contained in the substituents of the alkyl group or the phenyl group further have substituents, the number of the substituents is not within the range that does not hinder the purpose of the present invention The limit is preferably 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclic group have plural substituents, the plural substituents may be the same or different.

When R ^c12 is a carbazolyl group which may have a substituent, the type of the substituent that the carbazolyl group has is not particularly limited within a range that does not interfere with the purpose of the present invention. As a preferable example of the substituent which the carbazolyl group may have, it is the same as the example of the substituent when ^{R c11 is a carbazolyl group which may have a substituent.}

或下述式(c3)： [化50]

所示之基。In terms of the reactivity of the compound represented by the formula (c1), R ^{c12 is} preferably the following formula (c2): [化49]

Or the following formula (c3): [化50]

The base shown.

In the formula (c2), R ^c16 and R ^c17 are a monovalent organic group, b is 0 or 1. In formula (c3), R ^c18 is a group selected from the group consisting of monovalent organic groups, amine groups, halogens, nitro groups, and cyano groups, A ^c1 is S or O, and c is an integer from 0 to 4 .

^{R c16} in the formula (c2) can be selected from various organic groups within a range that does not hinder the purpose of the present invention. Preferred examples of R ^c16 include: hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, cycloalkyls with 3 to 10 carbon atoms, and saturated aliphatic alcohols with 2 to 20 carbon atoms. Groups, alkoxycarbonyl groups with 2 to 20 carbon atoms, phenyl groups which may have substituents, benzyl groups which may have substituents, phenoxycarbonyl groups which may have substituents, and carbon atoms which may have substituents Phenylalkyl with 7 or more and 20 or less, naphthyl which may have substituents, naphthyl which may have substituents, naphthyloxycarbonyl which may have substituents, and carbon atoms which may have substituents of 11 or more and 20 The following naphthylalkyl groups, heterocyclic groups which may have substituents, and heterocyclic carbonyl groups which may have substituents, and the like.

^Among R c16, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

^{R c17} in the formula (c2) is not particularly limited within a range that does not interfere with the purpose of the present invention, and it can be selected from various organic groups. Specific examples of preferred groups for R ^c17 include hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, phenyl groups which may have substituents, naphthyl groups which may have substituents, and groups which may have substituents.的heterocyclic group. As R ^c17 , among these groups, the optionally substituted phenyl group and the optionally substituted naphthyl group are more preferred, and the 2-methylphenyl group and the naphthyl group are particularly preferred.

As the phenyl group R ^c16 or R ^c17 included in the group, a naphthyl group, a heterocyclic group, and further having a substituent of substituent group, include: 1 or more carbon atoms of an alkyl group having 6 or less carbon atoms, one or more 6 The following alkoxy groups, saturated aliphatic acyl groups with 2 to 7 carbon atoms, alkoxycarbonyl groups with 2 to 7 carbon atoms, saturated aliphatic oxy groups with 2 to 7 carbon atoms, and carbon atoms The monoalkylamino group of an alkyl group with 1 to 6 atoms, a dialkylamino group with an alkyl group with 1 to 6 carbon atoms, lin-1-yl, piper-1-yl, halogen, Nitro, and cyano, etc. Phenyl in R ^c16 or R ^c17 included in the group, a naphthyl group, a heterocyclic group, and the case further has a substituent group, the number of the substituent group within the scope of the object of the present invention does not interfere defined, preferably It is 1 or more and 4 or less. Phenyl in R ^c16 or R ^c17 included, the naphthyl group, and a heterocyclic group having a plurality of groups of substituents case, a plurality of substituents may be identical or different.

^{When R c18} in the formula (c3) is an organic group, R ^c18 can be selected from various organic groups within a range that does not hinder the purpose of the present invention. In the formula (c3), a ^{preferable example when R c18} is an organic group includes: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a carbon number of 2 or more. Saturated aliphatic acyl group with 7 or less; alkoxycarbonyl group with 2 to 7 carbon atoms; saturated aliphatic acyloxy with 2 to 7 carbon atoms; phenyl; naphthyl; benzyl; naphthyl Benzyl group; benzyl group substituted with a group selected from the group consisting of alkyl having 1 to 6 carbon atoms, linolin-1-yl, piperid-1-yl, and phenyl; having carbon A monoalkylamino group of an alkyl group with 1 to 6 atoms; a dialkylamino group with an alkyl group with 1 to 6 carbon atoms; Nitro; cyano; 2-methylphenylcarbonyl; 4-(piperid-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

In R ^c18 , preferably benzyl; naphthyl; selected from the group consisting of alkyl having 1 to 6 carbon atoms, linolin-1-yl, piperid-1-yl, and phenyl Benzyl; nitro; more preferably benzyl; naphthyl; 2-methylphenylcarbonyl; 4-(piperid-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

Moreover, in formula (c3), c is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. When c is 1, ^{the position where R c18} is bonded is preferably a ^{para position relative to the bonding bond between the phenyl group to which R c18} is bonded and the sulfur atom is bonded.

R ^c13 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent. In the case of a phenyl group which may have a substituent, the substituent which the phenyl group may have is the ^{same as the case where R c11} is a phenyl group which may have a substituent. As R ^c13 , a methyl group, an ethyl group, or a phenyl group is preferable, and a methyl group or a phenyl group is more preferable.

As a compound which is also preferable among the compounds represented by the above formula (c1), a compound represented by the following formula (c4) can be exemplified. [化51]

In the above formula (c4), a, R ^c12 and R ^{c13 are} as described above. R ^c19 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, and d is an integer of 0 or more and 4 or less.

