KR20240002938A - Curable resins composition - Google Patents

Abstract

[Problem] A curable resin composition capable of forming a microlens having excellent solvent resistance and a high refractive index, a microlens made of a cured product of the curable resin composition, and a method for producing a microlens using the above-described curable resin composition. What it offers.
[Solution] A curable resin composition comprising a resin (A) and a solvent (S) and which can be cured by heating through a crosslinking reaction of epoxy groups and/or a crosslinking reaction of isocyanate groups, wherein the resin (A) As, it has a (meth)acrylate unit having a biphenyl group having one or more cyano groups, and also has at least one of a unit (a2a) having an epoxy group and a unit (a2b) having a functional group that reacts with and crosslinks the epoxy group. , or a resin having at least one of a unit (a3a) having a block isocyanate group and a unit (a3b) having a functional group that reacts with the isocyanate group and crosslinks is used.

Description

Curable resin composition {CURABLE RESINS COMPOSITION}

The present invention relates to a curable resin composition containing a structural unit of a specific structure, a microlens composed of a cured product of the curable resin composition, and a method for producing a microlens using the above-described curable resin composition.

Conventionally, solid-state imaging devices have been used in cameras, video cameras, etc. For this solid-state imaging device, a charge-coupled device (CCD) image sensor or a complementary metal-oxide semiconductor (CMOS) image sensor is used. The image sensor is equipped with a fine condensing lens (hereinafter referred to as a micro lens) for the purpose of improving light collection rate.

These microlenses are typically made of resin materials or cured products of curable compounds. As a composition for forming a microlens, a curable composition containing a curable acrylic resin containing a styrene-based unit has been proposed (for example, see Patent Document 1).

Elements including microlenses are often exposed to chemical solutions such as organic solvents when manufacturing devices including the elements. For this reason, excellent solvent resistance is required for microlenses. By using the curable composition described in Patent Document 1, a microlens with excellent solvent resistance can be formed.

[Patent Document 1] Japanese Patent Application Publication No. 2016-194079

Recently, miniaturization of micro lenses is progressing. For this reason, in order to improve the light collection rate to the photodiode, the microlens is required to have a high refractive index.

The present invention has been made in view of these circumstances, and includes a curable resin composition capable of forming a micro lens having excellent solvent resistance and a high refractive index, a micro lens made of a cured product of the curable resin composition, and the curable resin described above. The purpose is to provide a method for manufacturing a micro lens using the composition.

The present inventors have provided a curable resin composition comprising a resin (A) and a solvent (S) and which can be cured by a crosslinking reaction of epoxy groups and/or an isocyanate group by heating, wherein the resin (A) As, it has a (meth)acrylate unit having a biphenyl group having one or more cyano groups, and also has at least one of a unit (a2a) having an epoxy group and a unit (a2b) having a functional group that reacts with and crosslinks the epoxy group. , or by using a resin having at least one of a unit (a3a) having a block isocyanate group and a unit (a3b) having a functional group that reacts with and crosslinks the isocyanate group, it was found that the above problem could be solved, leading to the present invention. . Specifically, the following is provided.

The first aspect of the present invention is a curable resin composition comprising a resin (A) and a solvent (S), which can be cured by a crosslinking reaction of epoxy groups and/or a crosslinking reaction of isocyanate groups by heating. ,

The resin (A) contains a unit (a1) represented by the following formula (a),

The resin (A) has at least one of a unit (a2a) having an epoxy group and a unit (a2b) having a functional group that reacts with and crosslinks the epoxy group, or reacts with a unit (a3a) having a block isocyanate group and an isocyanate group. It is a curable resin composition that has at least one of the units (a3b) having a crosslinking functional group.

(In formula (a), R ¹ is a hydrogen atom or a methyl group, R ² is each independently a halogen atom or an organic group having 1 to 6 carbon atoms, x is an integer of 1 to 5, , y is an integer between 0 and 4, and z is an integer between 0 and 4.)

A second aspect of the present invention is a micro lens made of a cured product of the curable resin composition according to the first aspect.

A third aspect of the present invention includes applying the curable resin composition according to the first aspect to a substrate to form a coating film;

Heating the coating film to form a cured film,

Forming a mask with a shape according to the shape of the microlens to be formed on the cured film,

This is a method of manufacturing a micro lens, which includes forming a micro lens to which the shape of the mask is transferred by etching the cured film together with the mask.

According to the present invention, a curable resin composition capable of forming a microlens with excellent solvent resistance and a high refractive index, a microlens composed of a cured product of the curable resin composition, and production of a microlens using the above-described curable resin composition. A method can be provided.

