CN113031399A - Resin composition, cured product, and siloxane-modified (meth) acrylic resin - Google Patents

Abstract

The present invention relates to a resin composition, a cured product, and a silicone-modified (meth) acrylic resin. The present invention provides: a curable resin composition which provides a cured product having a low relative 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; a silicone-modified (meth) acrylic resin suitable for use as a component of the aforementioned resin composition. The resin composition contains a (meth) acrylic resin having an alicyclic epoxy group and a siloxane-modified (meth) acrylic resin which is a reaction product of an epoxy group-containing cyclic siloxane compound having a specific structure, as a curable component.

Description

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

Technical Field

The present invention relates to a curable resin composition containing a siloxane-modified (meth) acrylic resin (a1) having a specific structure, a cured product of the resin composition, a method for producing a cured product using the resin composition, a method for producing a patterned cured film using a specific photosensitive composition as the resin composition, and a siloxane-modified (meth) acrylic resin suitable for use as a component of the resin composition.

Background

The (meth) acrylate having an alicyclic epoxy group, which is an unsaturated carboxylic acid ester compound having an alicyclic epoxy group, is generally a compound useful in the fields of coating materials, inks, adhesives, sealants, and the like. In particular, a polymer obtained from a (meth) acrylate containing an alicyclic structure and an epoxy group and a cured product thereof are excellent in weather resistance and have characteristics suitable for outdoor use. This is because the polymer or cured product exhibits predetermined performance, generally, due to the ring-opening reactivity of an epoxy group present in an alicyclic structure, the reactivity of a radical polymerizable double bond in a (meth) acrylate structure, and the like.

Conventionally, as unsaturated carboxylic acid esters having an epoxy group in the molecule, for example, there are known: terminal epoxy group-containing (meth) acrylates such as glycidyl methacrylate and 1-methyl-1, 2-epoxyethyl methacrylate; and (meth) acrylates having an alicyclic epoxy group such as 3, 4-epoxycyclohexylmethyl acrylate and 3, 4-epoxycyclohexylmethyl methacrylate. In addition, patent document 1 discloses a β -hydroxyacrylate compound having an epoxy group in the molecule.

Further, patent document 2 discloses a 3, 4-epoxy group-containing tricyclo [5.2.1.0 ]^2,6]An unsaturated carboxylic acid ester having a decane skeleton, which is intended to provide the following resin composition: when used as a radiation-sensitive resin, the resin composition has excellent solubility in a solvent, can form a high-performance coating film having transparency, heat resistance, etching resistance, flatness, and developability, and has high storage stability.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 61-263968

Patent document 2: international publication No. 2006-059564

Disclosure of Invention

Technical problem to be solved by the invention

Films such as insulators in display panels for various image display devices are desired to have a low relative dielectric constant. However, the cured products of the curable compositions described in patent documents 1 and 2 have high relative dielectric constants. Therefore, it is difficult to apply the curable compositions described in patent documents 1 and 2 to a material for producing a film constituting a display panel.

In view of the above problems of the prior art, an object of the present invention is to provide: a curable resin composition which provides a cured product having a low relative 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 silicone-modified (meth) acrylic resin suitable for use as a component of the aforementioned resin composition.

Means for solving the problems

The present inventors have found that the above problems can be solved by incorporating a (meth) acrylic resin having an alicyclic epoxy group and a siloxane-modified (meth) acrylic resin, which is a reaction product of an epoxy group-containing cyclic siloxane compound having a specific structure, as a curable component in a resin composition, and have completed the present invention. More specifically, the present invention provides the following.

The 1 st embodiment of the present invention is a resin composition comprising a silicone-modified (meth) acrylic resin (A1),

the siloxane-modified (meth) acrylic resin (a1) is a reaction product of a (meth) acrylic resin (a-I) containing a structural unit derived from a (meth) acrylate having an alicyclic epoxy group and an epoxy group-containing cyclic siloxane compound (a-II) represented by the following formula (a-I).

[ chemical formula 1]

(formula (a)In the formula (I), R^a01And R^a02Represents a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x 1R^a01And x 1R^a02At least 2 of them are epoxy group-containing monovalent groups. )

The 2 nd aspect of the present invention is a cured product obtained by curing the resin composition according to the 1 st aspect by heating and/or exposure to light.

The 3 rd aspect of the present invention is a method for producing a cured product, which comprises heating and/or exposing the resin composition according to the 1 st aspect.

The 4 th aspect of the present invention is a method for producing a patterned cured film, including the steps of:

a step of applying a resin composition according to embodiment 1, which comprises a (meth) acrylic resin (a1) (which comprises a structural unit having an alkali-soluble group), a photopolymerizable monomer (B), and a photopolymerization initiator (C), onto a substrate to form a coating film;

a step of exposing the coating film in a position-selective manner;

a step of developing the exposed coating film with an alkaline developer to pattern the coating film; and

and a step of heating the patterned coating film.

The 5 th embodiment of the present invention is a siloxane-modified (meth) acrylic resin which is a reaction product of a (meth) acrylic resin (a-I) containing a structural unit derived from a (meth) acrylate having an alicyclic epoxy group and an epoxy group-containing cyclic siloxane compound (a-II) represented by the following formula (a-I).

[ chemical formula 2]

(in the formula (a-I), R^a01And R^a02Represents a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x 1R^a01And x 1R^a02In which at least 2 areA monovalent group having an epoxy group. )

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: a curable resin composition which provides a cured product having a low relative 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 silicone-modified (meth) acrylic resin suitable for use as a component of the aforementioned resin composition.

Detailed Description

Resin composition

The resin composition contains a silicone-modified (meth) acrylic resin (a 1). The siloxane-modified (meth) acrylic resin (a1) is a reaction product of a (meth) acrylic resin (a-I) containing a structural unit derived from a (meth) acrylate having an alicyclic epoxy group and an epoxy group-containing cyclic siloxane compound (a-II) represented by the following formula (a-I).

[ chemical formula 3]

(in the formula (a-I), R^a01And R^a02Represents a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x 1R^a01And x 1R^a02At least 2 of them are epoxy group-containing monovalent groups. )

In the specification and claims of the present application, "(meth) acrylic group" means both an acrylic group and a methacrylic group. In the specification and claims of the present application, "(meth) acrylate" means both acrylate and methacrylate. In the description and claims of the present application, "(meth) acryloyl" means both acryloyl and methacryloyl.

The above resin composition contains the above siloxane-modified (meth) acrylic resin (a1) as an epoxy compound, and thus can be cured by a reaction related to an epoxy group.

The method for curing the resin composition is not particularly limited. The resin composition to which the heat-sensitive curing agent is added as necessary can be cured by heating. In addition, the resin composition to which the photosensitive curing agent is added can be cured by exposure to light.

The resin composition may include a photopolymerizable compound and a photopolymerization initiator. The resin composition containing the following components, which can be cured only by exposure or by a combination of exposure and heating: the above-mentioned siloxane-modified (meth) acrylic resin (a1) as an epoxy compound; a photopolymerizable compound and a photopolymerization initiator.

Preferred embodiments of the silicone-modified (meth) acrylic resin (a1) and the resin composition are described below. The resin composition is not limited at all to the composition described below, as long as it contains the silicone-modified (meth) acrylic resin (a 1).

< Silicone-modified (meth) acrylic resin (A1) >)

As described above, the siloxane-modified (meth) acrylic resin (a1) is a reaction product of the (meth) acrylic resin (a-I) containing a structural unit derived from a (meth) acrylate having an alicyclic epoxy group and the aforementioned epoxy-containing cyclic siloxane compound (a-II).

The resin composition contains the siloxane-modified (meth) acrylic resin (a1), and thus the resin composition can provide a cured product having a low relative dielectric constant.

The following description will be made of the production methods of the (meth) acrylic resin (a-I), the epoxy group-containing cyclic siloxane compound (a-II), and the siloxane-modified (meth) acrylic resin (a 1).

[ (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 (a-I) may be a homopolymer of a (meth) acrylate having an alicyclic epoxy group, or may be a copolymer of a (meth) acrylate having an alicyclic epoxy group and another monomer.

(meth) acrylate having alicyclic epoxy group)

The alicyclic group constituting the (meth) acrylate having an alicyclic epoxy group may be monocyclic or polycyclic. In view of easy availability of a cured product having 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.

Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups.

Specific examples of the (meth) acrylate having an alicyclic epoxy group include compounds represented by the following formulas (a-4-1a) to (a-4-1 o). Among these, compounds represented by the following formulae (a-4-1a) to (a-4-1e) are preferable, and compounds represented by the following formulae (a-4-1a) to (a-4-1c) are more preferable, in order to keep the developability within a suitable range.

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

In the above formula, R^a20Represents a hydrogen atom or a methyl group, R^a21Represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R^a22Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t represents an integer of 0 to 10 inclusive. As R^a21The alkylene group is preferably a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R^a22For example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH₂-Ph-CH₂- (Ph represents phenylene).

A compound represented by the formula (1)

The (meth) acrylate having an alicyclic epoxy group is preferably a compound represented by the following formula (1) because a cured product having a low relative dielectric constant is easily formed. The compound represented by the formula (1) will be described below.

[ chemical formula 7]

(in the formula (1), ring A represents a ring containing a 5-or 6-membered alicyclic ring fused to ring B, ring B represents an alicyclic ring containing a bridging group bridging within ring B, fused to rings A and C, ring C represents a ring containing a 5-or 6-membered alicyclic ring fused to ring B, and R represents¹Represents a (meth) acryloyl group, R²Represents an alkyl group, an alkanoyl group, an aroyl group or a trihydrocarbylsilyl group, and ring A, ring B or ring C may or may not have a substituent. )

In the formula (1), the ring A is a ring containing a 5-or 6-membered alicyclic ring fused with the ring B. Ring B is an alicyclic ring fused to rings a and C and comprising a bridging group bridging within ring B. Ring C is a ring fused to ring B comprising a 5-or 6-membered alicyclic ring. Ring A, B and C may or may not have a substituent.

Ring A may or may not contain a bridging group bridging within ring A similar to ring B. The ring a is preferably a 6-membered alicyclic ring, because the compound represented by formula (1) can be easily synthesized.

Ring C may or may not contain a bridging group bridging within ring C as with ring B. The ring C is preferably a 5-membered alicyclic ring, from the viewpoint of ease of synthesis of the compound represented by formula (1). From the viewpoint of selectivity of the epoxy group ring-opening reaction at the time of production, a 5-membered alicyclic ring is preferable.

The ring B can contribute to heat resistance by having a bridging group bridging within the ring B.

Examples of the ring B include a 5-to 8-membered alicyclic ring containing the bridging group. As the ring B, an alicyclic ring of a 6-or 7-membered ring containing the above bridging group is preferable, and an alicyclic ring of a 6-membered ring containing the above bridging group is more preferable.

Examples of the bridging group bridging the ring B include divalent groups having 1 to 5 carbon atoms. The number of carbon atoms of the bridging group is more preferably 1 to 3, and still more preferably 1 or 2. The bridging group is preferably an alkylene group, an ether bond (-O-), a thioether bond (-S-), a carbonyl group (-CO-) or a divalent group comprising at least 2 of them, more preferably an alkylene group, an ether bond (-OR), a thioether bond (-OR), or a divalent group comprising at least 2 of them, particularly preferably an alkylene group, an ether bond (-OR), or a thioether bond (-OR), and most preferably an alkylene group.

Examples of the alkylene group include alkylene groups having 1 to 5 carbon atoms which may have a substituent. The number of carbon atoms of the alkylene group is more preferably 1 to 3, and still more preferably 1 or 2. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group, and a methylene group, an ethylene group, and a propylene group are preferable, and a methylene group and an ethylene group are more preferable.

Examples of the substituent that the alkylene group may have and the substituents that ring A, B and C may have include a halogen atom and a hydrocarbon group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the hydrocarbon group include hydrocarbon groups having 1 to 10 carbon atoms. Preferable examples of the hydrocarbon group include an alkyl group and the like.

Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups. Among these alkyl groups, preferred are alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

The alkyl group may have a substituent. When the alkyl group has a substituent, examples of the substituent include a halogen atom and the like.

The ring B is preferably a ring represented by the following formula (2).

[ chemical formula 8]

(in the formula (2), L represents the bridging group, the bridging group is alkylene, ether bond, thioether bond, ketone group or at least 2 of them combined divalent group, R³And R⁴Each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group, represents a bonding site to the ring A, and represents a bonding site to the ring C. )

Specific examples and preferred examples of the bridging group relating to L are as described above.

With respect to as R³And R⁴Specific examples and preferable examples of the halogen atom and the hydrocarbon group in (b) include "a substituent which the alkylene group may have, and a substituent which the ring A, B and C may have" the specific examples and preferable examples of the halogen atom and the hydrocarbon group described above. As R³And R⁴Preferably a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom.

In the formula (1), R²Is an alkyl, alkanoyl, aroyl, or trihydrocarbylsilyl group.

As R²The alkyl group (b) may be linear or branched, and is preferably linear. As R²The alkyl group (b) has preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2 carbon atoms. Specific examples of the alkyl group include methyl, ethyl and n-propylAnd (b) a group selected from the group consisting of an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group and the like. Among these alkyl groups, preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups which are alkyl groups having 1 to 4 carbon atoms, more preferred are methyl and ethyl groups, and still more preferred is methyl.

As R²The alkanoyl group (b) may be linear or branched, and is preferably linear. As R²The number of carbon atoms of the alkanoyl group(s) is preferably 2 to 10, more preferably 2 to 4, and still more preferably 2. Specific examples of the alkanoyl group include an acetyl group, a propionyl group, a butyryl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, and a decanoyl group. Among these alkanoyl groups, acetyl and propionyl are preferred, and acetyl is more preferred.

With respect to as R²Examples of the aroyl group of (2) include benzoyl group and naphthoyl group.

As R²The trihydrocarbylsilyl group of (2) is a group in which 3 hydrocarbon groups are bonded to a silicon atom.

The 3 hydrocarbon groups in the trihydrocarbylsilyl group may be the same or different. In producing the compound represented by the formula (1), it is preferable that 3 hydrocarbon groups in the trihydrocarbylsilyl group are the same, from the viewpoint of easy synthesis and availability of the silane compound for introducing the trihydrocarbylsilyl group.

In the trihydrocarbylsilyl group, the hydrocarbon group 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 hydrocarbon group bonded to the silicon atom is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may contain 1 or more unsaturated bonds.

In the trihydrocarbylsilyl group, when the hydrocarbon group bonded to the silicon atom is an aliphatic hydrocarbon group, the structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures.

In the trihydrocarbylsilyl group, the number of carbon atoms of the hydrocarbon group bonded to a silicon atom is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4, from the viewpoint that the molecular weight and epoxy equivalent of the compound represented by formula (1) do not become excessively large.

The hydrocarbyl group in the trihydrocarbylsilyl group is preferably, for example, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups. Among these alkyl groups, preferred are alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

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

Specific examples of the aryl group include a phenyl group, a naphthalen-1-yl group and a naphthalen-2-yl group.

Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

Preferable examples of the trihydrocarbylsilyl group described above include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a triisobutylsilyl group, a tri-sec-butylsilyl group, a tri-tert-butylsilyl group, an ethyldimethylsilyl group, an n-propyldimethylsilyl group, an isopropyldimethylsilyl group, an n-butyldimethylsilyl group, an isobutyl dimethylsilyl group, a sec-butyldimethylsilyl group, and a tert-butyldimethylsilyl group.

The compound represented by the above formula (1) is preferably a compound represented by the following formula (3) or (4).

[ chemical formula 9]

(in the formulae (3) and (4), the ring B represents an alicyclic ring containing the bridging group bridging the ring B, and R is¹Represents a (meth) acryloyl group, R²Represents an alkyl group, an alkanoyl group, an aroyl group, or a trihydrocarbylsilyl group, R¹¹Represents a single bond or-CHR¹⁵A divalent group represented by R¹¹In the case of a single bond, R¹²And R¹³Or R¹³And R¹⁴Bonded to each other to form an oxirane ring (epoxy group), R¹¹is-CHR¹⁵In the case of the divalent group represented by (A) or (B), R¹²And R¹³、R¹³And R¹⁴Or R¹⁴And R¹⁵Bonded to each other to form an oxirane ring, R¹²～R¹⁵Wherein the group not forming an oxirane ring represents a hydrogen atom. )

In the formulae (3) and (4), specific examples and preferred examples of the ring B include alicyclic rings similar to those of the formula (1). The ring B is preferably a ring represented by the formula (2).

As R¹¹preferably-CHR¹⁵A divalent group represented by, more preferably R¹¹is-CHR¹⁵A divalent group represented by, and R¹²And R¹³、R¹³And R¹⁴Or R¹⁴And R¹⁵Are bonded to each other to form an oxirane ring, and R¹²～R¹⁵Wherein the group not forming an oxirane ring represents a hydrogen atom.

The method for producing the compound represented by formula (1) is not particularly limited. A preferred production method includes the steps of:

a step of reacting a compound represented by the following formula (M1) with (meth) acrylic acid to produce a compound represented by the following formula (M2); and the number of the first and second groups,

a step of alkylating, alkanoylating, arylylating or trihydrocarbylsilylating a hydroxyl group of a compound represented by the following formula (M2).

[ chemical formula 10]

(in the formula (M1), Ring A represents a ring containing a 5-or 6-membered alicyclic ring fused to Ring B, Ring B represents an alicyclic ring fused to rings A and C and containing a bridging group bridging within Ring B, Ring C represents a ring containing a 5-or 6-membered alicyclic ring fused to Ring B, and Ring A, Ring B and Ring C may or may not have a substituent.)