In the above formula (c4), R ^c19 is not particularly limited as long as it does not interfere with the purpose of the present invention, and when it is an organic group, it is appropriately selected from various organic groups. Preferred examples of R ^c19 include: alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, which may have substituents The phenyl group, the phenoxy group which may have a substituent, the benzyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzyloxy group which may have a substituent, and the benzene which may have a substituent Alkyl, naphthyl which may have substituents, naphthyloxy which may have substituents, naphthyloxycarbonyl which may have substituents, naphthoxycarbonyl which may have substituents, naphthyloxycarbonyl which may have substituents Group, naphthylalkyl which may have substituents, heterocyclic group which may have substituents, amino group, amino group substituted by 1 or 2 organic groups, lin-1-yl, piper-1-yl , Halogen, nitro, and cyano, etc. When s is an integer of 2 or more and 4 or less, R ^c19 may be the same or different. In addition, the number of carbon atoms of a substituent does not include the number of carbon atoms of a substituent that the substituent has.

When R ^c19 is an alkyl group, it is preferably 1 or more and 20 or less carbon atoms, more preferably 1 or more and 6 or less carbon atoms. In addition, when R ^c19 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R ^c19 is an alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl , Isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl Base, and isodecyl, etc. In addition, when R ^c19 is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups with ether bonds in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc.

When R ^c19 is an alkoxy group, it is preferably 1 or more and 20 or less carbon atoms, more preferably 1 or more and 6 or less carbon atoms. In addition, when R ^c19 is an alkoxy group, it may be linear or branched. Specific examples when R ^c19 is an alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, Tertiary butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, tertiary pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy Oxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. In addition, when R ^c19 is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include: methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy Group, propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ^c19 is a cycloalkyl group or a cycloalkoxy group, it is preferably 3 or more and 10 or less carbon atoms, more preferably 3 or more and 6 or less carbon atoms. Specific examples when R ^c19 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As a ^{specific example when R c19} is a cycloalkoxy group, a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, etc. are mentioned.

When R ^c19 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^c19 is a saturated aliphatic acyl group include: acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethylpropane group. Nyl, n-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-thirteen, n-fourteen醯基, pentadecyl, and hexadecyl, etc. Specific examples when R ^c19 is a saturated aliphatic oxy group include: acetoxy group, propoxy group, n-butoxy group, 2-methylpropoxy group, n-pentoxy group, 2,2-Dimethylpropionyloxy, n-hexyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n- Dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy, etc.

When R ^c19 is an alkoxycarbonyl group, it is preferably 2 or more and 20 or less carbon atoms, more preferably 2 or more and 7 or less carbon atoms. Specific examples when R ^c19 is an alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl , Second butoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexoxycarbonyl, n-heptyloxy Carbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxy Group carbonyl and so on.

When R ^c19 is a phenylalkyl group, it is preferably 7 or more and 20 or less carbon atoms, more preferably 7 or more and 10 or less carbon atoms. Moreover, when R ^c19 is a naphthylalkyl group, it is preferably from 11 to 20 carbon atoms, and more preferably from 11 to 14 carbon atoms. Specific examples when R ^c19 is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when R ^c19 is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl) ) Ethyl. When R ^c19 is a phenylalkyl group or a naphthylalkyl group, R ^c19 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c19 is a heterocyclic group, the heterocyclic group is a monocyclic ring containing more than one of five or six members of N, S, and O, or the monocyclic ring is condensed with each other or the monocyclic ring and a benzene ring. Into the heterocyclic group. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 at most. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, azole, isoazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine , Da 𠯤, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoindole Quinoline, quinazoline, quinoline, quinoline, and quinoline, etc. When R ^c19 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^c19 is an amino group substituted with one or two organic groups, preferable examples of the organic group include: alkyl groups with 1 to 20 carbon atoms, and rings with 3 to 10 carbon atoms Alkyl group, saturated aliphatic acyl group having 2 to 20 carbon atoms, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted phenyl group having 7 to 20 carbon atoms An alkyl group, an optionally substituted naphthyl group, an optionally substituted naphthylmethyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclic group, and the like. The specific examples of these preferred organic groups are the same as ^{R c19.} As specific examples of the amino group substituted with one or two organic groups, there may be mentioned: methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, Isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decyl Amino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentanylamino, n-hexylamino, n-heptanylamino , N-octylamino, n-decanoylamino, benzylamino, α-naphthylamino, β-naphthylamino, etc.

Examples of the substituent when the phenyl, naphthyl, and heterocyclic group contained in R ^c19 further have a substituent include an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Oxy group, saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic oxy group with 2 to 7 carbon atoms, and 1 carbon atom The monoalkylamino group of the above 6 alkyl group, the dialkylamino group of the alkyl group having 1 to 6 carbon atoms, linolin-1-yl, piperid-1-yl, halogen, nitro, And cyano, etc. When the phenyl, naphthyl, and heterocyclic groups contained in R ^c19 further have substituents, the number of the substituents is not limited within a range that does not interfere with the purpose of the present invention, and it is preferably 1 or more. the following. When the phenyl group, naphthyl group, and heterocyclic group contained in R ^c19 have plural substituents, the plural substituents may be the same or different.

^Among R c19, in terms of chemical stability, less steric hindrance and easier synthesis of oxime ester compounds, etc., it is preferably selected from alkyl groups having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. The group of the following alkoxy groups and saturated aliphatic acyl groups having 2 to 7 carbon atoms is more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

Bonded to R ^c19 on the position of the phenyl group, are bonded to the phenyl group for R ^c19 junction, the position of the main skeleton with a phenyl oxime ester compound of bonding one set of keys, the position is set as methyl In the case of 2 digits, it is preferably 4 or 5 digits, and more preferably 5 digits. In addition, d is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.

^{R c13} in the above formula (c4) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent. The specific examples of R ^{c13 are} as described above with respect to formula (c1). ^{As R c13} in the formula (c4), methyl, ethyl, and phenyl are preferred, and methyl and phenyl are more preferred.

Among the oxime ester compounds, preferred examples of the compounds included in the formula (c1) but not included in the formula (c4) include the following compounds. [化52]

Moreover, as an oxime ester compound, the compound of the following formula is especially preferable among the oxime ester compound represented by the formula (c4). [化53]

[化54]

[化55]

[化56]

[化57]

[化58]

[化59]

In addition, in terms of the sensitivity of the resin composition and the transparency of the cured product, the oxime ester compound is particularly preferably an oxime ester compound represented by the following formula (1).

(式(1)中，R^c1 為氫原子、硝基或一價有機基，R^c2 及R^c3 分別為可具有取代基之鏈狀烷基、可具有取代基之環狀有機基、或氫原子，R^c2 與R^c3 可相互鍵結而形成環，R^c4 為一價有機基，R^c5 為氫原子、可具有取代基之碳原子數1以上11以下之烷基、或可具有取代基之芳基，n1為0以上4以下之整數，n2為0或1)[化60]

(In formula (1), R ^c1 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^c2 and R ^c3 are respectively a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or hydrogen Atoms, R ^c2 and R ^c3 can be bonded to each other to form a ring, R ^c4 is a monovalent organic group, R ^c5 is a hydrogen atom, optionally substituted alkyl with 1 to 11 carbon atoms, or optionally substituted The aryl group, n1 is an integer from 0 to 4, n2 is 0 or 1)

In the formula (1), R ^c1 is a hydrogen atom, a nitro group, or a monovalent organic group. R ^{c1 is} on the tea ring in formula (1), and is bonded to a six-membered aromatic ring different from the six-membered aromatic ring bonded to the group shown by _{-(CO) n2 -.} In the formula (1), R ^c1 is not particularly limited to the bonding position of the chrysanthemum ring. In the case where the compound represented by formula (1) has one or more R ^c1 , in terms of easy synthesis of the compound represented by formula (1), etc., it is preferably one or more of R ^c1 One bond is in the second position of the tea ring. When R ^c1 is plural, the plural R ^c1 may be the same or different.

When R ^c1 is an organic group, R ^c1 is not particularly limited within a range that does not interfere with the purpose of the present invention, and is appropriately selected from various organic groups. Preferable examples when R ^c1 is an organic group include: alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl group, saturated aliphatic acyloxy group, alkoxycarbonyl group, A phenyl group that may have a substituent, a phenoxy group that may have a substituent, a benzyl group that may have a substituent, a phenoxycarbonyl group that may have a substituent, a benzyloxy group that may have a substituent, and the Substituent phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyloxy, optionally substituted naphthyloxycarbonyl, optionally substituted Naphthyloxy, naphthylalkyl which may have substituents, heterocyclic groups which may have substituents, heterocyclic carbonyl groups which may have substituents, amino groups substituted with one or two organic groups, 𠰌line -1-yl, piper-1-yl and so on.

When R ^c1 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. In addition, when R ^c1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R ^c1 is an alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl , Isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl Base, and isodecyl, etc. In addition, when R ^c1 is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups with ether bonds in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc.

When R ^c1 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. In addition, when R ^c1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R ^c1 is an alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, Tertiary butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, tertiary pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy Oxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. In addition, when R ^c1 is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include: methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy Group, propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or a cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples when R ^c1 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As a ^{specific example when R c1} is a cycloalkoxy group, a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, etc. are mentioned.

When R ^c1 is a saturated aliphatic oxy group or a saturated aliphatic oxy group, the number of carbon atoms of the saturated aliphatic oxy group or saturated aliphatic oxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 the following. As ^{specific examples when R c1} is a saturated aliphatic aliphatic group, there may be mentioned: acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentanyl group, 2,2-dimethylpropane group Nyl, n-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-thirteen, n-fourteen醯基, pentadecyl, and hexadecyl, etc. Specific examples when R ^c1 is a saturated aliphatic oxy group include: acetoxy, propoxy, n-butoxy, 2-methylpropoxy, n-pentoxy, 2,2-Dimethylpropionyloxy, n-hexyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n- Dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy, etc.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when R ^c1 is an alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and isobutoxycarbonyl. , Second butoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexoxycarbonyl, n-heptyloxy Carbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxy Group carbonyl and so on.

When R ^c1 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. When R ^c1 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples when R ^c1 is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when R ^c1 is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl) ) Ethyl. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclic group, the heterocyclic group is a monocyclic ring containing more than one of five or six members of N, S, and O, or the monocyclic ring is condensed with each other or the monocyclic ring and the benzene ring. Into the heterocyclic group. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, azole, isoazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine , Da 𠯤, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoindole Quinoline, quinazoline, quinoline, quinazoline, quinoline, piperidine, piperidine, quinoline, piperidine, tetrahydropiperan, and tetrahydrofuran, etc. When R ^c1 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^c1 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as the case where ^{R c1 is a heterocyclic group.}

When R ^c1 is an amino group substituted with one or two organic groups, preferable examples of the organic group include: alkyl groups with 1 to 20 carbon atoms, and rings with 3 to 10 carbon atoms. Alkyl group, saturated aliphatic acyl group with 2 to 21 carbon atoms, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted phenyl group with 7 to 20 carbon atoms An alkyl group, an optionally substituted naphthyl group, an optionally substituted naphthylmethyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclic group, and the like. The specific examples of these preferred organic groups are the same as ^{R c1.} Specific examples of amino groups substituted with one or two organic groups include: methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, Isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decyl Amino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentanylamino, n-hexylamino, n-heptanylamino , N-octylamino, n-decanoylamino, benzylamino, α-naphthylamino, β-naphthylamino, etc.

Examples of the substituent when the phenyl, naphthyl, and heterocyclic group contained in R ^c1 further have a substituent include: an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms Oxy group, saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic oxy group with 2 to 7 carbon atoms, and 1 carbon atom The monoalkylamino group of the above 6 alkyl group, the dialkylamino group of the alkyl group having 1 to 6 carbon atoms, linolin-1-yl, piperid-1-yl, halogen, nitro, And cyano, etc. When the phenyl, naphthyl, and heterocyclic groups contained in R ^c1 further have substituents, the number of the substituents is not limited within the range that does not interfere with the purpose of the present invention, and it is preferably 1 or more 4 or less. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^c1 have plural substituents, the plural substituents may be the same or different.