[ chemical formula 11]

(in the formula (M2), Ring A, Ring B, and Ring C are the same as Ring A, Ring B, and Ring C in the formula (M1), and R is¹Represents a (meth) acryloyl group. )

The reaction of the compound represented by the formula (M1) with (meth) acrylic acid may be carried out under any conditions of acidic conditions and basic conditions, and is preferably carried out under basic conditions. The basic condition may be an inert solvent or a basic solvent (e.g., pyridine). Specifically, the reaction can be carried out under basic conditions using an alkylamine such as triethylamine, for example.

The reaction of the compound represented by the formula (M1) with (meth) acrylic acid may be carried out in the presence of a quaternary ammonium halide or other phase transfer catalyst such as benzyltriethylammonium chloride.

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

The ratio (molar ratio) of the compound represented by the formula (M1) to (meth) acrylic acid is not particularly limited, and is preferably 80/20 to 20/80, more preferably 70/30 to 30/70.

The total concentration of the compound represented by the formula (M1) and (meth) acrylic acid in the reaction solution is usually 0.001 mol/L or more and 6 mol/L or less, preferably 0.005 mol/L or more and 4 mol/L or less, and more preferably 0.01 mol/L or more and 3 mol/L or less.

The amount of the quaternary ammonium salt to be used is preferably in the range of 0.001 to 5 mol times, more preferably in the range of 0.005 to 1 mol times, and still more preferably in the range of 0.01 to 0.1 mol times, based on the compound represented by the formula (M1).

A solvent may be used in the above reaction. As the solvent that can be used, various solvents can be used, and for example, 1 or more selected from nitrile solvents such as acetonitrile, hydrocarbon solvents such as benzene, toluene, xylene, glycol solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, and 1, 4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, and cyclohexanone, and alcohol solvents such as ethanol, isopropanol, and butanol can be used.

The method for alkylating, alkanoylating, arylylating or trihydrocarbylsilylating the hydroxyl group of the compound represented by the formula (M2) is not particularly limited

Examples of the alkylation method include a method in which an alkylating agent such as a haloalkane, dialkyl sulfate, or dialkyl carbonate is reacted with a compound represented by formula (M2) in the presence of a base. Examples of the alkylating agent include methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl bromide, propyl 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, and lithium methoxide.

The solvent used in the alkylation process is not particularly limited as long as it is a solvent that does not react with the compound represented by formula (M2) and the alkylating agent, and can be appropriately selected from solvents that are commonly used in alkylation reactions of hydroxyl groups using the alkylating agent. The reaction temperature and the reaction time may be appropriately selected from the ranges generally used in the alkylation reaction using the alkylating agent.

As the method of alkanoylation, a method of reacting a fatty acid halide or a fatty acid anhydride corresponding to an alkanoyl group with a compound represented by the formula (M2) can be mentioned. Examples of the fatty acid halide include acetyl chloride, acetyl bromide, propionyl chloride, propionyl bromide, and the like. Examples of the fatty acid anhydride include acetic anhydride, propionic anhydride, and butyric anhydride.

In the case of using a fatty acid halide, for the purpose of capturing hydrogen halide by-produced by the reaction of a hydroxyl group with the fatty acid halide, it is preferable to carry out the alkanoylation in the presence of a base such as pyridine, triethylamine, sodium hydroxide, or potassium hydroxide.

When a fatty acid anhydride is used, it is preferable to perform the alkanoylation in the presence of a catalyst such as N, N-dimethyl-4-aminopyridine.

The solvent used in the alkylacylation method is not particularly limited as long as it is a solvent that does not react with the compound represented by formula (M2), the fatty acid halide, or the fatty acid anhydride, and can be appropriately selected from solvents that are commonly used in alkylacylation reactions using a hydroxyl group of a fatty acid halide or a fatty acid anhydride. The reaction temperature and the reaction time can be appropriately selected from the ranges generally used in the alkylacylation reaction using a fatty acid halide or a fatty acid anhydride.

As the method of arylation, a method of reacting an aromatic carboxylic acid halide corresponding to an aroyl group with a compound represented by the formula (M2) can be mentioned. Examples of the aromatic carboxylic acid halide include benzoyl chloride, benzoyl bromide, α -naphthoyl chloride, α -naphthoyl bromide, β -naphthoyl chloride, and β -naphthoyl bromide. The reaction of the aromatic carboxylic acid halide with the compound represented by the formula (M2) may be carried out 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 is a solvent that does not react with the compound represented by formula (M2) or the aromatic carboxylic acid halide, and can be appropriately selected from solvents that are generally used in the arylation reaction using the hydroxyl group of the aromatic carboxylic acid halide. The reaction temperature and the reaction time can be appropriately selected from the ranges generally used in the arylation reaction using an aromatic carboxylic acid.

As the trihydrocarbylsilylating method, there may be mentioned a method in which a compound represented by the formula (M2) is reacted with a silylating agent corresponding to the type of trihydrocarbylsilyl group. Examples of the silylating agent include trihydrocarbylmonohalosilanes such as trihydrocarbylmonochlorosilane and trihydrocarbylmonobromosilane, and trihydrocarbylmonoalkoxysilanes such as trihydrocarbylmonomethoxysilane and trihydrocarbylmonoethoxysilane.

Preferred examples of the trihydrocarbylmonohalosilane include trialkylmonochlorosilanes such as trimethylmonochlorosilane, triethylmonochlorosilane, tri-n-propylmonochlorosilane, triisopropylmonochlorosilane, tri-n-butylmonochlorosilane, triisobutylmonochlorosilane, tri-sec-butylmonochlorosilane, tri-tert-butylmonochlorosilane, ethyldimethylmonochlorosilane, n-propyldimethylmonochlorosilane, isopropyldimethylmonochlorosilane, n-butyldimethylmonochlorosilane, isobutyldimethylmonochlorosilane, sec-butyldimethylmonochlorosilane, and tert-butyldimethylmonochlorosilane;

trialkylmonobromosilanes such as trimethylmonobromosilane, triethylmonobromosilane, tri-n-propylmonobromosilane, triisopropylmonobromosilane, tri-n-butylmonobromosilane, triisobutylmonobromosilane, tri-sec-butylmonobromosilane, tri-tert-butylmonobromosilane, ethyldimethylmonobromosilane, n-propyldimethylmonobromosilane, isopropyldimethylmonobromosilane, n-butyldimethylmonobromosilane, isobutyldimethylmonobromosilane, sec-butyldimethylmonobromosilane, and tert-butyldimethylmonobromosilane;

trialkyl monomethoxysilanes such as trimethyl monomethoxysilane, triethyl monomethoxysilane, tri-n-propyl monomethoxysilane, triisopropyl monomethoxysilane, tri-n-butyl monomethoxysilane, triisobutyl monomethoxysilane, tri-sec-butyl monomethoxysilane, tri-tert-butyl monomethoxysilane, ethyl dimethyl monomethoxysilane, n-propyl dimethyl monomethoxysilane, isopropyl dimethyl monomethoxysilane, n-butyl dimethyl monomethoxysilane, isobutyl dimethyl monomethoxysilane, sec-butyl dimethyl monomethoxysilane, and tert-butyl dimethyl monomethoxysilane;

trialkylmonoethoxysilanes such as trimethylmonoethoxysilane, triethylmonoethoxysilane, tri-n-propylmonoethoxysilane, triisopropylmonoethoxysilane, tri-n-butylmonoethoxysilane, triisobutylmonoethoxysilane, tri-sec-butylmonoethoxysilane, tri-tert-butylmonoethoxysilane, ethyldimethylmonoethoxysilane, n-propyldimethylmonoethoxysilane, isopropyldimethylmonoethoxysilane, n-butyldimethylmonoethoxysilane, isobutyldimethylmonoethoxysilane, sec-butyldimethylmonoethoxysilane, and tert-butyldimethylmonoethoxysilane.

The amount of the silylating agent used in the reaction between the compound represented by the formula (M2) and the silylating agent is preferably not less than equimolar, more preferably not less than 1.2 times molar, still more preferably not less than 1.5 times molar, and particularly preferably not less than 2.0 times molar with respect to the number of moles of the compound represented by the formula (M2). The upper limit of the amount of the silylating agent to be used is not particularly limited, but is preferably 5.0 times by mole or less, more preferably 3.0 times by mole or less, based on the number of moles of the compound represented by the formula (M2), from the viewpoint of cost.

The reaction of the compound represented by the formula (M2) with the silylating agent is usually carried out in an organic solvent. As the organic solvent, an organic solvent having no functional group reactive with the silylating agent, such as a hydroxyl group, a carboxyl group, or an amino group, can be used.

Specific examples of the organic solvent include halogenated alkanes such as carbon tetrachloride, chloroform, methylene chloride, bromopropane, bromobutane, bromopentane, bromohexane, iodomethane, iodoethane, and iodopropane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, petroleum ether, gasoline (benzine), kerosene, toluene, xylene, mesitylene, and benzene are exemplified.

The temperature at which the compound represented by formula (M2) and the silylation agent are reacted is not particularly limited as long as the silylation reaction proceeds well. The reaction temperature is, for example, preferably from-20 ℃ to 100 ℃, more preferably from-10 ℃ to 80 ℃, and still more preferably from 0 ℃ to 50 ℃.

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

When the silylating agent is trihydrocarbylmonohalosilane, hydrogen halide is by-produced during the silylation reaction. In order to trap the hydrogen halide by-produced, a base such as triethylamine, pyridine, or N, N-dimethyl-4-aminopyridine may be added to the reaction solution.

The compound represented by the formula (1) produced in the above manner is preferably recovered from the reaction solution by a conventional method, and if necessary purified, used as a component of a resin composition or used as a raw material of the (meth) acrylic resin (a1) described below.

(other monomers)

As described above, the (meth) acrylic resin (a1) may be a copolymer of a (meth) acrylate having an alicyclic epoxy group and a monomer other than the (meth) acrylate having an alicyclic epoxy group.

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 or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, from the viewpoint of curability of the resin composition. 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 may be 95% by mass or less, 90% by mass or less, or 80% by mass or less.

Examples of the other monomer include unsaturated carboxylic acids, (meth) acrylic esters having no epoxy group, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and maleimides. These compounds may be used alone or in combination of 2 or more. From the viewpoint of storage stability of the resin composition and chemical resistance of a cured product formed using the resin composition to alkali or the like, the (meth) acrylic resin (a1) preferably does not contain units derived from an unsaturated carboxylic acid.

On the other hand, when the resin composition is a negative photosensitive composition which can be developed with an alkaline developer, the (meth) acrylic resin (a1) preferably contains a structural unit having an alkali-soluble group. The alkali-soluble group is not particularly limited, and examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.

The alkali-soluble group is preferably a carboxyl group from the viewpoint of the stability of the resin composition over time. That is, the (meth) acrylic resin (a1) preferably contains units derived from an unsaturated carboxylic acid.

Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (meth) acrylamide; butenoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids. Of these, (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% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and still more preferably 10% by mass or more and 30% by mass or less.

Examples of the (meth) acrylate having no epoxy group include linear or branched alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, and tert-octyl (meth) acrylate; chloroethyl (meth) acrylate, 2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate; (meth) acrylate having a group having an alicyclic skeleton. Among the (meth) acrylates having no epoxy group, a (meth) acrylate having a group having an alicyclic skeleton is preferable.

In the (meth) acrylate having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups.

Examples of the (meth) acrylate having a group having an alicyclic skeleton include compounds represented by the following formulae (a1-1) to (a 1-8). Among these, compounds represented by the following formulae (a1-3) to (a1-8) are preferable, and compounds represented by the following formulae (a1-3) or (a1-4) are more preferable.

[ chemical formula 12]

[ chemical formula 13]

In the above formula, R^A1Represents a hydrogen atom or a methyl group, R^A2Represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R^A3Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R^A2The alkylene group is preferably a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. As R^A3Methyl and ethyl are preferred.

When the (meth) acrylic resin (a1) contains a structural unit derived from a (meth) acrylate having a group having an alicyclic skeleton, the content of the structural unit derived from a (meth) acrylate having a group having an alicyclic skeleton in the (meth) acrylic resin (a1) 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 or less.

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

Examples of the allyl compounds include allyl esters such as allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and so on.

Examples of the vinyl ethers include aliphatic vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, and the like; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2, 4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether; and so on.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of the styrenes include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and so on.

In view of the low relative dielectric constant of the cured product of the resin composition, the amount of the structural unit derived from styrene in the (meth) acrylic resin (a1) is preferably smaller, and the (meth) acrylic resin (a1) is more preferably free of the structural unit derived from styrene.

Examples of the maleimide include maleimides N-substituted with an alkyl group having 1 to 10 carbon atoms such as N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide, N-isopropylmaleimide, N-N-butylmaleimide, N-N-pentylmaleimide, and N-N-hexylmaleimide; maleimides N-substituted with an alicyclic group having 3 to 20 carbon atoms such as N-cyclopentylmaleimide, N-cyclohexylmaleimide and N-cycloheptylmaleimide: n-arylmaleimides N-substituted with an aryl group having 6 to 20 carbon atoms such as N-phenylmaleimide, N- α -naphthylmaleimide and N- β -naphthylmaleimide; n-aralkyl maleimides obtained by N-substitution with an aralkyl group having 7 to 20 carbon atoms, such as N-benzylmaleimide and N-phenethylmaleimide.

The weight average molecular weight of the (meth) acrylic resin (a1) is not particularly limited as long as it does not interfere with the object of the present invention, and is preferably 3,000 to 30,000, more preferably 5,000 to 15,000 in terms of weight average molecular weight in terms of polystyrene.

[ epoxy group-containing Cyclic siloxane Compound (A-II) ]

As the epoxy group-containing cyclic siloxane compound (A-II), compounds represented by the following formula (a-I) can be used.

[ chemical formula 14]

In the formula (a-I), R^a01And R^a02Represents a monovalent group containing an epoxy group or an alkyl group. Wherein, x1 Rs in the compound represented by the formula (a-I)^a01And x 1R^a02At least 2 of them are epoxy group-containing monovalent groups. In the formula (a-I), x1 represents an integer of 3 or more. R in the compound represented by the formula (b1-III)^a01、R^a02May be the same or different. In addition, a plurality of R^a01May be the same or different. Plural R^a02May be the same or different.

Examples of the alkyl group include linear or branched alkyl groups having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. The number of carbon atoms of the alkyl group is preferably 1 to 6, and particularly preferably 1 to 3.

X1 in the formula (a-I) represents an integer of 3 or more, and among them, an integer of 3 or more and 6 or less is preferable from the viewpoint of excellent reactivity with the (meth) acrylic resin (a-I) and obtaining a silicone-modified (meth) acrylic resin (a1) having excellent curability.

The number of epoxy groups in the molecule of the compound represented by the formula (a-I) is 2 or more, and from the viewpoint of excellent reactivity with the (meth) acrylic resin (a-I) and the ability to obtain a siloxane-modified (meth) acrylic resin (a1) having excellent curability, the number is preferably 2 or more and 6 or less, and particularly preferably 2 or more and 5 or less.

The epoxy-containing monovalent group is preferably an alicyclic epoxy group or-D^A-O-R^a03The glycidyl ether group represented by the formula (a) is more preferably an alicyclic epoxy group, and still more preferably an alicyclic epoxy group represented by the following formula (a-Ia) or the following formula (a-Ib). D^ARepresents an alkylene group, R^a03Represents a glycidyl group.

AboutAs the above D^AExamples of the alkylene group of (b) include a linear or branched alkylene group having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, and a trimethylene group.

[ chemical formula 15]

(in the formulae (a-Ia) and (a-Ib), D¹And D²Each independently represents an alkylene group, and ms represents an integer of 0 to 2. )

More specifically, the compound represented by the formula (a-I) includes a cyclic siloxane represented by the following formula and having 2 or more glycidyl groups in the molecule. Further, as the compound represented by the formula (a-I), commercially available products such as "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738" and "X-40-2740" (manufactured by shin-Etsu chemical industries, Ltd.) can be used.

[ chemical formula 16]

[ chemical formula 17]

< method for producing Silicone-modified (meth) acrylic resin (A1)

The siloxane-modified (meth) acrylic resin (a1) is a reaction product of a (meth) acrylic resin (a-I) containing a structural unit derived from a (meth) acrylate having an alicyclic epoxy group and the aforementioned epoxy-containing cyclic siloxane compound (a-II).

The amount of the epoxy group-containing cyclic siloxane compound (a-II) which reacts with the (meth) acrylic resin (a-I) in producing the siloxane-modified (meth) acrylic resin (a1) is not particularly limited.

The amount of the epoxy group-containing cyclic siloxane compound (a-II) that reacts with the (meth) acrylic resin (a-I) is, for example, 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, per 100 parts by mass of the (meth) acrylic resin (a-I).

Typically, the reaction is carried out in the presence of an organic solvent. The organic solvent may be appropriately selected from, for example, organic solvents described later as components of the resin composition. The amount of the organic solvent used is, for example, preferably 50 to 5000 parts by mass, more preferably 100 to 3000 parts by mass, and still more preferably 150 to 2000 parts by mass, based on 100 parts by mass of the total of the mass of the (meth) acrylic resin (a-I) and the mass of the epoxy group-containing cyclic siloxane compound (a-II).

The reaction temperature and the reaction time are not particularly limited as long as the reaction can be carried out to a desired extent. From the viewpoint of allowing the desired reaction to proceed satisfactorily, the reaction temperature is preferably 0 ℃ to 150 ℃, more preferably 10 ℃ to 120 ℃, and still more preferably 20 ℃ to 100 ℃. The reaction time is preferably 5 minutes to 12 hours, and more preferably 10 minutes to 6 hours.

In order to promote the reaction, the reaction of the (meth) acrylic resin (a-I) with the epoxy group-containing cyclic siloxane compound (a-II) may be carried out in the presence of a catalyst. Preferred examples of the catalyst include imidazole compounds, secondary amine compounds, tertiary amine compounds, organophosphine compounds, and tetraphenyl boron salts, and imidazole compounds and tertiary amine compounds are more preferred.