Among the groups explained above, as R ^c1 , if it is a nitro group or a group represented by R ^c10 -CO-, the sensitivity tends to increase, which is preferable. R ^c10 is not particularly limited within a range that does not interfere with the purpose of the present invention, and it can be selected from various organic groups. Examples of preferable groups for R ^c10 include: alkyl groups having 1 to 20 carbon atoms, phenyl groups which may have substituents, naphthyl groups which may have substituents, and heterocyclic groups which may have substituents . As R ^c10 , among these groups, 2-methylphenyl, thien-2-yl, and α-naphthyl are particularly preferred. In addition, if R ^c1 is a hydrogen atom, transparency tends to become better, which is preferable. Furthermore, if R ^c1 is a hydrogen atom and R ^c4 is a group represented by the formula (1a) or (1b) described later, there is a tendency that transparency becomes better.

In the formula (1), R ^c2 and R ^c3 are each a linear alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c2 and R ^c3 may be bonded to each other to form a ring. Among these groups, R ^c2 and R ^{c3 are} preferably a chain alkyl group which may have a substituent. When R ^c2 and R ^c3 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c2 and R ^c3 are chain alkyl groups without substituents, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 the following. Specific examples when R ^c2 and R ^c3 are chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Base, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, iso Nonyl, n-decyl, and isodecyl, etc. In addition, when R ^c2 and R ^c3 are alkyl groups, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups with ether bonds in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc.

When R ^c2 and R ^c3 are chain alkyl groups with substituents, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less . In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear. The substitution that the alkyl group may have is not particularly limited as long as it does not interfere with the purpose of the present invention. Preferred examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. The cyclic organic group may, for example, be a cycloalkyl group, an aromatic hydrocarbon group, or a heterocyclic group. Specific examples of the cycloalkyl group are the same as the preferred examples when ^{R c1 is a cycloalkyl group.} Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. Specific examples of the heterocyclic group are the same as the preferable examples when ^{R c1 is a heterocyclic group.} When R ^c1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The preferred number of substituents varies according to the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When R ^c2 and R ^c3 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. The cyclic organic group may, for example, be an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. When R ^c2 and R ^c3 are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R ^c2 and R ^c3 are chain alkyl groups.

When R ^c2 and R ^c3 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by bonding a plurality of benzene rings via carbon-carbon bonds, or a condensation of a plurality of benzene rings. The basis of formation. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of plural benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more Preferably it is 2 or less, particularly preferably 1. Preferable specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl.

When R ^c2 and R ^c3 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, nordoxyl, isooxyl, tricyclononyl , Tricyclodecyl, tetracyclododecyl, and adamantyl, etc.

When R ^c2 and R ^c3 are heterocyclic groups, the heterocyclic group is a monocyclic ring containing more than one of five or six members of N, S, O, or the monocyclic rings or the monocyclic ring and benzene A heterocyclic group formed by ring condensation. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, azole, isoazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine , Da 𠯤, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoindole Quinoline, quinazoline, quinoline, quinazoline, quinoline, piperidine, piperidine, quinoline, piperidine, tetrahydropiperan, and tetrahydrofuran, etc.

R ^c2 and R ^c3 may be bonded to each other to form a ring. The group including ^{the ring formed by R c2} and R ^{c3 is} preferably a cycloalkylene group. When R ^c2 and R ^{c3 are} bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a five-membered ring or a six-membered ring, and more preferably a five-membered ring.

When ^{the group formed by the bonding of R c2} and R ^c3 is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring that can be condensed with the cycloalkylene ring include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a furan ring. , Thiophene ring, pyrrole ring, pyridine ring, pyridine ring, and pyrimidine ring.

As an example of a ^{preferable group among R c2} and R ^c3 described above, the group represented by the formula -A ⁰¹ -A ⁰² can be exemplified. In the formula, A ⁰¹ is a linear alkylene group, and A ⁰² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The ^{number of carbon atoms of the linear alkylene group of A 01} is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A ⁰² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A ⁰² is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. When A ⁰² is a halogenated alkane, the halogen atom contained in the halogenated alkane is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The alkyl halide may be linear or branched, preferably linear. When A ⁰² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that ^{R c2} and R ^{c3 have as substituents.} When A ⁰² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group that ^{R c2} and R ^{c3 have as substituents.}

Preferred specific examples of R ^c2 and R ^c3 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3-methoxy n-propyl, 4-methoxy n-butyl, 5-methoxy n-pentyl, 6-methoxy n-hexyl, 7-methoxy n-heptyl, 8-methoxy n Octyl, 2-ethoxyethyl, 3-ethoxy n-propyl, 4-ethoxy n-butyl, 5-ethoxy n-pentyl, 6-ethoxy n-hexyl, 7-ethoxy Alkoxyalkyl groups such as n-heptyl and 8-ethoxy n-octyl; 2-cyanoethyl, 3-cyano n-propyl, 4-cyano n-butyl, 5-cyano n-pentyl Cyanoalkyl groups such as 6-cyano n-hexyl, 7-cyano n-heptyl, and 8-cyano n-octyl; 2-phenylethyl, 3-phenyl n-propyl, 4-phenyl Phenyl alkyl groups such as n-butyl, 5-phenyl n-pentyl, 6-phenyl n-hexyl, 7-phenyl n-heptyl, and 8-phenyl n-octyl; 2-cyclohexyl ethyl, 3- Cyclohexyl n-propyl, 4-cyclohexyl n-butyl, 5-cyclohexyl n-pentyl, 6-cyclohexyl n-hexyl, 7-cyclohexyl n-heptyl, 8-cyclohexyl n-octyl, 2-cyclopentyl Ethyl, 3-cyclopentyl n-propyl, 4-cyclopentyl n-butyl, 5-cyclopentyl n-pentyl, 6-cyclopentyl n-hexyl, 7-cyclopentyl n-heptyl, and 8- Cycloalkyl alkyl such as cyclopentyl n-octyl; 2-methoxycarbonyl ethyl, 3-methoxycarbonyl n-propyl, 4-methoxycarbonyl n-butyl, 5-methoxycarbonyl n-pentyl Group, 6-methoxycarbonyl n-hexyl, 7-methoxycarbonyl n-heptyl, 8-methoxycarbonyl n-octyl, 2-ethoxycarbonyl ethyl, 3-ethoxycarbonyl n-propyl, 4-ethoxycarbonyl n-butyl, 5-ethoxycarbonyl n-pentyl, 6-ethoxycarbonyl n-hexyl, 7-ethoxycarbonyl n-heptyl, 8-ethoxycarbonyl n-octyl, etc. Alkoxycarbonylalkyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro N-octyl, 2-bromoethyl, 3-bromo n-propyl, 4-bromo n-butyl, 5-bromo n-pentyl, 6-bromo n-hexyl, 7-bromo n-heptyl, 8-bromo n-octyl , 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl and other halogenated alkanes.