Specific examples of the imidazole compound include 1-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and benzimidazole.

Specific examples of the tertiary amine compound include 1, 8-diaza-bicyclo [5.4.0] -7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylethanolamine, and tris (dimethylaminomethyl) phenol.

Specific examples of the secondary amine compound include diethylamine, dipropylamine, dibutylamine and the like.

Specific examples of the organic phosphine compound include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, and the like.

Specific examples of the tetraphenyl-boron salt include tetraphenylphosphonium tetraphenylboronate, 2-ethyl-4-methylimidazolium tetraphenylboronate, and N-methylmorpholinium tetraphenylboronate.

The amount of the catalyst used is not particularly limited, but is 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total of the mass of the (meth) acrylic resin (a-I) and the mass of the epoxy group-containing cyclic siloxane compound (a-II).

For example, when the (meth) acrylic resin (a-I) has a carboxyl group and an epoxycyclohexyl group, and the epoxy group-containing cyclic siloxane compound (a-II) has an epoxycyclohexyl group, the following reaction can be caused as the reaction between the (meth) acrylic resin (a-I) and the epoxy group-containing cyclic siloxane compound (a-II). The reaction involving water in the following reaction can be caused by a trace amount of water introduced into the reaction system by the addition of a trace amount of water, an organic solvent, or the like in the reaction apparatus.

[ chemical formula 18]

The siloxane-modified (meth) acrylic resin (a1) prepared according to the above method may be used as it is in the form of a reaction liquid for the preparation of a resin composition, or may be separated from the reaction liquid according to a conventional method and used in the state for the preparation of a resin composition.

[ preferred embodiment of the resin composition ]

Hereinafter, the 1 st resin composition and the 2 nd resin composition will be described with respect to preferred embodiments of the resin composition. The resin composition containing the silicone-modified (meth) acrylic resin (a1) is not limited to the 1 st resin composition and the 2 nd resin composition described below.

(the 1 st resin composition)

The 1 st resin composition is a resin composition containing a silicone-modified (meth) acrylic resin (a1) and a curing agent.

The 1 st resin composition contains a silicone-modified (meth) acrylic resin (a1) as an epoxy compound. The 1 st resin composition contains a curing agent for curing the siloxane-modified (meth) acrylic resin (a1) as an epoxy compound. The curing agent may be a photosensitive curing agent, a thermosensitive curing agent, or a combination thereof.

The 1 st resin composition may contain an epoxy compound and/or an oxetane compound which are not the siloxane-modified (meth) acrylic resin (a 1).

The kind of the epoxy compound and/or oxetane compound that can be used together with the siloxane-modified (meth) acrylic resin (a1) is not particularly limited as long as the object of the present invention is not impaired.

The proportion of the mass of the siloxane-modified (meth) acrylic resin (a1) to the total mass of the epoxy compound and the oxetane compound in the 1 st resin composition is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, further preferably 90 mass% or more, and particularly preferably 100 mass%, from the viewpoint of low relative dielectric constant of the cured product.

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

Onium salt (D1)

The onium salt (D1) may be used together with an epoxy compound, an oxetane compound or the like, and curing of the epoxy compound, the oxetane compound or the like is promoted by the action of light or heat.

Examples of the onium salt include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, and oxonium salts. Among these, sulfonium salts and iodonium salts are preferable from the viewpoint of obtaining ease and good curing.

Preferred examples of the onium salt (D1) are described below.

A preferable example of the onium salt (D1) is a sulfonium salt represented by the following formula (D-I) (hereinafter, also referred to as "sulfonium salt (Q)").

[ chemical formula 19]

(in the formula (D-I), R^D1And R^D2Independently represents an alkyl group which may be substituted with a halogen atom or a group represented by the following formula (D-II)^D1And R^D2May be bonded to each other to form a ring together with the sulfur atom in the formula R^D3Represents a group represented by the following formula (D-III) or a group represented by the following formula (D-IV), A^D1Denotes S, O, or Se, X^-Represents a monovalent anion, wherein R^D1And R^D2Not both being alkyl groups which may be substituted by halogen atoms. )

[ chemical formula 20]

(in the formula (D-II), ring Z^D1Represents an aromatic hydrocarbon ring, R^D4Represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, a thienyl group, a thienylcarbonyl group, a furyl carbonyl group, a selenophenyl group, a selenophenylcarbonyl group, a heterocyclic aliphatic hydrocarbon group, an alkylsulfinyl group, an alkylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group, a cyano group, a nitro group, or a halogen atom which may be substituted by a halogen atom, m1 represents an integer of 0 or more。)

[ chemical formula 21]

(in the formula (D-III), R^D5Represents an alkylene group which may be substituted by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, or a group represented by the following formula (D-V), R^D6Represents an alkyl group which may be substituted by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, or a group represented by the following formula (D-VI)^D2Represents a single bond, S, O, sulfinyl, or carbonyl group, and n1 represents 0 or 1. )

[ chemical formula 22]

(in the formula (D-IV), R^D7And R^D8Independently represents an alkylene group which may be substituted with a hydroxyl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxyl (poly) alkyleneoxy group, amino group which may be substituted, cyano group, nitro group, or halogen atom, or a group represented by the following formula (D-V), R^D9And R^D10Independently of each otherRepresents an alkyl group which may be substituted with a halogen atom or a group represented by the above formula (D-II), R^D9And R^D10May be bonded to each other to form a ring together with the sulfur atom in the formula A^D3Represents a single bond, S, O, sulfinyl, or carbonyl, X^-As previously mentioned, n2 represents 0 or 1, wherein R^D9And R^D10Not both being alkyl groups which may be substituted by halogen atoms. )

[ chemical formula 23]

(in the formula (D-V), ring Z^D2Represents an aromatic hydrocarbon ring, R^D11Represents an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, and m2 represents an integer of 0 or more. )

[ chemical formula 24]

(in the formula (D-VI), ring Z^D3Represents an aromatic hydrocarbon ring, R^D12Represents an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, and m3 represents an integer of 0. )

(sulfonium salt (Q))

The sulfonium salt (Q) is explained below. The sulfonium salt (Q) is characterized in that the benzene ring in the formula (D-I) is opposite to A^D1The bonded carbon atom is a carbon atom in the ortho position to which a methyl group is bonded. The sulfonium salt (Q) has a methyl group at the above-mentioned position, and therefore has higher sensitivity to active energy rays such as ultraviolet rays than conventional sulfonium salts.

In the above formula (D-I), R is preferred^D1And R^D2All are groups represented by the above formula (D-II). R^D1And R^D2May be the same or different from each other.

In the above formula (D-I), R^D1And R^D2When they 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 including the sulfur atom is preferably 3 to 10 inclusive, and more preferably 5 to 7 inclusive. The ring to be formed may be a polycyclic ring, and a polycyclic ring in which monocyclic rings having 5 to 7 ring atoms are condensed is preferable.

In the above formula (D-I), R is preferred^D1And R^D2Are all phenyl groups.

In the above formula (D-I), R is preferred^D3Is a group represented by the above formula (D-III).

In the above formula (D-I), A^D1Preferably S or O, more preferably S.

In the above formula (D-II), R^D4Preferably an alkyl group, a hydroxyl group, an alkylcarbonyl group, a thienylcarbonyl group, a furylcarbonyl group, a selenophenylcarbonyl group, a substitutable amino group, or a nitro group, which may be substituted with a halogen atom, and 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 may be according to ring Z^D1The number of (b) is selected, and may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

In the above formula (D-III), R^D5Preferably an alkylene group; alkylene substituted with a hydroxyl group, an amino group which may be substituted, or a nitro group; or a group represented by the above formula (D-V), more preferably a group represented by the above formula (D-V).

The above formula (D)in-III), R^D6Preferably an alkyl group; alkyl substituted with hydroxy, amino which may be substituted, or nitro; or a group represented by the above formula (D-VI), more preferably a group represented by the above formula (D-VI).

In the above formula (D-III), A^D2Preferably S or O, more preferably S.

In the above formula (D-III), n1 is preferably 0.

In the above formula (D-IV), R^D7And R^D8Independently preferably an alkylene group; alkylene substituted with a hydroxyl group, an amino group which may be substituted, or a nitro group; or a group represented by the above formula (D-V), more preferably a group represented by the above formula (D-V). R^D7And R^D8May be the same or different from each other.

In the above formula (D-IV), R is preferred^D9And R^D10All are groups represented by the above formula (D-II). R^D9And R^D10May be the same or different from each other.

In the above formula (D-IV), R^D9And R^D10When the sulfur atoms 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 including the sulfur atom is preferably 3 to 10, more preferably 5 to 7. The ring to be formed may be a polycyclic ring, and a polycyclic ring in which monocyclic rings having 5 to 7 ring atoms are condensed is preferable.

In the above formula (D-IV), A^D3Preferably S or O, more preferably S.

In the above formula (D-IV), n2 is preferably 0.

In the above formula (D-V), R^D11Preferred is an alkyl group which may be substituted with a halogen atom, a hydroxyl group, an amino group which may be substituted, or a nitro group, and more preferred is an alkyl group which may be substituted with a halogen atom.

In the above formula (D-V), m2 may be according to ring Z^D2The selection of (b) may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

In the above formula (D-VI), R^D12Preferably alkyl, hydroxy, alkylcarbonyl, thienylcarbonyl, furylcarbonyl, selenophene, which may be substituted by halogen atomsAlkylcarbonyl, amino which may be substituted, or nitro, more preferably alkyl, alkylcarbonyl, or thienylcarbonyl which may be substituted with a halogen atom.

In the above formula (D-VI), m3 may be according to ring Z^D3The selection of (b) may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

In the above formula (D-I), X^-Is a monovalent anion. As X^-Preferable examples thereof include monovalent polyatomic anions, and more preferable examples thereof are MY_a ^-、(Rf)_bPF_6-b ^-、R^x1 _cBY_4-c ^-、R^x1 _cGaY_4-c ^-、R^x2SO₃ ^-、(R^x2SO₂)₃C^-Or (R)^x2SO₂)₂N^-The anion shown. In addition, X^-Examples of the halogen anion 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 having 80 mol% or more of hydrogen atoms substituted with fluorine atoms (preferably an alkyl group having 1 to 8 carbon atoms). Examples of the alkyl group which is substituted with fluorine to form Rf include a straight-chain alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, and octyl), a branched-chain alkyl group (e.g., isopropyl, isobutyl, sec-butyl, and tert-butyl), and a cycloalkyl group (e.g., cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl). In Rf, the ratio of substitution of hydrogen atoms of these alkyl groups by fluorine atoms is preferably 80 mol% or more, more preferably 90% or more, and particularly preferably 100% based on the number of moles of hydrogen atoms of the original alkyl group. When the ratio of substitution with fluorine atoms is within these preferable ranges, the photosensitivity of the sulfonium salt (Q) becomes further favorable. Particularly preferred Rf includes CF₃ ^-、CF₃CF₂ ^-、(CF₃)₂CF^-、CF₃CF₂CF₂ ^-、CF₃CF₂CF₂CF₂ ^-、(CF₃)₂CFCF₂ ^-、CF₃CF₂(CF₃)CF^-And (CF)₃)₃C^-. b Rf's 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^x1Represents a phenyl group in which a part of hydrogen atoms is substituted with at least 1 element or an electron-withdrawing group. Examples of such 1 element include a halogen atom, and include a fluorine atom, a chlorine atom, a bromine atom and the like. Examples of the electron-withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Of these, a phenyl group in which at least 1 hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. c number of R^x1Are 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^x2The alkyl group and the fluoroalkyl group may be linear, branched or cyclic, and the alkyl group, the fluoroalkyl group or the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxyl group, an amino group which may be substituted, and a nitro group. Examples of the amino group which may be substituted include those exemplified in the following description relating to the above formulae (D-II) to (D-VI).

In addition, R^x2The carbon chain in the alkyl group, fluoroalkyl group, or aryl group may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. In particular, R^x2The carbon chain in the alkyl group or fluoroalkyl group represented may have a divalent functional group (for example, an ether bond, a carbonyl bond, an ester bond, an amino bond, an amide bond, an imide bond, a sulfonyl amide bond, a sulfonyl imide bond, a urethane bond, or the like).

R^x2When the alkyl group, fluoroalkyl group or aryl group represented by the above-mentioned formula has the substituent, hetero atom or functional group, the above-mentioned groupThe number of the substituents, hetero atoms, or functional groups may be 1, or 2 or more.

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 to 6.

b is preferably an integer of 1 to 5, more preferably an integer of 2 to 4, and particularly preferably 2 or 3.

c is preferably an integer of 1 to 4, more preferably 4.

As MY_a ^-Examples of the anion include SbF₆ ^-、PF₆ ^-Or BF₄ ^-The anions shown, and the like.

As (Rf)_bPF_6-b ^-Examples of the anion include (CF)₃CF₂)₂PF₄ ^-、(CF₃CF₂)₃PF₃ ^-、((CF₃)₂CF)₂PF₄ ^-、((CF₃)₂CF)₃PF₃ ^-、(CF₃CF₂CF₂)₂PF₄ ^-、(CF₃CF₂CF₂)₃PF₃ ^-、((CF₃)₂CFCF₂)₂PF₄ ^-、((CF₃)₂CFCF₂)₃PF₃ ^-、(CF₃CF₂CF₂CF₂)₂PF₄ ^-Or (CF)₃CF₂CF₂CF₂)₃PF₃ ^-The anions shown, and the like. Of these, (CF) is preferred₃CF₂)₃PF₃ ^-、(CF₃CF₂CF₂)₃PF₃ ^-、((CF₃)₂CF)₃PF₃ ^-、((CF₃)₂CF)₂PF₄ ^-、((CF₃)₂CFCF₂)₃PF₃ ^-Or ((CF)₃)₂CFCF₂)₂PF₄ ^-The anion shown.

As R^x1 _cBY_4-c ^-The anion is preferably

R^x1 _cBY_4-c ^-

(in the formula, R^x1Represents a phenyl group in which at least a part of the hydrogen atoms is substituted with a halogen atom or an electron-withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4. ),

for example, there may be mentioned (C)₆F₅)₄B^-、((CF₃)₂C₆H₃)₄B^-、(CF₃C₆H₄)₄B^-、(C₆F₅)₂BF₂ ^-、C₆F₅BF₃ ^-Or (C)₆H₃F₂)₄B^-The anions shown, and the like. Of these, (C) is preferred₆F₅)₄B^-Or ((CF)₃)₂C₆H₃)₄B^-The anion shown.

As R^x1 _cGaY_4-c ^-Examples of the anion represented are (C)₆F₅)₄Ga^-、((CF₃)₂C₆H₃)₄Ga^-、(CF₃C₆H₄)₄Ga^-、(C₆F₅)₂GaF₂ ^-、C₆F₅GaF₃ ^-Or (C)₆H₃F₂)₄Ga^-The anions shown, and the like. Of these, (C) is preferred₆F₅)₄Ga^-Or ((CF)₃)₂C₆H₃)₄Ga^-The anion shown.

As R^x2SO₃ ^-Examples of the anion includeFluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutanesulfonic acid anion, pentafluorophenylsulfonic acid anion, p-toluenesulfonic acid anion, benzenesulfonic acid anion, camphorsulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, propanesulfonic acid anion, butanesulfonic acid anion, and the like. Of these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion or p-toluenesulfonate anion are preferable.

As (R)^x2SO₂)₃C^-Examples of the anion include (CF)₃SO₂)₃C^-、(C₂F₅SO₂)₃C^-、(C₃F₇SO₂)₃C^-Or (C)₄F₉SO₂)₃C^-The anions shown, and the like.

As (R)^x2SO₂)₂N^-Examples of the anion include (CF)₃SO₂)₂N^-、(C₂F₅SO₂)₂N^-、(C₃F₇SO₂)₂N^-Or (C)₄F₉SO₂)₂N^-The anions shown, and the like.

As monovalent polyatomic anions, other than MY_a ^-、(Rf)_bPF_6-b ^-、R^x1 _cBY_4-c ^-、R^x1 _cGaY_4-c ^-、R^x2SO₃ ^-、(R^x2SO₂)₃C^-Or (R)^x2SO₂)₂N^-In addition to the anions shown, perhalogenated ions (ClO) may be used₄ ^-、BrO₄ ^-Etc.), halogenated sulfonate ion (FSO)₃ ^-、ClSO₃ ^-Etc.), sulfate ion (CH)₃SO₄ ^-、CF₃SO₄ ^-、HSO₄ ^-Etc.), carbonate ion (HCO)₃ ^-、CH₃CO₃ ^-Etc.), aluminate ions (AlCl)₄ ^-、AlF₄ ^-Etc.), hexafluorobismuthate ion (BiF)₆ ^-) Carboxylate ion (CH)₃COO^-、CF₃COO^-、C₆H₅COO^-、CH₃C₆H₄COO^-、C₆F₅COO^-、CF₃C₆H₄COO^-Etc.), arylborate ion (B (C)₆H₅)₄ ^-、CH₃CH₂CH₂CH₂B(C₆H₅)₃ ^-Etc.), thiocyanate ions (SCN)^-) And nitrate ion (NO)₃ ^-) And the like.