As R ^c2 and R ^c3 , among the above-mentioned preferred groups are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl , 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5 ,5,5-Heptafluoro-n-pentyl.

Examples of preferable organic groups for R ^c4 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, and saturated aliphatic groups in the same way ^{as R c1.} A oxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent group, a benzyl group which may have a substituent group, a phenoxycarbonyl group which may have a substituent group, a benzyloxy group which may have a substituent group Group, optionally substituted phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthyloxy group, optionally substituted naphthyloxy group, optionally substituted naphthoxycarbonyl group, Substituent naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl group, amine substituted with 1 or 2 organic groups Group, linolin-1-yl, and piperidine-1-yl, etc. The specific examples of the bases are the same as the specific examples of the bases described with respect to R ^c1. Moreover, as R ^c4 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in ^{R c1 may have.}

Among the organic groups, R ^{c4 is} preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, or a thiophenylalkyl group which may have a substituent on the aromatic ring. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is particularly preferred, and methyl is most preferred. base. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among cycloalkylalkyls, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups that may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.

Moreover, as R ^c4 , the group represented by ^{-A 03} -CO-OA ^{04 is} also preferable. A ⁰³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁰⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ⁰³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ⁰³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

Preferred examples of A ⁰⁴ include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred specific examples of A ⁰⁴ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, n-hexyl Group, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, etc.

Preferred specific examples of the group shown in -A ⁰³ -CO-OA ⁰⁴ include: 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl , 2-n-butoxycarbonylethyl, 2-n-pentoxycarbonylethyl, 2-n-hexoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3- Methoxycarbonyl n-propyl, 3-ethoxycarbonyl n-propyl, 3-n-propoxycarbonyl n-propyl, 3-n-butoxycarbonyl n-propyl, 3-n-pentoxycarbonyl n-propyl , 3-n-hexyloxycarbonyl n-propyl, 3-benzyloxycarbonyl n-propyl, and 3-phenoxycarbonyl n-propyl, etc.

(式(1a)及式(1b)中，R^c7 及R^c8 分別為有機基，n3為0以上4以下之整數，於R^c7 及R^c8 位於苯環上相鄰之位置之情形時，R^c7 與R^c8 可相互鍵結而形成環，n4為1以上8以下之整數，n5為1以上5以下之整數，n6為0以上(n5＋3)以下之整數，R^c9 為有機基)As mentioned above, R ^c4 has been described, and R ^{c4 is} preferably a group represented by the following formula (1a) or the following formula (1b). [化61]

(In formula (1a) and formula (1b), R ^c7 and R ^c8 are organic groups, respectively, n3 is an integer from 0 to 4, and when R ^c7 and R ^{c8 are} located at adjacent positions on the benzene ring, R ^c7 and R ^c8 can be bonded to each other to form a ring, n4 is an integer of 1 to 8 and n5 is an integer of 1 to 5, n6 is an integer of 0 to (n5+3), and R ^c9 is an organic group)

The examples of the organic groups of ^{R c7} and R ^c8 in formula (1a) are the same as those of ^{R c1.} As R ^c7 , an alkyl group or a phenyl group is preferred. When R ^c7 is an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, R ^{c7 is} most preferably a methyl group. When R ^c7 and R ^{c8 are} bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by the formula (1a) and the group ^{forming a ring between R c7} and R ^c8 include: naphth-1-yl, 1,2,3,4-tetrahydronaphthalen-5-yl Wait. In the above formula (1a), n3 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula (1b), R ^c9 is an organic group. The organic group may, for example, be the same as the organic group explained ^{for R c1.} Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. As R ^c9 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. are preferably exemplified, and among these, a methyl group is more preferable.

In the above formula (1b), n5 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (1b), n6 is 0 or more (n5+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (1b), n4 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

In the formula (1), R ^c5 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. Examples of substituents that may be possessed when R ^c5 is an alkyl group include phenyl, naphthyl, and the like. In addition, ^{examples of substituents that may be possessed when R c1} is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom, and the like.

In formula (1), as R ^c5 , hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, methylphenyl, naphthyl, etc. can be preferably exemplified Among these, methyl or phenyl is more preferred.

Preferred specific examples of the compound represented by formula (1) include the following PI-43 to PI-83. [化62]

[化63]

The content of the photopolymerization initiator (C) is preferably 0.5% by mass or more and 30% by mass or less with respect to the mass of the resin composition other than the mass of the solvent (S) described below (total solid content), more preferably 1 The mass% is above 20 mass%. By setting the content of the photopolymerization initiator (C) in the above range, a resin composition with good curability can be obtained.

A photoinitiator auxiliary agent can be combined with the photopolymerization initiator (C). As the photo-initiating auxiliary, there may be mentioned: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4 -Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine , 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethyl Oxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxy Thiol compounds such as benzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, 3-mercaptopropionate, etc. These photoinitiating assistants can be used alone or in combination of two or more kinds.

・Organic solvent (S) Typically, the second resin composition may contain an organic solvent (S) for the purpose of adjusting coatability. As the organic solvent (S), the same organic solvent as the organic solvent explained for the first resin composition can be used.

The use amount of the organic solvent (S) can be appropriately determined according to the use of the resin composition. As an example of the usage amount of the organic solvent (S), the solid content concentration of the resin composition may be an amount in the range of 1% by mass to 50% by mass.