These X' s^-Of these, MY is preferred from the viewpoint of cationic polymerization performance_a ^-、(Rf)_bPF_6-b ^-、R^x1 _cBY_4-c ^-、R^x1 _cGaY_4-c ^-And (R)^x2SO₂)₃C^-The anion represented by (A), more preferably SbF₆ ^-、PF₆ ^-、(CF₃CF₂)₃PF₃ ^-、(C₆F₅)₄B^-、((CF₃)₂C₆H₃)₄B^-、(C₆F₅)₄Ga^-、((CF₃)₂C₆H₃)₄Ga^-And (CF)₃SO₂)₃C^-Further, R is preferable^x1 _cBY_4-c ^-。

In the above formulae (D-II), (D-V) and (D-VI), examples of the aromatic hydrocarbon ring include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring and the like. The fused polycyclic aromatic hydrocarbon ring is preferably a fused 2-4 cyclic aromatic hydrocarbon ring such as a fused bicyclic aromatic hydrocarbon ring or a fused tricyclic aromatic hydrocarbon ring. As the fused bicyclic hydrocarbon ring, for example, C such as naphthalene ring is preferable_8-20Fused bicyclic hydrocarbon ring, more preferably C_10-16A fused bicyclic hydrocarbon ring. As the fused tricyclic aromatic hydrocarbon ring, for example, an anthracycline, a phenanthrylene ring, and the like are preferable. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

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

In the formulae (D-I) to (D-VI), examples of the alkyl group include a straight-chain alkyl group having 1 to 18 carbon atoms, a branched-chain alkyl group having 3 to 18 carbon atoms, and a cycloalkyl group having 3 to 18 carbon atoms. In particular, in the above formulae (D-I), (D-II), and (D-IV) to (D-VI), the alkyl group which may be substituted with a halogen atom means an alkyl group and an alkyl group substituted with a halogen atom. Examples of the alkyl group substituted with a halogen atom include the above-mentioned straight-chain alkyl group, branched-chain alkyl group, and cycloalkyl group in which at least 1 hydrogen atom is substituted with a halogen atom. Preferable specific examples of the linear alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl. Preferable specific examples of the branched alkyl group include isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and isooctadecyl groups. Preferable specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and 4-decylcyclohexyl. Preferable specific examples of the alkyl group substituted with a halogen atom include a monofluoromethyl group, a difluoromethyl group, and a trifluoromethyl group. In the alkyl group which may be substituted by halogen atoms, with respect to R^D1、R^D2、R^D9Or R^D10Trifluoromethyl is particularly preferred, with respect to R^D4、R^D6、R^D11Or R^D12Particularly preferred is a methyl group.

In the formulae (D-II) to (D-VI), examples of the alkoxy group include a linear or branched alkoxy group having 1 to 18 carbon atoms. Preferable specific examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy.

In the formulae (D-II) to (D-VI), examples of the alkyl group in the alkylcarbonyl group include the above-mentioned straight-chain alkyl group having 1 to 18 carbon atoms, branched-chain alkyl group having 3 to 18 carbon atoms, or cycloalkyl group having 3 to 18 carbon atoms. Examples of the alkylcarbonyl group include a linear, branched or cyclic alkylcarbonyl group having 2 to 18 carbon atoms. Preferable specific examples of the alkylcarbonyl group include acetyl, propionyl, butyryl, 2-methylpropionyl, heptanoyl, 2-methylbutyryl, 3-methylbutyryl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, cyclopentanoyl, and cyclohexanoyl.

In the formulae (D-III) to (D-VI), the arylcarbonyl group includes arylcarbonyl groups having 7 to 11 carbon atoms. Preferable specific examples of the arylcarbonyl group include benzoyl group and naphthoyl group.

In the formulae (D-II) to (D-VI), the alkoxycarbonyl group includes a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms. Preferred examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an octyloxycarbonyl group, a tetradecyloxycarbonyl group, and an octadecyloxycarbonyl group.

In the formulae (D-III) to (D-VI), examples of the aryloxycarbonyl group include an aryloxycarbonyl group having 7 to 11 carbon atoms. Preferred examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a naphthyloxycarbonyl group.

In the formulae (D-III) to (D-VI), the arylthiocarbonyl group includes an arylthiocarbonyl group having 7 to 11 carbon atoms. Preferred examples of the arylthiocarbonyl group include phenylthiocarbonyl group and naphthyloxy-thiocarbonyl group.

In the formulae (D-II) to (D-VI), examples of the acyloxy group include a linear or branched acyloxy group having 2 to 19 carbon atoms. Preferred specific examples of the acyloxy group include an acetoxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, an octylcarbonyloxy group, a tetradecylcarbonyloxy group, and an octadecylcarbonyloxy group.

In the formulae (D-III) to (D-VI), examples of the arylthio group include arylthio groups having 6 to 20 carbon atoms. Preferable specific examples of the arylthio group include a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, a 2-chlorophenylthio group, a 3-chlorophenylthio group, a 4-chlorophenylthio group, a 2-bromophenylthio group, a 3-bromophenylthio group, a 4-bromophenylthio group, a 2-fluorophenylthio group, a 3-fluorophenylthio group, a 4-fluorophenylthio group, a 2-hydroxyphenylthio group, a 4-methoxyphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 4- [4- (phenylthio) benzoyl ] phenylthio group, a 4- [4- (phenylthio) phenoxy ] phenylthio group, a, 4- [4- (phenylthio) phenyl ] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio, 4- (p-isopropylbenzoyl) phenylthio, and 4- (p-tert-butylbenzoyl) phenylthio, and the like.

In the formulae (D-II) to (D-VI), examples of the alkylthio group include a linear or branched alkylthio group having 1 to 18 carbon atoms. Preferable specific examples of the alkylthio group include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio.

In the formulae (D-III) to (D-VI), examples of the aryl group include aryl groups having 6 to 10 carbon atoms. Preferable specific examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a naphthyl group, and the like.

In the formula (D-II), examples of the heterocyclic aliphatic group include a heterocyclic aliphatic group having 2 to 20 carbon atoms, preferably 4 to 20 carbon atoms. Preferred specific examples of the heterocyclic aliphatic group include a pyrrolidinyl group, a tetrahydrofuryl group, a tetrahydrothienyl group, a piperidyl group, a tetrahydropyranyl group, a tetrahydrothiopyranyl group, and a morpholinyl group.

In the formulae (D-III) to (D-VI), examples of the heterocyclic aromatic group include heterocyclic aromatic groups having 4 to 20 carbon atoms. Preferred examples of the heterocyclic aromatic group include thienyl, furyl, selenophenyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthyl, thianthrenyl, phenoxazinyl, phenoxathiin, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl groups.

Examples of the aryloxy group in the formulae (D-III) to (D-VI) include aryloxy groups having 6 to 10 carbon atoms. Preferred examples of the aryloxy group include phenoxy and naphthoxy.

In the formulae (D-II) to (D-VI), examples of the alkylsulfinyl group include a linear or branched sulfinyl group having 1 to 18 carbon atoms. Preferable examples of the alkylsulfinyl group include methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, and isooctadecylsulfinyl.

In the formulae (D-III) to (D-VI), the arylsulfinyl group includes an arylsulfinyl group having 6 to 10 carbon atoms. Preferable examples of the arylsulfinyl group include phenylsulfinyl group, tolylsulfinyl group, and naphthylsulfinyl group.

In the formulae (D-II) to (D-VI), the alkylsulfonyl group may be a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms. Preferable specific examples of the alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, pentylsulfonyl group, isopentylsulfonyl group, neopentylsulfonyl group, tert-pentylsulfonyl group, octylsulfonyl group, and octadecylsulfonyl group.

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

In the above formulae (D-II) to (D-VI), the hydroxy (poly) alkyleneoxy group includes HO (AO)_qA hydroxy (poly) alkyleneoxy group represented by the formula (I), and the like. In the formula, AO independently represents an ethyleneoxy group and/or an propyleneoxy group, and q represents an integer of 1 to 5.

In the above formulae (D-II) to (D-VI), examples of the amino group which may be substituted include an amino group (-NH)₂) And substituted amino groups having 1 to 15 carbon atoms. Preferred examples of the substituted amino group include a methylamino group, a dimethylamino group, an ethylamino group, a methylethylamino group, a diethylamino group, a n-propylamino group, a methyl-n-propylamino group, an ethyl-n-propylamino group, a n-propylamino group, an isopropylamino group, an isopropylmethylamino group, an isopropylethylamino group, a diisopropylamino group, a phenylamino group, a diphenylamino group, a methylphenylamino group, an ethylphenylamino group, a n-propylphenylamino group, and an isopropylphenylamino group.

In the above formulae (D-III) and (D-IV), examples of the alkylene group include a linear or branched alkylene group having 1 to 18 carbon atoms. Preferable specific examples of the alkylene group include methylene, 1, 2-ethylene, 1-ethylene, propane-1, 3-diyl, propane-1, 2-diyl, 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 and 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, hexadecane-1, 16-diyl, and the like.

Specific examples of the cation portion of the sulfonium salt (Q) represented by the above formula (D-I) include the following cations. Specific examples of the anion portion of the sulfonium salt (Q) represented by the formula (D-I) include those represented by the formula X^-Examples of the anion include conventionally known anions. The sulfonium salt (Q) represented by the above formula (D-I) can be synthesized by the above synthesis route, and if necessary, the cation part can be combined with a desired anion part by salt exchange, particularly preferably with R^x1 _cBY_4-c ^-(in the formula, R^x1Represents a phenyl group in which at least a part of the hydrogen atoms is substituted with a halogen atom or an electron-withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4. ) Combinations of anions as indicated.

[ chemical formula 25]

Among the above preferred cationic moiety groups, the cationic moiety represented by the following formula is more preferred.

[ chemical formula 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 can be satisfactorily performed. In terms of ease of good curing of the resin composition, the content of the onium salt (D1) in the resin composition is typically 0.01 to 50 parts by mass, preferably 0.01 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, further preferably 0.05 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass, per 100 parts by mass of a material cured with the onium salt (D1) such as an epoxy compound and/or an oxetane compound.

Curing agent for epoxy Compound or oxetane Compound (D2)

The curing agent (D2) (hereinafter, also referred to as curing agent (D2)) for the epoxy compound or the oxetane compound can be appropriately selected from conventionally known curing agents other than the onium salt (D1). The curing agent (D2) was used together with an epoxy compound or an oxetane compound to facilitate curing upon heating.

Examples of the curing agent (D2) include a phenol curing agent, an acid anhydride curing agent, a polyamine curing agent, and a catalyst curing agent.

The amount of the phenol-based curing agent and the acid anhydride-based curing agent used is preferably 1 part by mass or more and 200 parts by mass or less, more preferably 50 parts by mass or more and 150 parts by mass or less, and particularly preferably 80 parts by mass or more and 120 parts by mass or less, based on 100 parts by mass of the total amount of the epoxy compound and the oxetane compound in the resin composition. The phenol-based curing agent and the acid anhydride-based curing agent may be used alone or in combination of 2 or more.

The amount of the polyamine-based curing agent to be used is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, and particularly preferably 1 to 15 parts by mass, based on 100 parts by mass of the total amount of the epoxy compound and the oxetane compound in the resin composition. These polyamine-based curing agents may be used alone, or 2 or more of them may be used in combination.

The amount of the catalyst-type curing agent to be used is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 80 parts by mass or less, and particularly preferably 1 part by mass or more and 50 parts by mass or less, based on 100 parts by mass of the total amount of the epoxy compound and the oxetane compound in the resin composition. These catalyst-type curing agents may be used alone, or 2 or more of them may be used in combination.

Curing agent for producing an alkali component by Heat (D3)

As the curing agent (D3) which generates an alkali component by heat, a compound which has been conventionally used as a heat alkali generator can be used without particular limitation.

For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one can be used as an agent that utilizes heat to produce an alkaline component. 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butan-1-one can also generate a base by the action of light.

Further, a compound which generates an imidazole compound represented by the following formula (d1) by heating (hereinafter, also referred to as a thermal imidazole generator) is also preferably used as the curing agent.

[ chemical formula 27]

(in the formula (d1), R^d1、R^d2And R^d3Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, a sulfonate group, a phosphinyl group, a phosphonate group, or an organic group. )

As R^d1、R^d2And R^d3Examples of the organic group in (3) include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than the hydrocarbon group, such as a heteroatom. The organic group may be linear, branched, or cyclic. The organic group is usually monovalent, and may form a divalent or more organic group when a cyclic structure is formed.

With respect to R^d1And R^d2These may be bonded to form a cyclic structure, and may further contain a bond of a hetero atom. Examples of the cyclic structure include a heterocycloalkyl group, a heteroaryl group, and the like, and may be a condensed ring.

R is not particularly limited as long as the effect of the present invention is not impaired^d1、R^d2And R^d3The bond contained in the organic group (b) is not particularly limited, and the organic group may contain a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, a silicon atom or the like. Specific examples of the heteroatom-containing bond include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond and an imino bond (-N ═ C (-R)^d0)-、-C(＝NR^d0)-：R^d0Represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, or the like.

As R^d1、R^d2And R^d3The organic group (b) may have a heteroatom-containing bond, and from the viewpoint of heat resistance of the imidazole compound, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (-N ═ C (-R) are preferable^d0)-、-C(＝NR^d0)-：R^d0Represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond.

R^d1、R^d2And R^d3When the organic group(s) is a substituent other than a hydrocarbon group, R is not particularly limited as long as the effect of the present invention is not impaired^d1、R^d2And R^d3There is no particular limitation. As R^d1、R^d2And R^d3Specific examples of the (B) include halogen atoms, hydroxyl groups, mercapto groups, thioether groups, cyano groups, isocyano groups, cyanate groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, silyl groups, silanol groups, alkoxy groups, alkoxycarbonyl groups, carbamoyl groups, thiocarbamoyl groups, nitro groups, nitroso groups, carboxylate groups, acyl groups, acyloxy groups, sulfino groups, sulfonate groups, phosphine groups, phosphino groups, phosphonate groups, alkyl ether groups, alkenyl ether groups, alkyl thioether groups, alkenyl thioether groups, aryl ether groups, aryl thioether groupsAnd the like. The hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

As R^d1、R^d2And R^d3The alkyl group having 1 to 12 carbon atoms, the aryl group having 6 to 12 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, and the halogen atom are preferable, and the hydrogen atom is more preferable.

The thermal imidazole generator is not particularly limited as long as it is a compound capable of generating an imidazole compound represented by the above formula (d1) by heating. A compound (thermal alkali-generating agent) which is conventionally incorporated in various compositions and generates an amine by the action of heat can be obtained by replacing the skeleton derived from the amine generated upon heating with the skeleton derived from the imidazole compound represented by the above formula (d 1).

Preferred examples of the thermal imidazole-generating agent include compounds represented by the following formula (d 2):

[ chemical formula 28]

(in the formula (d2), R^d1、R^d2And R^d3Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group. R^d4And R^d5Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group. R^d6、R^d7、R^d8、R^d9And R^d10Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate groupA phosphate group, a phosphine group, a phosphinyl group, a phosphonyl group, a phosphonate group, an amino group, an ammonium group, or an organic group. Then R^d6、R^d7、R^d8、R^d9And R^d10In addition, 2 or more of them may be bonded to form a cyclic structure, or may contain a heteroatom bond. ).

In the formula (d2), R^d1、R^d2And R^d3And R described for formula (d1)^d1、R^d2And R^d3The same is true.

In the formula (d2), R^d4And R^d5Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group.

As R^d4And R^d5Examples of the organic group in (1) include those for R^d1、R^d2And R^d3The organic groups exemplified. The organic group and R^d1、R^d2And R^d3In the same manner, a hetero atom may be contained in the organic group. The organic group may be linear, branched, or cyclic.

In the above, as R^d4And R^d5Each of which is independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having a cyano group and having 2 to 11 carbon atoms, an alkyl group having a hydroxyl group and having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR)^d、-OCOR^d：R^dA hydrocarbon group), an aryl group having 6 to 20 carbon atoms substituted with an electron-donating substituent and/or an electron-withdrawing substituent, and an aryl group having 6 to 20 carbon atoms substituted with an electron-donating substituent and/or an electron-withdrawing substituentBenzyl, cyano, methylthio substituted with an electron-withdrawing substituent and/or an electron-withdrawing substituent. More preferably R^d4And R^d5Both are hydrogen atoms, or R^d4Is methyl and R^d5Is a hydrogen atom.

In the formula (d2), R^d6、R^d7、R^d8、R^d9And R^d10Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group, or an organic group.

As R^d6、R^d7、R^d8、R^d9And R^d10Examples of the organic group in (1) include those mentioned in R^d1、R^d2And R^d3The organic group exemplified in (1). The organic group and R^d1And R^d2In the same manner, the organic group may contain a bond or a substituent other than the hydrocarbon group, such as a heteroatom. The organic group may be linear, branched, or cyclic.

Then R^d6、R^d7、R^d8、R^d9And R^d10In addition, 2 or more of them may be bonded to form a cyclic structure, and may contain a bond of a heteroatom. Examples of the cyclic structure include a heterocycloalkyl group, a heteroaryl group, and the like, and may be a condensed ring. For example, with respect to R^d6、R^d7、R^d8、R^d9And R^d10At least 2 of them may be bonded, and have R in common^d6、R^d7、R^d8、R^d9And R^d10Atoms of the bonded benzene rings form condensed rings such as naphthalene, anthracene, phenanthrene, indene, and the like.

In the above, as R^d6、R^d7、R^d8、R^d9And R^d10Each of which is independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, or an aryloxyalkyl group having 7 to 20 carbon atomsAn aralkyl group having a cyano group, an alkyl group having 2 to 11 carbon atoms, an alkyl group having a hydroxyl group and having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms which is substituted with an electron donating substituent and/or an electron withdrawing substituent, a benzyl group which is substituted with an electron donating substituent and/or an electron withdrawing substituent, a cyano group, a methylthio group, and a nitro group.

In addition, as R^d6、R^d7、R^d8、R^d9And R^d10Also, the following is preferable: 2 or more of them are bonded and have R in common^d6、R^d7、R^d8、R^d9And R^d10Atoms of the bonded benzene rings form condensed rings such as naphthalene, anthracene, phenanthrene, indene, and the like.

Among the compounds represented by the above formula (d2), preferred is a compound represented by the following formula (d 3):

[ chemical formula 29]

(in the formula (d3), R^d1、R^d2And R^d3The same as those of the formulae (d1) and (d 2). R^d4～R^d9The same as in the formula (d 2). R^d11Represents a hydrogen atom or an organic group. R^d6And R^d7Not to be a hydroxyl group. Then R^d6、R^d7、R^d8And R^d9In addition, 2 or more of them may be bonded to form a cyclic structure and may contain a bond of a hetero atom. ).

The compound represented by the formula (d3) has a substituent-O-R^d11Therefore, the solubility in an organic solvent is excellent.

In the formula (d3), R^d11Is a hydrogen atom or an organic group. R^d11In the case of an organic group, as the organic group, there may beAre exemplified in R^d1、R^d2And R^d3The organic group exemplified in (1). As for the organic group, a hetero atom may be contained in the organic group. The organic group may be linear, branched, or cyclic. As R^d11The alkyl group or alkoxyalkyl group having 1 to 12 carbon atoms is preferably a hydrogen atom, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxymethyl group, or a butoxymethyl group.

Specific examples of compounds particularly preferable as the thermal imidazole-generating agent are shown below.

[ chemical formula 30]

Organic solvent (S)

Typically, the resin composition may contain an organic solvent (S) for the purpose of adjusting coatability and the like. Examples of the organic solvent (S) include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol 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, and tripropylene glycol monoethyl ether; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol ethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl butyrate, methyl butyrate, n-propyl butyrate, n-butyl butyrate, ethyl butyrate, methyl pyruvate, ethyl butyrate, methyl butyrate, ethyl butyrate, Other esters such as ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone, or 2 or more of them may be used in combination.

The amount of the organic solvent (S) used may be determined as appropriate depending on the use of the resin composition. The amount of the organic solvent (S) used may be, for example, an amount in which the solid content concentration of the resin composition is in the range of 1 mass% to 50 mass%.

Other ingredients

The resin composition may contain various additives other than the above components as required. Specifically, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, thermal polymerization inhibitors, defoaming agents, surfactants, and the like can be exemplified.

The resin composition may contain an epoxy group-containing cyclic siloxane compound (a-II) which does not react with the (meth) acrylic resin (a-I). The resin composition preferably does not contain an epoxy group-containing cyclic siloxane compound, because a cured product having a low relative dielectric constant can be easily formed. When the resin composition contains the epoxy group-containing cyclic siloxane compound (a-II), the content thereof is preferably 40% by mass or less, more preferably 10% by mass or less, and still more preferably 1% by mass or less, with respect to the mass of the resin composition excluding the mass of the organic solvent (S).

(the 2 nd resin composition)

The 2 nd resin composition contains the aforementioned silicone-modified (meth) acrylic resin (a1), a photopolymerizable monomer (B), and a photopolymerization initiator (C). Among them, the siloxane-modified (meth) acrylic resin (a1) contains a (meth) acrylic resin containing a structural unit having an alkali-soluble group as an alkali-soluble resin. The alkali-soluble group is not particularly limited, and examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.

The 2 nd resin composition is cured by exposure to light by containing a photopolymerizable monomer (B) and a photopolymerization initiator (C). On the other hand, the 2 nd resin composition in an unexposed state is soluble in an alkaline developer because it contains the siloxane-modified (meth) acrylic resin (a1) containing a structural unit having an alkali-soluble group. Therefore, in the case of using the 2 nd resin composition, patterning of a cured film by photolithography using a negative photomask becomes possible.

The 2 nd resin composition may be cured by heating because it contains the siloxane-modified (meth) acrylic resin (a1) having an epoxy group. The 2 nd resin composition may contain no curing agent for epoxy compounds. This is because the curing reaction of the epoxy group proceeds by the action of the alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group which the siloxane-modified (meth) acrylic resin has.

Hereinafter, essential components or optional components that the 2 nd resin composition may contain are described.

Siloxane-modified (meth) acrylic resin (A1)

The siloxane-modified (meth) acrylic resin (a1) containing a structural unit having an alkali-soluble group is as described above.

Other resins

As the resin other than the silicone-modified (meth) acrylic resin (a1) in the 2 nd resin composition, various alkali-soluble resins may be contained.

In view of the low relative dielectric constant of the cured product, the mass ratio of the silicone-modified (meth) acrylic resin (a1) to the total mass of the silicone-modified (meth) acrylic resin (a1) and the other resins in the 2 nd resin composition is preferably 50 mass% or more, more preferably 70 mass% or more, still more preferably 80 mass% or more, still more preferably 90 mass% or more, and particularly preferably 100 mass%.

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

A preferred alkali-soluble resin is a resin (a-1) having a Cardo structure (hereinafter also referred to as "Cardo resin (a-1)").

As the resin (a-1) having a Cardo structure, a resin having a Cardo structure in its structure and having a predetermined alkali solubility can be used. The Cardo structure is a structure in which the 2 nd and 3 rd ring structures are bonded to 1 ring carbon atom constituting the 1 st ring structure. The 2 nd ring structure and the 3 rd ring structure may be the same structure or different structures.

As a typical example of the Cardo structure, there is a structure in which 2 aromatic rings (e.g., benzene rings) are bonded to the carbon atom at the 9-position of the fluorene ring.

The Cardo resin (a-1) is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferable.

[ chemical formula 31]

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

[ chemical formula 32]

In the above formula (a-2), R^a1Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R^a2Each independently represents a hydrogen atom or a methyl group, R^a3Each independently represents a linear or branched alkylene group, t2 represents 0 or 1, W^aRepresents a group represented by the following formula (a-3).

[ chemical formula 33]

In the formula (a-2), as R^a3The alkylene group has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and most preferably ethane-1, 2-diyl, propane-1, 2-diyl, and propane-1, 3-diyl.

Ring A in formula (a-3)¹An aliphatic ring which may have a substituent and which may be fused to an aromatic ring. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.

Examples of the alicyclic ring include monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane.

Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.

The aromatic ring which may be fused to the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and an aromatic hydrocarbon ring is preferable. Specifically, benzene ring and naphthalene ring are preferable.

Preferred examples of the divalent group represented by the formula (a-3) include the following groups.

[ chemical formula 34]

In the formula (a-1)A divalent group X of^aBy providing a residue Z^aThe tetracarboxylic dianhydride (a) is introduced into the Cardo resin (a-1) by reacting with a diol compound represented by the following formula (a-2 a).

[ chemical formula 35]

In the formula (a-2a), R^a1、R^a2、R^a3And t2 are as described for formula (a-2). With respect to ring A in formula (a-2a)¹As described for formula (a-3).

The diol compound represented by the formula (a-2a) can be produced, for example, by the following method.

First, if necessary, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is replaced with-R by a conventional method^a3A group represented by-OH, and then glycidylated using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2 c).

Then, the epoxy compound represented by the formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by the formula (a-2 a).

In the formulae (a-2b) and (a-2c), R^a1、R^a3And t2 are as described for formula (a-2). With respect to ring A in formulae (a-2b) and (a-2c)¹As described for formula (a-3).

The method for producing the diol compound represented by the formula (a-2a) is not limited to the above-described method.

[ chemical formula 36]

Preferable examples of the diol compound represented by the formula (a-2b) include the following diol compounds.

[ chemical formula 37]

In the above formula (a-1), R^a0Is a hydrogen atom or-CO-Y^a-COOH, or a group represented by the formula. Here, Y^aIt represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

In the above formula (a-1), Z^aThe residue is obtained by removing 2 acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride include tetracarboxylic acid dianhydride represented by the following formula (a-4), pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl ether tetracarboxylic acid dianhydride, and the like. Among them, pyromellitic dianhydride and biphenyltetracarboxylic dianhydride are preferable, and pyromellitic dianhydride is preferable in view of a wide developing process margin.

In the above formula (a-1), t1 represents an integer of 0 to 20 inclusive.

[ chemical formula 38]

(in the formula (a-4), R^a4、R^a5And R^a6Each independently represents 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 an integer of 0 to 12. )

As R in the formula (a-4)^a4An optional alkyl group is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms of the alkyl group within this range, the heat resistance of the obtained carboxylic ester can be further improved. R^a4In the case of an alkyl group, the number of carbon atoms is preferably 1 or more in view of easy availability of a Cardo resin having excellent heat resistanceAnd 6 or less, more preferably 1 or more and 5 or less, further preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less.

R^a4In the case of an alkyl group, the alkyl group may be linear or branched.

As R in the formula (a-4)^a4Each of the alkyl groups is more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, independently, from the viewpoint of easily obtaining a Cardo resin having excellent heat resistance. R in the formula (a-4)^a4More preferred is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferred is a hydrogen atom or a methyl group.

The plurality of R in the formula (a-4) is preferred in view of easy preparation of a tetracarboxylic dianhydride with high purity^a4Preferably the same groups.

T3 in the formula (a-4) represents an integer of 0 to 12 inclusive. When the value of t3 is 12 or less, the tetracarboxylic dianhydride can be easily purified.

The upper limit of t3 is preferably 5, more preferably 3, from the viewpoint of ease of purification of tetracarboxylic dianhydride.

The lower limit of t3 is preferably 1, more preferably 2, from the viewpoint of chemical stability of the tetracarboxylic dianhydride.

T3 in formula (a-4) is particularly preferably 2 or 3.

As R in the formula (a-4)^a5And R^a6An optional alkyl group having 1 to 10 carbon atoms and R as the substituent^a4The optional alkyl groups having 1 to 10 carbon atoms are the same.

R is easy to purify the tetracarboxylic dianhydride^a5And R^a6A hydrogen atom or an alkyl group having 1 to 10 (preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, and particularly preferably 1 to 3) carbon atoms is preferable, and a hydrogen atom or a methyl group is particularly preferable.

Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride (otherwise known as "norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride"), methylnorbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ″ - (methylnorbornane) -5,5 ″,6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro- α -cyclohexanone- α ' -spiro-2 ″ -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride (distinguished by the name "norbornane-2-spiro-2 ' -cyclohexanone-6 ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride"), methylnorbornane-2-spiro-alpha-cyclohexanone-alpha ' -spiro-2 ' - (methylnorbornane) -5,5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclopropanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclobutanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cycloheptanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclooctanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclononanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclodecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cycloundecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclododecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclotridecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclotetradecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclopentadecanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha- (methylcyclopentanone) -alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha- (methylcyclohexanone) -alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, and the like.

The weight average molecular weight of the Cardo resin (a-1) is preferably 1000 or more and 40000 or less, more preferably 1500 or more and 30000 or less, and further preferably 2000 or more and 10000 or less. When the amount is within the above range, not only good developability but also sufficient heat resistance and mechanical strength can be obtained for the cured product.

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

As the Novolac resin (a-2), various Novolac resins conventionally blended in photosensitive compositions can be used. The Novolac resin (a-2) is preferably a resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol") and an aldehyde in the presence of an acid catalyst.

Examples of the phenols used for producing the Novolac resin (a-2) include: phenol; cresols such as o-cresol, m-cresol and p-cresol; xylenols such as 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3, 5-trimethylphenol and 3,4, 5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl polyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (all of alkyl groups have 1 to 4 carbon atoms); alpha-naphthol; beta-naphthol; hydroxybiphenyl; and bisphenol A; and so on. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and m-cresol and p-cresol are more preferable in combination. In this case, by adjusting the blending ratio of the two, various properties such as heat resistance of a cured product formed using the resin composition can be adjusted.

The mixing ratio of m-cresol and p-cresol is not particularly limited, and is preferably 3/7 or more and 8/2 or less in terms of a molar ratio of m-cresol/p-cresol. By using m-cresol and p-cresol in the ratio of the above range, a resin composition capable of forming a cured product having excellent heat resistance can be easily obtained.

In addition, a Novolac resin produced by using m-cresol and 2,3, 5-trimethylphenol in combination is also preferable. When the Novolac resin is used, a resin composition which can form a cured product that is not easily excessively fluidized by heating at the time of post-baking can be obtained particularly easily.

The mixing ratio of m-cresol and 2,3, 5-trimethylphenol is not particularly limited, and is preferably 70/30 or more and 95/5 or less in terms of a molar ratio of m-cresol/2, 3, 5-trimethylphenol.

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

Examples of the acid catalyst used for producing the Novolac resin (a-2) include: inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfate, and p-toluenesulfonic acid; and metal salts such as zinc acetate; and so on. These acid catalysts may be used alone or in combination of two or more.

The weight average molecular weight (Mw; hereinafter, also simply referred to as "weight average molecular weight") of the Novolac resin (a-2) in terms of polystyrene is preferably 2000 as the lower limit value, more preferably 5000, particularly preferably 10000, further preferably 15000, most preferably 20000, and is preferably 50000, more preferably 45000, further preferably 40000, most preferably 35000, from the viewpoint of resistance of a cured product formed using the photosensitive composition to flow due to heating.

The Novolac resin (a-2) may be a combination of at least 2 resins having different weight average molecular weights in terms of polystyrene. By using a combination of resins having different weight average molecular weights, the developability of the photosensitive composition and the heat resistance of a cured product formed using the photosensitive composition can be balanced.

The modified epoxy resin (a-3) is also preferably used as an alkali-soluble resin together with the siloxane-modified (meth) acrylic resin (a 1).

The epoxy resin composition may contain an adduct obtained by adding a polybasic acid anhydride (a-3c) to a reaction product of an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3b), because the cured product is easily formed and is not easily deformed by heating and has high water resistance. The adduct is also referred to as "modified epoxy resin (a-3)".

In the specification and claims of the present application, a compound that satisfies the above definition but does not belong to the resin (a-1) having a Cardo structure is used as the modified epoxy resin (a-3).

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

The epoxy compound (a-3a) is not particularly limited as long as it is a compound having an epoxy group, and may be an aromatic epoxy compound having an aromatic group, or an aliphatic epoxy compound having no aromatic group, and is preferably an aromatic epoxy compound having an aromatic group.

The epoxy compound (a-3a) may be a monofunctional epoxy compound, or may be a 2-or more-functional polyfunctional epoxy compound, and is preferably a polyfunctional epoxy compound.

Specific examples of the epoxy compound (a-3a) include 2-functional epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxy resins such as tetraglycidyl aminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl m-xylylenediamine, and tetraglycidyl bisaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; 3-functional epoxy resins such as 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-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol; 4-functional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether and tetracyclooxypropoxybiphenyl.

The epoxy compound (a-3a) is preferably an epoxy compound having a biphenyl skeleton.

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 2 or more epoxy groups.

By using an epoxy compound having a biphenyl skeleton, a resin composition which is excellent in the balance between sensitivity and developability and which can form a cured product excellent in adhesion to a substrate can be easily obtained.

[ chemical formula 39]

(in the formula (a-3a-1), R^a7Each independently represents a hydrogen atom, an alkyl group having 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. )

R^a7In the case of an alkyl group having 1 to 12 carbon atoms, specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, an n-decyl group, an isodecyl group.

R^a7In the case of a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R^a7May have a substituentIn the case of a phenyl group, 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 the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aliphatic acyl group having 2 to 4 carbon atoms, a halogen atom, a cyano group, and a nitro group.

The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited, and examples thereof include epoxy compounds represented by the following formula (a-3 a-2).

[ chemical formula 40]

(in the formula (a-3a-2), for R^a7And j, in the same way as in the formula (a-3a-1), k is the average number of repetitions of the structural unit in parentheses, and is 0 to 10 inclusive. )

Among the epoxy compounds represented by the formula (a-3a-2), compounds represented by the following formula (a-3a-3) are preferable in terms of particularly easy availability of a resin composition having an excellent balance between sensitivity and developability.

[ chemical formula 41]

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

In the preparation of the modified epoxy compound (a-3), the epoxy compound (a-3a) is reacted with the unsaturated group-containing carboxylic acid (a-3 b).

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 -styrylacrylic acid, β -furfurylacrylic acid, α -cyanocinnamic acid, cinnamic acid, and the like. The unsaturated group-containing carboxylic acids (a-3b) may be used alone or in combination of two or more.

The epoxy compound (a-3a) can be reacted with the unsaturated group-containing carboxylic acid (a-3b) by a known method. Preferred examples of the reaction method include the following methods: the epoxy compound (a-3a) and the carboxylic acid (a-3b) having an unsaturated group are reacted in an organic solvent at a reaction temperature of 50 ℃ to 150 ℃ in the presence of a tertiary amine such as triethylamine or benzylethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine, or triphenylphosphine as a catalyst for several hours to several tens of hours.

The ratio of the amounts of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) used in the reaction is preferably 1: 0.5-1: 2, more preferably 1: 0.8-1: 1.25, particularly preferably 1: 0.9-1: 1.1.

the ratio of the amount of the epoxy compound (a-3a) to the amount of the unsaturated group-containing carboxylic acid (a-3b) used is 1: 0.5-1: 2, the crosslinking efficiency tends to be improved, and is preferable.

The polybasic acid anhydride (a-3c) is an anhydride of a carboxylic acid having 2 or more carboxyl groups.

The polybasic acid anhydride (a-3c) is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, compounds represented by the following formula (a-3c-1), phthalic anhydride, And a compound represented by the following formula (a-3 c-2). The polybasic add anhydrides (a-3c) may be used alone or in combination of two or more.

[ chemical formula 42]

(in the formula (a-3c-2), R^a8Represents an alkylene group which may have a substituent and has 1 to 10 carbon atoms. )

The polybasic add anhydride (a-3c) is preferably a compound having 2 or more benzene rings, because a resin composition having an excellent balance between sensitivity and developability can be easily obtained. The polybasic acid anhydride (a-3c) more preferably contains at least one of the compound represented by the formula (a-3c-1) and the compound represented by the formula (a-3 c-2).