・Other ingredients The resin composition may optionally contain various additives other than the above-mentioned components. Specifically, examples thereof include dispersion aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, thermal polymerization inhibitors, defoamers, surfactants, and the like.

In addition, the second resin composition may contain an epoxy group-containing cyclic silicone compound (A-II) that does not react with the (meth)acrylic resin (A-I). In terms of easy formation of a cured product with a low relative permittivity, the resin composition preferably does not contain an epoxy group-containing cyclic siloxane compound. When the resin composition contains the epoxy-containing cyclic silicone compound (A-II), its content is preferably 40 relative to the mass of the resin composition other than the mass of the organic solvent (S) % By mass or less, more preferably 10% by mass or less, and still more preferably 1% by mass or less.

≪The hardened product and the manufacturing method of the hardened product≫ The cured product can be produced by heating and/or exposing the above-mentioned resin composition. When manufacturing a cured product, which of heating, exposure, and heating and exposure is performed is appropriately determined in consideration of the composition of the cured product composition. Since the cured product of the above-mentioned resin composition exhibits a relatively low relative permittivity, it is suitably used as a material for films such as insulators in display panels for various image display devices.

The relative permittivity of the cured product is measured at a frequency of 0.1 MHz, and is preferably 3.3 or less, more preferably 3.2 or less, and still more preferably 3.1 or less. As a method of measuring the relative permittivity, the mercury probe method is preferably used. As an apparatus capable of measuring relative permittivity by the mercury probe method, for example, SSM-495 (manufactured by Semilab Japan) can be cited. As a preferable example of the method of measuring the relative permittivity, the following method can be cited: After forming a film-like cured product using the steps 1) to 4) below, the formed cured product is compared with the mercury probe method. Determination of dielectric constant. 1) Coating the resin composition on the silicon wafer to form a coating film. 2) Heat the formed coating film at 100°C for 120 seconds. 3) When the resin composition contains a photopolymerization initiator or a photosensitive curing agent, the coating film is arbitrarily exposed with an exposure amount of ^{1 kJ/cm 2.} 4) If necessary, heat the exposed coating film at 230°C for 20 minutes.

The shape of the cured product is not particularly limited, but a film shape is preferred. When the cured product is a film, its thickness is preferably 10 nm or more and 30000 nm or less, more preferably 50 nm or more and 1500 nm or less, and still more preferably 100 nm or more and 1000 nm or less.

When the shape of the cured product is a film, it is preferable to heat and/or expose the coating film of the resin composition coated on the substrate. The coating method is not particularly limited. For example, a roller coater, a reverse coater, a bar coater, etc. contact transfer type coating device, or a spinner (rotary coating device), A method of coating with non-contact coating devices such as curtain flow coaters.

It is preferable to dry (pre-bake) the coated film after the above-mentioned coating. The drying method is not particularly limited. For example, the following methods can be exemplified: (1) Using a hot plate to dry at a temperature of 80°C or more and 120°C or less, preferably 90°C or more and 100°C or less, for 60 seconds or more and 120 seconds or less Methods; (2) Put it at room temperature for several hours to several days; (3) Put it in a hot air heater or infrared heater for several tens of minutes to several hours to remove the solvent, etc. Furthermore, the resin composition can be cured simultaneously with drying.

When the resin composition is heated to form a cured product, the heating temperature and heating time are not particularly limited as long as the curing progresses well and the cured product does not undergo thermal degradation or thermal decomposition. The heating temperature is, for example, preferably 80°C or higher and 300°C or lower, more preferably 100°C or higher and 280°C or lower, and still more preferably 120°C or higher and 250°C or lower. The heating time is, for example, preferably 10 seconds or more and 12 hours or less, more preferably 1 minute or more and 6 hours or less, and more preferably 2 minutes or more and 3 hours or less.

When exposing the resin composition to form a cured product, the exposure conditions are not particularly limited as long as the curing progresses well. Exposure is performed by irradiating active energy rays, such as ultraviolet rays and excimer laser light, for example. The amount of energy rays to be irradiated is not particularly limited. For example, 3 mJ/cm ² or more and 2000 mJ/cm ² or less can be mentioned.

≪Method of manufacturing patterned hardened film≫ When the first resin composition or the second resin composition containing a photosensitive curing agent is used as the resin composition, a cured film patterned by applying a photolithography method can be formed. Specifically, a patterned hardened film is manufactured by a method including the following steps: Coating the above-mentioned first resin composition or the above-mentioned second resin composition containing a photosensitive curing agent on a substrate to form a coating film; For the coated film, the position is selectively exposed; Use a developer to develop the exposed coating film to pattern the coating film; and The patterned coating film is heated.

Regarding the patterned cured film, the film thickness is as described above for the cured film. In the manufacturing method of the above-mentioned patterned cured film, the coating method is as described above with respect to the manufacturing method of a cured film. The exposure conditions are as described above with regard to the production method of the cured film. Position-selective exposure is performed, for example, through a negative type photomask. Regarding the heating conditions after exposure, the thermal curing conditions described above for the production method of the cured film can be applied.

The development method is not particularly limited, and for example, a dipping method, a spray method, etc. can be used. Specific examples of the developer include: organic solvent (S) that the resin composition may contain; organic developer such as monoethanolamine, diethanolamine, triethanolamine, etc.; for example, it contains at a concentration of 0.02% by mass to 10% by mass Alkaline aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt, etc. When the resin composition is the first resin composition containing a photosensitive hardener, it is preferably an organic solvent (S) that the resin composition can contain. When the resin composition is the second resin composition, the developer is preferably an alkaline developer. As the alkaline developer, for example, a tetramethylammonium hydroxide aqueous solution having a concentration of 0.05% by mass or more and 10% by mass or less, and preferably a concentration of 0.05% by mass or more and 3% by mass or less is preferable. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples.