The method of reacting the polybasic acid anhydride (a-3c) after reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) can be appropriately selected from known methods.

The amount ratio of the epoxy compound (a-3a) to the unsaturated group-containing carboxylic acid (a-3b) is usually 1: 1-1: 0.1, preferably 1: 0.8-1: 0.2. when the content is within the above range, a resin composition having good developability can be easily obtained.

The acid value of the modified epoxy resin (a-3) is preferably 10mgKOH/g or more and 150mgKOH/g or less, more preferably 70mgKOH/g or more and 110mgKOH/g or less, in terms of the solid content of the resin. By setting the acid value of the resin to 10mgKOH/g or more, sufficient solubility in a developer can be obtained, and by setting the acid value to 150mgKOH/g or less, sufficient curability can be obtained, and the surface properties of a cured product can be improved.

The weight average molecular weight of the modified epoxy resin (a-3) is preferably 1000 or more and 40000 or less, and more preferably 2000 or more and 30000 or less. By making the weight average molecular weight 1000 or more, a cured product excellent in heat resistance and strength is easily formed. Further, by setting the weight average molecular weight to 40000 or less, a resin composition exhibiting sufficient solubility in a developer can be easily obtained.

The (meth) acrylic resin (a-4) which is a resin other than the (meth) acrylic resin (a1) may also be used as a component constituting the alkali-soluble resin.

In the case where the (meth) acrylic resin (a-I) which is not modified with the epoxy group-containing cyclic siloxane compound (a-II) has an alkali-soluble group, the (meth) acrylic resin (a-I) can also be used as the (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 another monomer such as (meth) acrylate can be used. The (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 object of the present invention.

[ chemical formula 43]

In the above formula (a-4-1), R^a9Is a hydrogen atom or a methyl group, R^a10Is a monovalent organic group. The organic group may contain a bond or a substituent other than the hydrocarbon group, such as a heteroatom. The organic group may be linear, branched, or cyclic.

As R^a10The substituent other than the hydrocarbon group in the organic group(s) is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a cyano group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate/ester group, an acyl group, an acyloxy group, a sulfino group, a sulfo group, a sulfonate/ester group, a phosphino group, aPhosphonate, hydroxyimino, alkylether, arylether, arylthioether, amino (-NH-) groups₂-NHR, -NRR': r and R' each independently represents a hydrocarbon group), and the like. The hydrogen atoms contained in the above substituents may be substituted with hydrocarbon groups. The hydrocarbon group included in the substituent may be linear, branched, or cyclic.

In addition, as R^a10The organic group (2) may have a reactive functional group such as an acryloyloxy group, a methacryloyloxy group, an epoxy group, an oxetanyl group, or the like.

An acyl group having an unsaturated double bond such as an acryloyloxy group or a methacryloyloxy group can be produced, for example, by the following method: an unsaturated carboxylic acid such as acrylic acid or methacrylic acid is reacted with at least a part of the epoxy groups in the (meth) acrylic resin (a-4) containing a structural unit having an epoxy group.

After at least a part of the epoxy groups are reacted with the unsaturated carboxylic acid, the group formed by the reaction may be reacted with a polybasic acid anhydride.

Specific examples of the polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, and 4-ethyltetrahydrophthalic anhydride.

Specifically, when 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 produced. The structural unit having a hydroxyl group is reacted with a polybasic acid anhydride such as tetrahydrophthalic acid to produce a structural unit having a carboxyl group and an unsaturated double bond and imparting alkali solubility to the resin.

[ chemical formula 44]

As R^a10Preferably, an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, which may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. In addition, in the case where these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When the alkyl group is linear or branched, the number of carbon atoms in 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, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl.

When the alkyl group is an alicyclic group or a group containing an alicyclic group, preferable alicyclic groups contained in the alkyl group include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl, and polycyclic alicyclic groups such as adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

The compound represented by the formula (a-4-1) contains a chain group having an epoxy group as R^a10Specific examples of the compound represented by the formula (a-4-1) include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate and other epoxyalkyl (meth) acrylates.

The compound represented by the formula (a-4-1) may be a (meth) acrylate containing an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups.

Specific examples of the case where the compound represented by the formula (a-4-1) is an alicyclic epoxy group-containing (meth) acrylate include compounds represented by the following formulas (a-4-1a) to (a-4-1 o). Among these, in order to keep the developability within a suitable range, compounds represented by the following formulae (a-4-1a) to (a-4-1e) are preferable, and compounds represented by the following formulae (a-4-1a) to (a-4-1c) are more preferable.

[ chemical formula 45]

[ chemical formula 46]

[ chemical formula 47]

In the above formula, R^a20Represents a hydrogen atom or a methyl group, R^a21Represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R^a22Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t represents an integer of 0 to 10 inclusive. As R^a21The alkylene group is preferably a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R^a22For example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH₂-Ph-CH₂- (Ph represents phenylene).

The (meth) acrylic resin (a-4) may be a copolymer obtained by further polymerizing a monomer other than a (meth) acrylate ester. Examples of the monomer other than the (meth) acrylic acid ester include (meth) acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These monomers may be used alone or in combination of 2 or more. Preferred examples of these monomers are as described for the (meth) acrylic resin (a 1).

The amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from another monomer in the (meth) acrylic resin (a-4) are not particularly limited within the range not interfering with the object of the present invention. The amount of the structural unit derived from (meth) acrylic acid in the (meth) acrylic resin (a-4) is preferably 5 to 50 mass%, more preferably 10 to 30 mass%, based on the mass of the (meth) acrylic resin (a-4).

When the (meth) acrylic resin (a-4) contains a structural unit having an unsaturated double bond, the amount of the structural unit having an unsaturated double bond in the (meth) acrylic resin (a-4) is preferably 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.

When the (meth) acrylic resin (a-4) contains the structural unit having an unsaturated double bond in an amount within the above range, the crosslinking reaction of the acrylic resin into the resist film can be uniformized, and therefore, the improvement of the heat resistance and mechanical properties of the cured film is effective.

The weight average molecular weight of the (meth) acrylic resin (a-4) is preferably 2000 to 50000, more preferably 3000 to 30000. When the content is within the above range, the following tendency is exhibited: the balance between the film forming ability of the resin composition and the developability after exposure is easily obtained.

The total mass of the (meth) acrylic resin (a1) and other resins in the 2 nd resin composition is preferably 20 to 85 mass%, more preferably 25 to 75 mass%, with respect to the mass of the resin composition (the whole solid content) excluding the mass of the organic solvent (S) described later. When the content is in the above range, a resin composition having excellent developability can be easily obtained.

Photopolymerizable monomer (B)

The 2 nd resin composition contains a photopolymerizable monomer (B). As the photopolymerizable monomer (B), compounds conventionally compounded in photosensitive compositions can be used without particular limitation.

Examples of the monofunctional photopolymerizable monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, methyl (meth) acrylamide, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, t-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like, 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) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivatives, and the like. These monofunctional photopolymerizable monomers may be used alone or in combination of two or more.

Examples of the polyfunctional photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) 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, pentaerythritol penta (meth) acrylate, and mixtures thereof, Dipentaerythritol hexa (meth) acrylate, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), a reaction product of 2-hydroxyethyl (meth) acrylate with trimethylhexamethylene diisocyanate, etc., a reaction product of 2-hydroxyethyl (meth) acrylate with a reaction product of 2, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, Polyfunctional monomers such as methylenebis (meth) acrylamide, (meth) acrylamidomethylene ether, and condensates of polyhydric alcohols and N-methylol (meth) acrylamide, and 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine. These polyfunctional photopolymerizable monomers may be used alone or in combination of two or more.

Among these photopolymerizable monomers (B), from the viewpoint of a tendency to improve the adhesion between the resin composition and the substrate and the strength of the resin composition after curing, a polyfunctional photopolymerizable monomer having 3 or more functions is preferable, a polyfunctional monomer having 4 or more functions is more preferable, and a polyfunctional photopolymerizable monomer having 5 or more functions is even more preferable.

The content of the photopolymerizable monomer (B) in the resin composition is preferably 1 mass% or more and 50 mass% or less, and more preferably 5 mass% or more and 40 mass% or less, with respect to the mass of the resin composition (the whole solid content) excluding the mass of the organic solvent (S) described later. By setting the range to the above range, it is easy to obtain the balance among sensitivity, developability, and resolution.

Photopolymerization initiator (C)

As the photopolymerization initiator, a compound which has been conventionally known and used for the purpose of curing a photopolymerizable monomer having an unsaturated bond in a photosensitive composition can be used without particular limitation.

Specific examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (4-dimethylaminophenyl) one, and, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 4-benzoyl-4' -methyldimethylsulphide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl- β -methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl O-benzoylbenzoate, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioton, 2, 4-diethylthioxanthene, 2-methylthio-ton, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (O-chlorophenyl) -4, 5-bis (m-methoxyphenyl) -dimer imidazolyl, m-methoxyphenyl-dihydroxanthene, methyl 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 1-methylanthraquinone, 1, 2-methylanth, Benzophenone, 2-chlorobenzophenone, p ' -bisdimethylaminobenzophenone, 4 ' -bisdiethylaminobenzophenone, 4 ' -dichlorobenzophenone, 3-dimethyl-4-methoxybenzophenone, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropylketone, dichloroacetophenone, trichloroacetophenone, p-tert-butylbenzophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, alpha-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1, 7-bis- (9-acridinyl) heptane, 1, 5-bis- (9-acridinyl) pentane, 1, 3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4, 6-tris (trichloromethyl) s-triazine, 2-methyl-4, 6-bis (trichloromethyl) s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl s-triazine Oxy) phenyl s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl s-triazine, and the like.

These photopolymerization initiators (C) may be used alone or in combination of 2 or more.

In addition, an oxime ester compound is preferable as the photopolymerization initiator (C) from the viewpoint of the sensitivity of the resin composition.

The oxime ester compound is preferably an oxime ester compound represented by the following formula (c1), for example.

[ chemical formula 48]

In the above formula (c1), R^c11Represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. a is 0 or 1. R^c12To representAn alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. R^c13Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent.

R^c11In the case of an alkyl group having 1 to 10 carbon atoms which may have a substituent, the kind of the substituent which the alkyl group has is not particularly limited within a range which does not impair the object of the present invention.

Examples of the preferable substituent which may be contained in the alkyl group having 1 to 10 carbon atoms include an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a phenyloxy group which may have a substituent, a phenyl, A naphthyloxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent having 11 to 20 carbon atoms, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen group, a nitro group, a cyano group, and the like.

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 to 8, more preferably 1 to 5.

R^c11In the case of a phenyl group which may have a substituent, the kind of the substituent is not particularly limited within a range not interfering with the object of the present invention. Preferable examples of the substituent which the phenyl group may have include an alkyl group, an alkoxy group, and a cycloalkaneExamples of the substituent include a cyclic alkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, a cyano group, and the like. R^c11When 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 to 20, more preferably 1 to 10, even more preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1. The alkyl group may be linear or branched. Specific examples of the substituent of the phenyl group as an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, an n-decyl group, and. In addition, the alkyl group may contain an ether bond (-O-) in the carbon chain. In this case, examples of the substituent group of the phenyl group include an alkoxyalkyl group and an alkoxyalkoxyalkyl group. When the substituent of the phenyl group is an alkoxyalkyl group, the substituent is preferably-R^c14-O-R^c15The group shown. R^c14Is an alkylene group having 1 to 10 carbon atoms and which may be straight or branched. R^c15Is an alkyl group having 1 to 10 carbon atoms, which may be linear or branched. R^c14The number of carbon atoms of (b) is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. R^c15The number of carbon atoms of (b) is preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When the substituent of the phenyl group is an alkoxy group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 6. The alkoxy group may be linear or branched. Specific examples of the substituent of the phenyl group as the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. In addition, alkoxy groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a 2-methoxy-1-methylethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When the substituent of the phenyl group is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 6. Specific examples of the substituent group of the phenyl group include a cycloalkyl group, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the substituent group of the phenyl group include a cycloalkoxy group, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

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 to 20, more preferably 2 to 7. Specific examples of the saturated aliphatic acyl group as the substituent of the phenyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. Specific examples of the saturated aliphatic acyloxy group as the substituent of the phenyl group include an acetoxy group, a propionyloxy group, a n-butyryloxy group, a 2-methylpropionyloxy group, a n-valeryloxy group, a 2, 2-dimethylpropionyloxy group, a n-hexanoyloxy group, a n-heptanoyloxy group, a n-octanoyloxy group, a n-nonanoyloxy group, a n-decanoyloxy group, a n-undecanoyloxy group, a n-dodecanoyloxy group, a n-tridecanoyloxy group, a n-tetradecanoyloxy group, a n-pentadecanoyloxy group, a n-hexadecanoyloxy group and the like.

When the substituent of the phenyl group is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. Specific examples of the substituent of the phenyl group as the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.

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

When the substituent of the phenyl group is a heterocyclic group, the heterocyclic group may be a 5-or 6-membered monocyclic ring containing 1 or more N, S, O atoms or a heterocyclic group in which the monocyclic rings are fused with each other or with a benzene ring. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 or less. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. 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 amino group substituted with 1 or 2 organic groups, preferable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group which may have a substituent having 11 to 20 carbon atoms and may have a heterocyclic group, and the like. Specific examples of these preferable organic groups include those similar to the groups described above for the substituents of the phenyl group. Specific examples of the amino group substituted with 1 or 2 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-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, N-butyrylamino, N-valerylamino, N-hexanoylamino, N-heptanoylamino, N-octanoylamino, N-decanoylamino, benzoylamino, α -naphthoylamino, β -naphthoylamino, and N-acetyl-N-acetyloxyamino.

Examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclic group, which are included in the substituents contained in the phenyl group, further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group and a cyano group. When the phenyl group, the naphthyl group and the heterocyclic group included in the substituents of the phenyl group further have a substituent, the number of the substituents is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclic group, which are included in the substituents of the phenyl group, have a plurality of substituents, the plurality of substituents may be the same or different.

Above, for R^c11The substituents in the case of phenyl groups which may have substituents are described, and among these substituents, alkyl groups or alkoxyalkyl groups are preferred.

R^c11In the case of a phenyl group which may have a substituent, the number of substituents and the bonding position of the substituent are not particularly limited within a range not interfering with the object of the present invention. R^c11In the case of a phenyl group which may have a substituent, the phenyl group which may have a substituent is excellent in the efficiency of producing a baseThe o-tolyl group which may have a substituent is preferred.

R^c11In the case of the carbazolyl group which may have a substituent, the kind of the substituent is not particularly limited within a range not interfering with the object of the present invention. Examples of the preferable substituent which may be present on a carbon atom in the carbazolyl group include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a phenylcarbonyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a phenyl, Naphthyloxy which may have a substituent, naphthylcarbonyl which may have a substituent, naphthoyl which may have a substituent, naphthyloxycarbonyl which may have a substituent, naphthoyloxy which may have a substituent, naphthylalkyl which may have a substituent and has a carbon number of 11 to 20, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino substituted with 1 or 2 organic groups, morpholin-1-yl, and piperazin-1-yl, halogen, nitro, and cyano, and the like.

R^c11In the case of a carbazolyl group which may have a substituent(s), examples of preferable substituents which may be present on the nitrogen atom of the carbazolyl group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent(s), a benzoyl group which may have a substituent(s), a phenoxycarbonyl group which may have a substituent(s), a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent(s), a naphthyl group which may have a substituent(s), a naphthoyl group which may have a substituent(s), and a naphthoxy group which may have a substituent(s)A carbonyl group, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, 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.

Specific examples of the substituent which the carbazolyl group may have are alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenylalkyl which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, and amino substituted with 1 or 2 organic groups, and R^c11The same applies to the substituent of the phenyl group in the case of the phenyl group which may have a substituent.

R^c11In the above-mentioned formula, examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclic group contained in the substituent of the carbazolyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; piperazin-1-yl; halogen; a nitro group; a cyano group. When the phenyl group, naphthyl group, and heterocyclic group included in the substituent group of the carbazolyl group further have a substituent group, the number of the substituent group is not limited within a range not interfering with the object of the present invention, and is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

R^c12An optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group,Or a carbazolyl group which may have a substituent.

R^c12When the alkyl group has 1 to 10 carbon atoms and may have a substituent, the alkyl group may be a straight chain or a branched chain. In this case, the number of carbon atoms of the alkyl group is preferably 1 to 8, more preferably 1 to 5.

R^c12In the above formula, the substituent group of the alkyl group or the phenyl group is not particularly limited as long as the object of the present invention is not hindered.

Examples of the preferable substituent which may be contained in the alkyl group on the carbon atom include an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, Naphthoyloxy which may have a substituent, naphthylalkyl which may have a substituent having 11 to 20 carbon atoms, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino substituted with 1 or 2 organic groups, morpholin-1-yl, and piperazin-1-yl, halogen, nitro, and cyano, and the like.

Examples of the preferable substituent that the phenyl group may have on a carbon atom include, in addition to the groups exemplified above as the preferable substituent that the alkyl group may have on a carbon atom, an alkyl group having 1 to 20 carbon atoms.

Specific examples of the substituent which the alkyl group or the phenyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, an optionally substituted alkyl groupPhenylalkyl which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, and amino substituted with 1 or 2 organic groups, and R^c11The same applies to the substituent of the phenyl group in the case of the phenyl group which may have a substituent.

R^c12In the above-mentioned formula, examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclic group contained in the alkyl group or the substituent contained in the phenyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; piperazin-1-yl; halogen; a nitro group; a cyano group. When the phenyl group, naphthyl group, and heterocyclic group included in the substituent of the alkyl group or phenyl group further have a substituent, the number of the substituents is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

R^c12In the case of the carbazolyl group which may have a substituent, the kind of the substituent which the carbazolyl group has is not particularly limited within a range not interfering with the object of the present invention. As preferable examples of the substituent which the carbazolyl group may have, with R^c11The same applies to the substituent in the case of a carbazolyl group which may have a substituent.

From the viewpoint of reactivity of the compound represented by the formula (c1), R is^c12Preferably, a group represented by the following formula (c2) or the following formula (c 3):

[ chemical formula 49]

[ chemical formula 50]

In the formula (c2), R^c16And R^c17Are each a monovalent organic group, and b is 0 or 1. In the formula (c3), R^c18Is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, A^c1Is S or O, and c is an integer of 0 to 4.

R in the formula (c2)^c16The organic group may be selected from various organic groups within a range not interfering with the object of the present invention. As R^c16Preferable examples of (3) include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

R^c16Among them, 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 in the formula (c2)^c17The organic group is not particularly limited as long as the object of the present invention is not impaired, and may be selected from various organic groups. With respect to as R^c17Specific examples of the preferable group include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclic group. As R^c17These radicalsAmong them, phenyl which may have a substituent and naphthyl which may have a substituent are more preferable, and 2-methylphenyl and naphthyl are particularly preferable.

As R^c16Or R^c17The substituents in the case where the phenyl group, naphthyl group and heterocyclic group contained in (a) further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like. R^c16Or R^c17When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. R^c16Or R^c17When the phenyl group, naphthyl group and heterocyclic group contained in (1) have a plurality of substituents, the plurality of substituents may be the same or different.

R in the formula (c3)^c18In the case of an organic radical, R^c18The organic group may be selected from various organic groups within a range not interfering with the object of the present invention. In the formula (c3), R is^c18Preferable examples of the organic group include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; piperazin-1-yl; halogen; a nitro group; a cyano group; 2-methylphenylcarbonyl; 4- (piperazin-1-yl) phenylcarbonyl; 4- (phenyl)) A phenylcarbonyl group.

R^c18Among them, benzoyl is preferred; a naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; nitro, more preferably benzoyl; a naphthoyl group; 2-methylphenylcarbonyl; 4- (piperazin-1-yl) phenylcarbonyl; 4- (phenyl) phenylcarbonyl.

In the formula (c3), c is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When c is 1, R^c18Is preferably relative to R^c18The bonding site at which the bonded phenyl group is bonded to the sulfur atom is para.

R^c13Is 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 and R^c11The same applies to the case of a phenyl group which may have a substituent. As R^c13Preferably, a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or a phenyl group.

Among the compounds represented by the above formula (c1), preferable compounds include compounds represented by the following formula (c 4).

[ chemical formula 51]

In the above formula (c4), a and R^c12And R^c13As described above. R^c19Is 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 to 4.

In the above formula (c4), R^c19The organic group is not particularly limited as long as it does not interfere with the object of the present invention, and may be appropriately selected from various organic groups. As R^c19Preferred examples thereof include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, and the likeA substituted phenyl group, a substituted phenoxy group, a substituted benzoyl group, a substituted phenoxycarbonyl group, a substituted benzoyloxy group, a substituted phenylalkyl group, a substituted naphthyl group, a substituted naphthyloxy group, a substituted naphthoyl group, a substituted naphthoxycarbonyl group, a substituted naphthoyloxy group, a substituted naphthylalkyl group, a substituted heterocyclic group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, and the like. When s is an integer of 2 to 4, R^c19May be the same or different. The number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further included in the substituent.

R^c19In the case of an alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 6. In addition, R^c19When the alkyl group is used, the alkyl group may be linear or branched. As R^c19Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. In addition, R^c19In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

R^c19In the case of an alkoxy group, the number of carbon atoms is preferably 1 to 20, and more preferably 1 to 6. In addition, R^c19When the alkoxy group is used, the alkoxy group may be linear or branched. As R^c19Specific examples of the alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxyOxy, t-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, t-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, t-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. In addition, R^c19In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxyethoxy, and methoxypropyloxy.

R^c19In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 6. As R^c19Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. As R^c19Specific examples of the cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

R^c19In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. As R^c19Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. As R^c19Specific examples of the saturated aliphatic acyloxy group include an acetoxy group, a propionyloxy group, an n-butyryloxy group, a 2-methylpropionyloxy group, an n-pentanoyloxy group, a 2, 2-dimethylpropionyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy groupOxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy, and the like.

R^c19In the case of an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. As R^c19Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propyloxycarbonyl group, an isopropyloxycarbonyl group, a n-butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, a tert-butyloxycarbonyl group, a n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, a n-hexyloxycarbonyl group, a n-heptyloxycarbonyl group, a n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, a n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

R^c19In the case of a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, more preferably 7 to 10. In addition, R^c19In the case of a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, more preferably 11 to 14. As R^c19Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As R^c19Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a 2- (. alpha. -naphthyl) ethyl group, and a 2- (. beta. -naphthyl) ethyl group. R^c19In the case of phenylalkyl or naphthylalkyl, R^c19The phenyl group or naphthyl group may further have a substituent.

R^c19In the case of a heterocyclic group, the heterocyclic group may be a 5-or 6-membered monocyclic ring containing 1 or more N, S, O atoms or a heterocyclic group in which the monocyclic rings are fused with each other or with a benzene ring. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 or less. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole and thiadiazoleIsothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, and the like. R^c19In the case of a heterocyclic group, the heterocyclic group may further have a substituent.

R^c19In the case of an amino group substituted with 1 or 2 organic groups, preferable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group and the like. Specific examples of these preferred organic groups and R^c19The same is true. Specific examples of the amino group substituted with 1 or 2 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-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-valerylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino, β -naphthoylamino and the like.

As R^c19The substituent in the case where the phenyl group, naphthyl group and heterocyclic group contained in (a) further have a substituent(s) includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and a heterocyclic groupDialkylamino group having an alkyl group of 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, halogen, nitro group, cyano group, and the like. R^c19When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. R^c19When the phenyl group, naphthyl group and heterocyclic group contained in (1) have a plurality of substituents, the plurality of substituents may be the same or different.

R^c19Among them, from the viewpoints of chemical stability, small steric hindrance, easiness in synthesis of oxime ester compounds, and the like, a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.

With respect to R^c19Bonding position on phenyl for R^c19The phenyl group bonded to the oxime ester compound is preferably at the 4-or 5-position, more preferably at the 5-position, when the position of the bonding site between the phenyl group and the main skeleton of the oxime ester compound is the 1-position and the position of the methyl group is the 2-position. D is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R in the above formula (c4)^c13Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent. With respect to R^c13The specific example of (a) is as described above for the formula (c 1). As R in formula (c4)^c13Methyl, ethyl, and phenyl are preferred, and methyl and phenyl are more preferred.

Among the oxime ester compounds, preferable examples of the compounds contained in the formula (c1) but not contained in the formula (c4) include the following compounds.

[ chemical formula 52]

Among the oxime ester compounds represented by the formula (c4) which are particularly preferable as the oxime ester compounds, compounds represented by the following formula are mentioned.

[ chemical formula 53]

[ chemical formula 54]

[ chemical formula 55]

[ chemical formula 56]

[ chemical formula 57]

[ chemical formula 58]

[ chemical formula 59]

In addition, from the viewpoint of the sensitivity of the resin composition and the transparency of the cured product, an oxime ester compound represented by the following formula (1) is particularly preferable as the oxime ester compound.

[ chemical formula 60]

(in the formula (1), R^c1Is a hydrogen atom, a nitro group or a monovalent organic group, R^c2And R^c3Each independently is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R^c2And R^c3May be bonded to each other to form a ring, R^c4Is a monovalent organic radical, R^c5Is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, n1 is an integer of 0 to 4, and n2 is 0 or 1. )

In the formula (1), R^c1Is a hydrogen atom, a nitro group or a monovalent organic group. R^c1Bound to the fluorene ring in formula (1) with- (CO)_n26-membered aromatic rings different from the 6-membered aromatic ring of the group represented by (A) and (B). In the formula (1), R^c1The bonding position to the fluorene ring is not particularly limited. The compound represented by the formula (1) has 1 or more R^c1In the case (2), from the viewpoint of ease of synthesis of the compound represented by the formula (1), it is preferable that R is 1 or more^c11 in (b) is bonded to the 2-position in the fluorene ring. R^c1In the case of plural, plural R^c1May be the same or different.

R^c1In the case of an organic radical, R^c1The organic solvent is not particularly limited as long as it does not interfere with the object of the present invention, and may be appropriately selected from various organic groups. As R^c1Preferable examples of the organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, and a naphthyloxycarbonyloxycarbonyl group which may have a substituentA naphthyl group, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, and the like.

R^c1In the case of an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6. In addition, R^c1When the alkyl group is used, the alkyl group may be linear or branched. As R^c1Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. In addition, R^c1In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

R^c1In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 6. In addition, R^c1When the alkoxy group is used, the alkoxy group may be linear or branched. As R^c1Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propyloxy group, an isopropyloxy group, a n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, a n-nonyloxy group, an isononyloxy group, a n-decyloxy group, and an. In addition, R^c1In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxyAnd methoxyethoxy, propyloxyethoxyethoxyethoxy, methoxypropyloxy, and the like.

R^c1In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. As R^c1Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. As R^c1Specific examples of the cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

R^c1In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. As R^c1Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. As R^c1Specific examples of the saturated aliphatic acyloxy group include an acetyloxy group, a propionyloxy group, an n-butyryloxy group, a 2-methylpropionyloxy group, an n-pentanoyloxy group, a 2, 2-dimethylpropionyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group.

R^c1In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. As R^c1Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, and an n-butyl groupAn oxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, a tert-butyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, an n-decyloxycarbonyl group, an isodecyloxycarbonyl group and the like.

R^c1In the case of a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. In addition, R^c1In the case of a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. As R^c1Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As R^c1Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a 2- (. alpha. -naphthyl) ethyl group, and a 2- (. beta. -naphthyl) ethyl group. R^c1In the case of phenylalkyl or naphthylalkyl, R^c1The phenyl group or naphthyl group may further have a substituent.

R^c1In the case of a heterocyclic group, the heterocyclic group may be a 5-or 6-membered monocyclic ring containing 1 or more N, S, O atoms or a heterocyclic group in which the monocyclic rings are fused with each other or with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings in a single ring constituting the condensed ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like. R^c1In the case of a heterocyclic group, heteroThe cyclic group may further have a substituent.

R^c1In the case of a heterocyclylcarbonyl group, the heterocyclyl group and R contained in the heterocyclylcarbonyl group^c1The same applies to heterocyclic groups.

R^c1In the case of an amino group substituted with 1 or 2 organic groups, preferable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group and the like. Specific examples of these preferred organic groups and R^c1The same is true. Specific examples of the amino group substituted with 1 or 2 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-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-valerylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino, β -naphthoylamino and the like.

As R^c1The substituents in the case where the phenyl group, naphthyl group and heterocyclic group contained in (a) further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like. R^c1Contained in (A), phenyl, naphthyl, andwhen the heterocyclic group further has a substituent, the number of the substituent is not limited within a range not interfering with the object of the present invention, and is preferably 1 to 4. R^c1When the phenyl group, naphthyl group and heterocyclic group contained in (1) have a plurality of substituents, the plurality of substituents may be the same or different.

In the above-described groups, as R^c1Is nitro, or R^c10The group represented by-CO-is preferable because the sensitivity tends to be improved. R^c10The organic group is not particularly limited as long as the object of the present invention is not impaired, and may be selected from various organic groups. With respect to as R^c10Examples of the preferable group include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclic group. As R^c10Among these groups, 2-methylphenyl, thiophen-2-yl and α -naphthyl are particularly preferable.

In addition, R^c1In the case of a hydrogen atom, the transparency tends to be good, and it is preferable. In addition, R is^c1Is a hydrogen atom and R^c4In the case of a group represented by the following formula (1a) or (1b), the transparency tends to be more excellent.

In the formula (1), R^c2And R^c3Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R^c2And R^c3May be bonded to each other to form a ring. Of these groups, as R^c2And R^c3A chain alkyl group which may have a substituent is preferable. R^c2And R^c3When the alkyl group is a linear alkyl group which may have a substituent, the linear alkyl group may be a linear alkyl group or a branched alkyl group.

R^c2And R^c3In the case of a chain alkyl group having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. As R^c2And R^c3Specific examples of the chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl and isopropylButyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, isodecyl and the like. In addition, R^c2And R^c3In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

R^c2And R^c3In the case of a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. 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 straight.

The substituent that the alkyl group may have is not particularly limited within a range that does not interfere with the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atom, chlorine atom and bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. As specific examples of cycloalkyl, with R^c1The same applies to the preferred case of cycloalkyl. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and the like. As specific examples of heterocyclic groups, with R^c1The same applies to the preferred examples in the case of heterocyclic groups. R^c1In the case of 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 to 10, more preferably 1 to 6.

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

R^c2And R^c3In the case of a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. R^c2And R^c3In the case of a cyclic organic group, the substituent which the cyclic organic group may have and R^c2And R^c3The same applies to the case of a chain alkyl group.

R^c2And R^c3In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group in which a plurality of benzene rings are bonded via a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed. When the aromatic hydrocarbon group is a phenyl group or a group in which a plurality of benzene rings are bonded or condensed, the number of the benzene rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. As preferable specific examples of the aromatic hydrocarbon group, phenyl, naphthyl, biphenyl, anthryl, phenanthryl, and the like can be cited.

R^c2And R^c3In the case of an alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, and is preferably 3 to 20, and more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.

R^c2And R^c3In the case of a heterocyclic group, the heterocyclic group may be a 5-or 6-membered monocyclic ring containing 1 or more N, S, O atoms or a heterocyclic group in which the monocyclic rings are fused with each other or with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings in a single ring constituting the condensed ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. As a constitutionExamples of the heterocyclic ring of the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.

R^c2And R^c3May be bonded to each other to form a ring. Comprising R^c2And R^c3The radical of the ring formed is preferably cycloalkylene. R^c2And R^c3When the cyclic alkylene group is bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring.

R^c2And R^c3When the group to which the bond is formed is a cycloalkylene group, the cycloalkylene group may be fused with 1 or more other rings. Examples of the ring which may be fused with a cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and the like.

R as described above^c2And R^c3Examples of preferred groups in (A) include formula (A)⁰¹-A⁰²The group shown. Can lift out of formula⁰¹Is a linear alkylene radical, A⁰²Is an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, or an alkoxycarbonyl group.

A⁰¹The number of carbon atoms of the linear alkylene group (2) is preferably 1 to 10, more preferably 1 to 6. A. the⁰²In the case of an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. A. the⁰²When the halogen atom is used, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferable, and a fluorine atom, a chlorine atom or a bromine atom is more preferable. A. the⁰²In the case of haloalkyl, haloThe halogen atom contained in the alkyl group 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 haloalkyl group may be linear or branched, and is preferably linear. A. the⁰²In the case of a cyclic organic group, examples of the cyclic organic group are as defined above with R^c2And R^c3The cyclic organic group included as a substituent is the same. A. the⁰²In the case of alkoxycarbonyl, examples of alkoxycarbonyl are given with R^c2And R^c3The alkoxycarbonyl group included as a substituent is the same.

As R^c2And R^c3Preferable specific examples of the (C) include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; alkoxyalkyl groups such as 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-n-heptyl, and 8-ethoxy-n-octyl; cyanoalkyl groups such as 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; phenylalkyl groups such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; cycloalkylalkyl groups such as 2-cyclohexylethyl, 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-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-hexylAlkoxycarbonyl alkyl groups such as an ethoxycarbonyl n-heptyl group and an 8-ethoxycarbonyl n-octyl group; haloalkyl groups such as 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.

As R^c2And R^c3Among the above groups, preferred 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.

As R^c4Examples of preferred organic radicals of (1), with R^c1Examples thereof include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups and for R^c1The same applies to the specific examples of said radicals specified. In addition, as R^c4Also preferred are cycloalkylalkyl groups, phenoxyalkyl groups which may have a substituent on the aromatic ring, and phenylthioalkyl groups which may have a substituent on the aromatic ring. Phenoxyalkyl group, and phenylthioalkyl group-optionally-substituted group and R^c1The same applies to the substituents which the phenyl group contained in (1) may have.

In the organic radical, as R^c4Preferably an alkyl group, a cycloalkyl group, an optionally substituted groupPhenyl group, cycloalkylalkyl group, phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among cycloalkylalkyl groups, 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 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylsulfanylalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl is preferable.

In addition, as R^c4Further preferred is-A⁰³-CO-O-A⁰⁴The group shown. A. the⁰³Is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A. the⁰⁴Is a monovalent organic group, preferably a monovalent hydrocarbon group.

A⁰³In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. A. the⁰³In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

As A⁰⁴Preferable examples thereof 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. As A⁰⁴Preferable specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α -naphthylmethyl, and β -naphthylmethyl groups.

As a⁰³-CO-O-A⁰⁴Preferred of the groups representedExamples thereof include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonylethyl, 2-n-butyloxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propyloxycarbonyl-n-propyl, 3-n-butyloxycarbonyl-n-propyl, 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl and 3-phenoxycarbonyl-n-propyl.

Above, for R^c4Has been described as R^c4The group represented by the following formula (1a) or the following formula (1b) is preferable.