[Example 1] After replacing the inside of a glass three-necked flask with a capacity of 300 mL with a nitrogen atmosphere, the internal temperature of the flask was set to 80°C. Next, 5.18 g of diethylene glycol methyl ethyl ether (MEDG) was added to the flask. In addition, a glass sample bottle with a capacity of 300 mL was filled with 12% by mass of methacrylic acid ^{, 17% by mass of tricyclo[5.2.1.0 2,6} ]decyl methacrylate, and 3,4-epoxy methacrylate. 29 g of a monomer mixture of 71% by mass of cyclohexyl methyl ester, 5 g of 2,2'-azobis(2-methylpropionic acid) dimethyl as a polymerization initiator, and 62 g of MEDG to prepare a polymerization solution . After dropping the resulting polymerization solution into a three-necked flask at 80°C for 2 hours, stirring was continued for 2 hours at 80°C to continue the polymerization reaction. As a result, a MEDG solution (concentration 30% by mass) of (meth)acrylic resin containing 50 g of (meth)acrylic resin (resin P1) in the following structural unit ratio was obtained. The value at the bottom right of the bracket is the ratio (mass %) of each structural unit. Regarding the obtained (meth)acrylic resin, the molecular weight in terms of polystyrene was measured by gel permeation chromatography. As a result, the weight average molecular weight (Mw) was 9,000. [化64]

Then, to the obtained solution of the resin P1, 3 g of the epoxy-containing cyclic siloxane compound C1 3 g and 1-methylimidazole 1 g of the following structure were added. Thereafter, the contents of the flask were stirred at 80°C for 30 minutes to react the resin P1 with the epoxy-containing cyclic silicone compound to obtain the resin P2 as a silicone-modified (meth)acrylic resin. By FT-IR (fourier transform infrared radiation, Fourier transform infrared spectroscopy) measurement, it was confirmed that ester bonds and hydroxyl groups were formed due to the reaction between resin P1 and epoxy-containing cyclic siloxane compounds. Regarding the obtained resin P2, the molecular weight in terms of polystyrene was measured by gel permeation chromatography. As a result, the weight average molecular weight (Mw) was 13,000. [化65]

[Example 2, Comparative Example 1, and Comparative Example 2] In Example 2, Comparative Example 1, and Comparative Example 2, dipentaerythritol hexaacrylate was used as the photopolymerizable monomer.

In Example 2, Comparative Example 1, and Comparative Example 2, the compound of the following formula was used as the photopolymerization initiator. [化66]

In Example 2, Comparative Example 1, and Comparative Example 2, IR1010 (manufactured by BASF Japan) was used as the antioxidant. Use 3-glycidoxypropyltrimethoxysilane as the silane coupling agent. As the surfactant, BYK-310 (manufactured by BYK-Chemie) was used. MEDG and propylene glycol monomethyl ether acetate (PGMEA) were used as organic solvents.

Each component of the type described in Table 1 below was mixed with the ratio (% by mass) described in Table 1 below to obtain curable resin compositions of Example 2, Comparative Example 1, and Comparative Example 2. Using the obtained resin compositions of Example 2, Comparative Example 1, and Comparative Example 2, the relative dielectric constant of the cured product and the light transmittance of the cured product (wavelength 380-780 nm) were measured according to the following formula. The evaluation results are shown in Table 1.

＜Measurement of relative permittivity＞ The resin composition is coated on the silicon wafer with a spinner to form a coating film. After heating the formed coating film at 100°C for 120 seconds, it was further heated at 230°C for 20 minutes to form a cured film with a film thickness of 1 μm. For the formed cured film, SSM-495 (manufactured by Semilab Japan) was used to measure the relative permittivity of the cured film at a measuring frequency of 0.1 MHz.

<Measurement of light transmittance> The resin composition was coated on a glass substrate with a spinner to form a coating film. The formed coating film was heated at 100°C for 120 seconds. For the coated film after heating, an exposure device (TME-150PRO, manufactured by TOPCON Corporation) was used to expose the coated film with an exposure amount of ^{20 mW/cm 2.} The coated film after exposure was heated at 230°C for 20 minutes to obtain a cured film with a thickness of 3 μm. The light transmittance (wavelength 380-780 nm) of the obtained cured film was measured with MCPD-3700 (manufactured by Otsuka Electronics Co., Ltd.).

[Table 1] Example 2 Comparative example 1 Comparative example 2 Silicone modified (meth)acrylic resin type Resin P2 - - quality% 14.48 - - (Meth) acrylic resin type - Resin P1 Resin P1 quality% - 14.48 12.9 Cyclic siloxane compounds containing epoxy groups type - - Compound C1 quality% - - 1.58 Photopolymerizable monomer quality% 7.25 7.25 7.25 Photopolymerization initiator quality% 0.88 0.88 0.88 Antioxidants quality% 0.10 0.10 0.10 Silane coupling agent quality% 0.22 0.22 0.22 Surfactant quality% 0.04 0.04 0.04 MEDG quality% 30.80 30.80 30.80 PGMEA quality% 46.23 46.23 46.23 Relative permittivity 3.3 3.6 3.5 Light transmittance 99% 99% 99%

According to Table 1, the resin composition of Example 2 containing resin P2 can provide a relatively low dielectric constant and transparent cured product. (Meth)acrylic resin, which is the structural unit of acrylate, and silicone modified (meth)acrylic resin obtained by reacting with epoxy-containing silicone compound. On the other hand, it can be seen that it contains (meth)acrylic resin that has not been modified by epoxy-containing silicone compound, or is a combination of (meth)acrylic resin and epoxy-containing silicone compound in Comparative Example 1 And the resin composition of Comparative Example 2 can provide a cured product that is transparent but has a relatively high dielectric constant.

[Example 3] The monomer mixture used in Example 1 was replaced with 14% by mass of methacrylic acid ^{, 17% by mass of tricyclo[5.2.1.0 2,6} ]decyl methacrylate, and 3,4-ring of acrylic acid Except for the monomer mixture of 69% by mass of oxotricyclic [5.2.1.0 ^2,6 ]decane-1-yl ester, in the same manner as in Example 1, (methyl) containing the following structural unit ratio was obtained Acrylic resin (resin P3) 50 g (meth)acrylic resin MEDG solution (concentration 30% by mass). The value at the bottom right of the bracket is the ratio (mass %) of each structural unit. Regarding the obtained (meth)acrylic resin, the molecular weight in terms of polystyrene was measured by gel permeation chromatography. As a result, the weight average molecular weight (Mw) was 9,500.