[ chemical formula 61]

(in the formulae (1a) and (1b), R^c7And R^c8Each is an organic group, n3 is an integer of 0 to 4, R^c7And R^c8In the case of presence in adjacent positions on the benzene ring, R^c7And R^c8Can form a ring by bonding with each other, n4 is an integer of 1 to 8 inclusive, n5 is an integer of 1 to 5 inclusive, n6 is an integer of 0 to (n5+3), R^c9Is an organic group. )

With respect to R in the formula (1a)^c7And R^c8Examples of organic radicals of (2) with R^c1The same is true. As R^c7Preferably an alkyl group or a phenyl group. R^c7In the case of an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Namely, R^c7Most preferred is methyl. R^c7And R^c8When a ring is bonded to form a bond, the ring may be an aromatic ring or an aliphatic ring. R is represented by the formula (1a)^c7And R^c8Preferred examples of the group forming a ring include naphthalen-1-yl and 1,2,3, 4-tetrahydronaphthalen-5-yl. In the above formula (1a), n3 is an integer of 0 to 4, preferably 0 or 1More preferably 0.

In the above formula (1b), R^c9Is an organic group. Examples of the organic group include those related to R^c1The organic groups illustrated are the same groups. Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R^c9Preferable examples thereof include methyl, ethyl, propyl, isopropyl, butyl and the like, and among them, methyl is more preferable.

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

In the formula (1), R^c5Is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As R^c5As the substituent which may be contained in the case of an alkyl group, a phenyl group, a naphthyl group, and the like are preferably exemplified. In addition, as R^c1Examples of the substituent which may be contained in the case of an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In the formula (1), as R^c5Preferred examples thereof include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like, and among them, methyl group or phenyl group is more preferred.

Preferable specific examples of the compound represented by the formula (1) include the following PI-43 to PI-83.

[ chemical formula 62]

[ chemical formula 63]

The content of the photopolymerization initiator (C) is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, based on the mass of the resin composition (the whole solid content) excluding the mass of the solvent (S) described later. When the content of the photopolymerization initiator (C) is in the above range, a resin composition having good curability can be obtained.

The photopolymerization initiator (C) may be combined with a photoinitiator. Examples of the photo-initiation assistant include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone, 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, triisopropanolamine, methyl 4-dimethylaminobenzoate, isobutyl 4-dimethylaminobenzoate, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxya, And thiol compounds such as 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate. These photoinitiating auxiliaries may be used alone or in combination of 2 or more.

Organic solvent (S)

Typically, the 2 nd resin composition may contain an organic solvent (S) for the purpose of adjusting coatability, etc. As the organic solvent (S), the same organic solvents as those described for the resin composition 1 can be used.

The amount of the organic solvent (S) to be used may be determined as appropriate depending on the use of the resin composition. The amount of the organic solvent (S) used may be, for example, an amount in which the solid content concentration of the resin composition is in the range of 1 mass% to 50 mass%.

Other ingredients

The resin composition may contain various additives other than the above components as required. Specifically, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, thermal polymerization inhibitors, defoaming agents, surfactants, and the like can be exemplified.

The 2 nd resin composition may contain an epoxy group-containing cyclic siloxane compound (A-II) which does not react with the (meth) acrylic resin (A-I). The resin composition preferably does not contain an epoxy group-containing cyclic siloxane compound, because a cured product having a low relative dielectric constant can be easily formed. When the resin composition contains the epoxy group-containing cyclic siloxane compound (a-II), the content thereof is preferably 40% by mass or less, more preferably 10% by mass or less, and still more preferably 1% by mass or less, with respect to the mass of the resin composition excluding the mass of the organic solvent (S).

Cured product and method for producing cured product

The cured product can be produced by heating and/or exposing the resin composition. When producing a cured product, the operations of heating, exposure, and both heating and exposure are appropriately determined in consideration of the composition of the cured product composition. The cured product of the resin composition exhibits a low relative permittivity, and therefore can be suitably used as a material for films such as insulators in display panels for various image display devices.

The relative dielectric constant of the cured product is preferably 3.3 or less, more preferably 3.2 or less, and still more preferably 3.1 or less, as measured at a frequency of 0.1 MHz.

As a method for measuring the relative permittivity, a mercury probe method is preferably used. An example of an apparatus capable of measuring the relative permittivity by the mercury probe method is SSM-495 (manufactured by Semilab Japan KK).

As a preferred example of the method for measuring the relative dielectric constant, the following method can be mentioned: after a film-like cured product was formed by the following steps 1) to 4), the relative permittivity measurement by the mercury probe method was performed on the formed cured product.

1) A coating film is formed by coating a silicon wafer with a resin composition.

2) The formed coating film was heated at 100 ℃ for 120 seconds.

3) When the resin composition contains a photopolymerization initiator or a photosensitive curing agent, the concentration is optionally 1kJ/cm²The exposure amount of (2) exposes the coating film.

4) The exposed coating film was heated at 230 ℃ for 20 minutes as necessary.

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

When the shape of the cured product is a film shape, it is preferable to heat and/or expose a coating film of the resin composition coated on the substrate. The coating method is not particularly limited, and examples thereof include a method of coating using a contact transfer type coating apparatus such as a roll coater, a reverse coater, or a bar coater, a non-contact type coating apparatus such as a spinner (rotary coating apparatus) or a curtain coater.

The coated film after the coating is preferably dried (prebaked). The drying method is not particularly limited, and examples thereof include: (1) a method of drying the mixture at a temperature of 80 to 120 ℃ inclusive, preferably 90 to 100 ℃ inclusive, for 60 to 120 seconds inclusive by a hot plate; (2) standing at room temperature for several hours to several days; (3) a method of removing the solvent by placing the mixture in a hot air heater or an infrared heater for several tens of minutes to several hours; and so on.

The resin composition may be cured while being dried.

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 is favorably advanced and the cured product is not thermally degraded or thermally decomposed. The heating temperature is, for example, preferably 80 ℃ to 300 ℃, more preferably 100 ℃ to 280 ℃, and still more preferably 120 ℃ to 250 ℃. The heating time is, for example, preferably 10 seconds to 12 hours, more preferably 1 minute to 6 hours, and still more preferably 2 minutes to 3 hours.

When a resin composition is exposed to light to form a cured product, the exposure conditions are not particularly limited as long as curing is satisfactorily performed. The exposure may be performed by, for example, irradiation with active energy rays such as ultraviolet rays and excimer laser. The dose of the energy ray to be irradiated is not particularly limited, and examples thereof include 3mJ/cm²Above 2000mJ/cm²The following.

Method for producing patterned cured film

When the 1 st and 2 nd resin compositions containing a photosensitive curing agent are used as the resin composition, a patterned cured film can be formed by applying a photolithography method.

Specifically, the patterned cured film can be manufactured by a method including the steps of:

a step of forming a coating film by coating the 1 st resin composition or the 2 nd resin composition containing a photosensitive curing agent on a substrate;

a step of exposing the coating film in a position-selective manner;

a step of patterning the coating film by developing the exposed coating film with a developing solution; and

and a step of heating the patterned coating film.

With respect to the patterned cured film, the film thickness thereof is as described above for the cured film.

In the above-described method for producing a patterned cured film, the coating method is as described above for the method for producing a cured film. The exposure conditions were as described above for the method of producing the cured film. The position-selective exposure is performed, for example, via a negative photomask. As for the heating conditions after exposure, the heat curing conditions described hereinbefore for the manufacturing method of the cured film can be applied.

The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Specific examples of the developer include an organic solvent (S) that the resin composition may contain; organic developer such as monoethanolamine, diethanolamine, triethanolamine and the like; for example, an alkaline aqueous solution containing sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, a quaternary ammonium salt, or the like at a concentration of 0.02% by mass or more and 10% by mass or less.

In the case where the resin composition is the 1 st resin composition containing a photosensitive curing agent, the organic solvent (S) that the resin composition may contain is preferable.

When the resin composition is the 2 nd resin composition, an alkaline developer is preferred as the developer. As the alkaline developer, for example, an aqueous tetramethylammonium hydroxide solution having a concentration of 0.05 to 10% by mass, preferably 0.05 to 3% by mass, is preferable.

[ examples ]

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

[ example 1]

After the inside of a glass three-necked flask having a capacity of 300mL was replaced with a nitrogen atmosphere, the internal temperature of the flask was set to 80 ℃. Next, 5.18g of diethylene glycol methyl ethyl ether (MEDG) was added to the flask.

Separately, a sample bottle made of glass and having a capacity of 300mL, containing 12 mass% of methacrylic acid and tricyclo [5.2.1.0 ] methacrylate^2,6]A polymerization solution was prepared from 29g of a monomer mixture of 17 mass% of decyl ester and 71 mass% of 3, 4-epoxycyclohexylmethyl methacrylate, 5g of dimethyl-2, 2' -azobis (2-methylpropionate) as a polymerization initiator, and MEDG62 g.

The resulting polymerization solution was added dropwise to a three-necked flask at 80 ℃ for 2 hours, and then stirred at 80 ℃ for 2 hours to continue the polymerization reaction.

As a result, 50g of a (meth) acrylic resin (resin P1) containing the following structural unit ratios of a MEDG solution (concentration: 30 mass%) of the (meth) acrylic resin was obtained. The numerical values below the brackets on the right are the ratio (% by mass) of each structural unit.

The molecular weight of the obtained (meth) acrylic resin was measured in terms of polystyrene by gel permeation chromatography, and the weight average molecular weight (Mw) was 9000.

[ chemical formula 64]

Then, 3g of an epoxy group-containing cyclic siloxane compound C1 having the following structure and 1g of 1-methylimidazole were added to the obtained solution of the resin P1. Then, the contents of the flask were stirred at 80 ℃ for 30 minutes to react the resin P1 with an epoxy group-containing cyclic siloxane compound, thereby obtaining a resin P2 as a siloxane-modified (meth) acrylic resin.

The formation of ester bonds and hydroxyl groups was confirmed by the reaction of the resin P1 with an epoxy group-containing cyclic siloxane compound by FT-IR measurement.

The molecular weight of the obtained resin P2 was measured by gel permeation chromatography in terms of polystyrene, and the weight average molecular weight (Mw) was 13000.

[ chemical formula 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, a compound represented by the following formula was used as a photopolymerization initiator.

[ chemical formula 66]

In example 2, comparative example 1, and comparative example 2, IR1010 (manufactured by BASF Japan) was used as an antioxidant. As the silane coupling agent, 3-glycidoxypropyltrimethoxysilane was used. As the surfactant, BYK-310(BYK Co., Ltd.) was used. As the organic solvent, MEDG, and Propylene Glycol Monomethyl Ether Acetate (PGMEA) were used.

The curable resin compositions of example 2, comparative example 1, and comparative example 2 were obtained by mixing the respective components of the types described in table 1 in the ratios (mass%) described in table 1 below. Using the resin compositions of example 2, comparative example 1 and comparative example 2 thus obtained, the relative dielectric constant of the cured product and the light transmittance of the cured product (wavelength 380 to 780nm) were measured according to the following formulations. The evaluation results are shown in table 1.

< determination of relative dielectric constant >

A coating film is formed by coating a resin composition on a silicon wafer by a spinner. The coating film thus formed was heated at 100 ℃ for 120 seconds, and then further heated at 230 ℃ for 20 minutes to form a cured film having a thickness of 1 μm.

The relative dielectric constant of the formed cured film was measured using SSM-495 (manufactured by Semilab Japan KK) at a measurement frequency of 0.1 MHz.

< measurement of light transmittance >

A resin composition is applied to a glass substrate by a spinner to form a coating film. The formed coating film was heated at 100 ℃ for 120 seconds. The heated coating film was exposed to 20mW/cm of light using an exposure apparatus (TME-150PRO, Topcon Co., Ltd.)²The coating film is exposed. The exposed coating film was heated at 230 ℃ for 20 minutes to obtain a cured film having a film thickness of 3 μm. The light transmittance (wavelength: 380 to 780nm) of the obtained cured film was measured by MCPD-3700 (available from Otsuka electronics Co., Ltd.).

[ Table 1]

As is apparent from table 1, the resin composition of example 2 containing the resin P2 as a siloxane-modified (meth) acrylic resin obtained by the reaction of a (meth) acrylic resin containing a structural unit derived from a (meth) acrylate having an alicyclic epoxy group with an epoxy group-containing siloxane compound provided a transparent cured product having a low relative dielectric constant.

On the other hand, the resin compositions of comparative examples 1 and 2, which include the (meth) acrylic resin not modified with the epoxy group-containing siloxane compound or the (meth) acrylic resin and the epoxy group-containing siloxane compound in combination, provide transparent cured products having high relative dielectric constants.

[ example 3]

The monomer mixture used in example 1 was changed to contain 14 mass% of methacrylic acid and tricyclo [5.2.1.0 ] methacrylate^2,6]17 mass% of decyl ester, and 3, 4-epoxy tricyclo [5.2.1.0 ] acrylate^2,6]In the same manner as in example 1 except for using a monomer mixture of 69 mass% of decan-1-yl ester, 50g of a (meth) acrylic resin (resin P3) containing the following structural unit ratios was obtained as a MEDG solution (concentration: 30 mass%). The numerical values below the brackets on the right are the ratio (% by mass) of each structural unit.

The molecular weight of the obtained (meth) acrylic resin was measured by gel permeation chromatography in terms of polystyrene, and the weight average molecular weight (Mw) was 9500.

[ chemical formula 67]

Next, in the same manner as in example 1, resin P3 was reacted with the epoxy group-containing cyclic siloxane compound used in example 1 to obtain resin P4 as a siloxane-modified (meth) acrylic resin.

The formation of ester bonds and hydroxyl groups was confirmed by the reaction of the resin P3 with an epoxy group-containing cyclic siloxane compound by FT-IR measurement.

The molecular weight of the obtained resin P4 was measured by gel permeation chromatography in terms of polystyrene, and the weight average molecular weight (Mw) was 125000.

[ example 4, comparative example 3, and comparative example 4]

Curable resin compositions of example 4, comparative example 3 and comparative example 4 were obtained in the same manner as in example 2, comparative example 1 and comparative example 2, except that the resin P1 was changed to the resin P3 and the resin P2 was changed to the resin P4, according to the following table 2. Using the resin compositions of example 4, comparative example 3 and comparative example 4 thus obtained, the relative dielectric constant of the cured product and the light transmittance of the cured product (wavelength 380 to 780nm) were measured in the same manner as in example 2, comparative example 1 and comparative example 2. The evaluation results are shown in Table 2.

[ Table 2]

As is apparent from table 2, the resin composition of example 4 containing the resin P4 as a siloxane-modified (meth) acrylic resin obtained by the reaction of a (meth) acrylic resin containing a structural unit derived from a (meth) acrylate having an alicyclic epoxy group with an epoxy group-containing siloxane compound provided a transparent cured product having a low relative dielectric constant.

On the other hand, the resin compositions of comparative examples 3 and 4, which include a (meth) acrylic resin that is not modified with an epoxy group-containing siloxane compound, or a (meth) acrylic resin and an epoxy group-containing siloxane compound in combination, provide transparent cured products having a high relative dielectric constant.

Claims (12)

1. A resin composition comprising a silicone-modified (meth) acrylic resin (A1),

the siloxane-modified (meth) acrylic resin (A1) is a reaction product of a (meth) acrylic resin (A-I) containing a structural unit derived from a (meth) acrylate having an alicyclic epoxy group and an epoxy group-containing cyclic siloxane compound (A-II) represented by the following formula (a-I),

[ chemical formula 1]

In the formula (a-I), R^a01And R^a02Represents a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x 1R^a01And x 1R^a02At least 2 of them are epoxy group-containing monovalent groups.

2. The resin composition according to claim 1, wherein the amount of the structural unit derived from a (meth) acrylate having an alicyclic epoxy group in the (meth) acrylic resin (A-I) is 50% by mass or more.

3. The resin composition according to claim 1 or 2, wherein the siloxane-modified (meth) acrylic resin (a1) is a reaction product obtained by reacting 100 parts by mass of the (meth) acrylic resin (a-I) with 1 part by mass or more and 50 parts by mass or less of the epoxy group-containing cyclic siloxane compound (a-II).

4. The resin composition according to claim 1 or 2, wherein the (meth) acrylate having an alicyclic epoxy group contains a polycyclic alkane skeleton.

5. The resin composition according to claim 1 or 2, comprising the silicone-modified (meth) acrylic resin (A1), a photopolymerizable monomer (B), and a photopolymerization initiator (C),

the siloxane-modified (meth) acrylic resin (a1) contains a structural unit having an alkali-soluble group.

6. A cured product obtained by curing the resin composition according to any one of claims 1 to 5 by heating and/or exposure to light.

7. A method for producing a cured product, which comprises heating and/or exposing the resin composition according to any one of claims 1 to 5.

8. A method for producing a patterned cured film, comprising the steps of:

a step of applying the resin composition according to claim 5 onto a substrate to form a coating film;

a step of exposing the coating film in a position-selective manner;

a step of developing the exposed coating film with an alkaline developer to pattern the coating film; and

a step of heating the patterned coating film.

9. A siloxane-modified (meth) acrylic resin which is a reaction product of a (meth) acrylic resin (A-I) containing a structural unit derived from a (meth) acrylate having an alicyclic epoxy group and an epoxy group-containing cyclic siloxane compound (A-II) represented by the following formula (a-I),

[ chemical formula 2]

In the formula (a-I), R^a01And R^a02Represents a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x 1R^a01And x 1R^a02At least 2 of them are epoxy group-containing monovalent groups.

10. The siloxane-modified (meth) acrylic resin according to claim 9, wherein the amount of the structural unit derived from a (meth) acrylate having an alicyclic epoxy group in the (meth) acrylic resin (a-I) is 50% by mass or more.

11. The silicone-modified (meth) acrylic resin according to claim 9 or 10, which is a reaction product obtained by reacting 100 parts by mass of the (meth) acrylic resin (a-I) with 1 part by mass or more and 50 parts by mass or less of the epoxy group-containing cyclic siloxane compound (a-II).

12. The siloxane-modified (meth) acrylic resin according to claim 9 or 10, wherein the (meth) acrylate having an alicyclic epoxy group contains a polycyclic alkane skeleton.