[化67]

Then, in the same manner as in Example 1, the resin P3 was reacted with the epoxy-containing cyclic siloxane compound used in Example 1 to obtain a resin as a siloxane-modified (meth)acrylic resin P4. By FT-IR measurement, it was confirmed that an ester bond and a hydroxyl group were formed due to the reaction between the resin P3 and the epoxy-containing cyclic silicone compound. Regarding the obtained resin P4, the molecular weight in terms of polystyrene was measured by gel permeation chromatography. As a result, the weight average molecular weight (Mw) was 125,000.

[Example 4, Comparative Example 3, and Comparative Example 4] Except that the resin P1 was replaced with the resin P3 and the resin P2 was replaced with the resin P4, in the same manner as in Example 2, Comparative Example 1, and Comparative Example 2, Example 4, Comparative Example 3, and Comparison were obtained in accordance with Table 2 below. The curable resin composition of Example 4. Using the obtained resin compositions of Example 4, Comparative Example 3, and Comparative Example 4, the relative permittivity of the cured product and the light of the cured product were measured in the same manner as in Example 2, Comparative Example 1 and Comparative Example 2. Measurement of transmittance (wavelength 380 ~ 780 nm). The evaluation results are shown in Table 2.

[Table 2] Example 4 Comparative example 3 Comparative example 4 Silicone modified (meth)acrylic resin type Resin P4 - - quality% 14.48 - - (Meth) acrylic resin type - Resin P3 Resin P3 quality% - 14.48 12.9 Cyclic siloxane compounds containing epoxy groups type - - Compound C1 quality% - - 1.58 Photopolymerizable monomer quality% 7.25 7.25 7.25 Photopolymerization initiator quality% 0.88 0.88 0.88 Antioxidants quality% 0.10 0.10 0.10 Silane coupling agent quality% 0.22 0.22 0.22 Surfactant quality% 0.04 0.04 0.04 MEDG quality% 30.80 30.80 30.80 PGMEA quality% 46.23 46.23 46.23 Relative permittivity 3.0 3.3 3.2 Light transmittance 99% 99% 99%

According to Table 2, the resin composition of Example 4 containing resin P4 can provide a relatively low dielectric constant and a transparent cured product. The resin P4 is made by containing (a (Meth)acrylic resin, which is the structural unit of acrylate, and silicone modified (meth)acrylic resin obtained by reacting with epoxy-containing silicone compound. On the other hand, containing (meth)acrylic resin that has not been modified by epoxy-containing silicone compound, or a combination of (meth)acrylic resin and epoxy-containing silicone compound in Comparative Example 3 and The resin composition of Comparative Example 4 can provide a cured product that is transparent but has a relatively high dielectric constant.

Claims (12)

A resin composition containing a silicone-modified (meth)acrylic resin (A1). The silicone-modified (meth)acrylic resin (A1) contains ( [化1]

(In formula (aI), ^Ra01 and ^Ra02 represent monovalent groups or alkyl groups containing epoxy groups, x1 represents an integer of 3 or more, and at least two of ^{x1 Ra01} and x1 ^{Ra02 contain epoxy} One valence basis). The resin composition of claim 1, wherein the amount of the structural unit derived from the (meth)acrylate having an alicyclic epoxy group in the (meth)acrylic resin (A-I) is 50% by mass or more. The resin composition of claim 1 or 2, wherein the silicone-modified (meth)acrylic resin (A1) is made of 100 parts by mass of the (meth)acrylic resin (AI) and 1 part by mass or more and 50 parts by mass The following reactants formed by the reaction of the above-mentioned epoxy-containing cyclic siloxane compound (A-II). The resin composition of claim 1 or 2, wherein the (meth)acrylate having an alicyclic epoxy group includes a polycyclic alkane skeleton. The resin composition of claim 1 or 2, which contains the above-mentioned silicone modified (meth)acrylic resin (A1), a photopolymerizable monomer (B), and a photopolymerization initiator (C), and The above-mentioned silicone modified (meth)acrylic resin (A1) contains a structural unit having an alkali-soluble group. A hardened product obtained by hardening the above-mentioned resin composition according to any one of claims 1 to 5 by heating and/or exposure. A method for manufacturing a hardened product, which heats and/or exposes the above-mentioned resin composition according to any one of claims 1 to 5. A method for manufacturing a patterned hardened film, which includes the following steps: Coating the resin composition of claim 5 on the substrate to form a coating film; For the above-mentioned coated film, position-selective exposure is performed; Use an alkaline developer to develop the exposed coating film to pattern the coating film; and The patterned coating film is heated. A siloxane-modified (meth)acrylic resin, which is a (meth)acrylic resin (AI) containing structural units derived from (meth)acrylates with alicyclic epoxy groups, and the following formula The reactant of the epoxy-containing cyclic siloxane compound (A-II) shown in (aI), [化2]

(In formula (aI), ^Ra01 and ^Ra02 represent monovalent groups or alkyl groups containing epoxy groups, x1 represents an integer of 3 or more, and at least two of ^{x1 Ra01} and x1 ^{Ra02 contain epoxy} One valence basis). Such as the silicone-modified (meth)acrylic resin of claim 9, wherein the above-mentioned (meth)acrylic resin (AI) is derived from a structural unit of (meth)acrylate having an alicyclic epoxy group The amount is 50% by mass or more. For example, the silicone-modified (meth)acrylic resin of claim 9 or 10, which is made of 100 parts by mass of the above-mentioned (meth)acrylic resin (AI) and 1 part by mass or more and 50 parts by mass or less of the above-mentioned epoxy group The cyclic siloxane compound (A-II) is a reactant. The silicone-modified (meth)acrylic resin according to claim 9 or 10, wherein the (meth)acrylate having an alicyclic epoxy group contains a polycyclic alkane skeleton.