≪Curable resin composition≫

The curable resin composition contains a resin (A) and a solvent (S).

The curable resin composition can be cured by heating through a crosslinking reaction of epoxy groups and/or a crosslinking reaction of isocyanate groups.

Resin (A) has at least one of a unit (a1) represented by formula (a), a unit (a2a) having an epoxy group, and a unit (a2b) having a functional group that reacts with and crosslinks the epoxy group, or a block isocyanate It has at least one of a unit (a3a) having a group and a unit (a3b) having a functional group that reacts with and crosslinks an isocyanate group.

If necessary, the curable resin composition may include a compound (B) having a functional group that reacts with and crosslinks an epoxy group, a compound (C) that has an epoxy group, a compound (D) that has a functional group that reacts and crosslinks an isocyanate group, and a compound (D) that has a block isocyanate group. It may contain a compound selected from compound (E).

In the curable resin composition, it is preferable that the resin (A) has a unit (a1), a unit (a2a), and a unit (a2b).

In the curable resin composition, the resin (A) has units (a1) and units (a2a), and the curable resin composition further includes a compound (B) having a functional group that reacts with and crosslinks an epoxy group. desirable.

In the curable resin composition, it is preferable that the resin (A) has a unit (a1) and a unit (a2b), and that the curable resin composition further contains a compound (C) that has an epoxy group.

Because it is easy to adjust the curable resin composition, it is preferable that the resin (A) has a unit (a1), a unit (a2a), and a unit (a2b).

Moreover, in the curable resin composition, it is preferable that the resin (A) has a unit (a1), a unit (a3a), and a unit (a3b).

In the curable resin composition, the resin (A) has a unit (a1) and a unit (a3a), and the curable resin composition further includes a compound (D) having a functional group that reacts with an isocyanate group and crosslinks. desirable.

In the curable resin composition, it is preferable that the resin (A) has the unit (a1) and the unit (a3b), and the curable resin composition further contains a compound (E) that has a blocked isocyanate group.

Because it is easy to adjust the curable resin composition, it is preferable that the resin (A) has a unit (a1), a unit (a3a), and a unit (a3b).

Hereinafter, essential or optional components that the curable resin composition may contain are explained.

[Suzy (A)]

The resin (A) contains a unit (a1) represented by the following formula (a), and has at least one of a unit (a2a) having an epoxy group and a unit (a2b) having a functional group that reacts with and crosslinks the epoxy group, or Alternatively, it has at least one of a unit (a3a) having a block isocyanate group and a unit (a3b) having a functional group that reacts with and crosslinks the isocyanate group.

(In formula (a), R ¹ is a hydrogen atom or a methyl group, R ² is each independently a halogen atom or an organic group having 1 to 6 carbon atoms, x is an integer of 1 to 5, , y is an integer between 0 and 4, and z is an integer between 0 and 4.)

Additionally, the resin (A) includes units other than unit (a1), unit (a2a), unit (a2b), unit (a3a), and unit (a3b), to the extent that the desired purpose is not impaired. You can do it.

These units may exist in the resin in a block shape or may exist randomly. In terms of the reactivity of the resin (A), it is preferable that each unit constituting the resin (A) exists randomly in the resin (A).

The resin (A) is not particularly limited as long as it contains the unit (a) and can be cured by heating through a crosslinking reaction of epoxy groups and/or a crosslinking reaction of isocyanate groups. Acrylic resin is preferable as the resin (A) because it is easy to synthesize and obtain. Here, the acrylic resin is a resin containing a unit derived from (meth)acrylic acid or a unit derived from a (meth)acrylic acid derivative. Examples of (meth)acrylic acid derivatives include (meth)acrylic acid ester, (meth)acrylic acid amide, N-substituted (meth)acrylic acid amide, and (meth)acrylonitrile.

Hereinafter, for the case where the resin (A) is an acrylic resin, unit (a1), unit (a2a), unit (a2b), unit (a3a), and unit (a3b) will be described.

[Unit(a1)]

The unit (a1) is a structural unit represented by the above formula (a). In formula (a), R ¹ is a hydrogen atom or a methyl group.

In formula (a), R ² is each independently a halogen atom or an organic group having 1 to 6 carbon atoms. Examples of organic groups include alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aliphatic acyl groups having 2 to 6 carbon atoms, and nitro groups. group, and cyano group.

As R ² , a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. An alkyl group of 3 or less is more preferred, and a methyl group is particularly preferred.

In formula (a), x is an integer between 1 and 5. y and z are each independently integers from 0 to 4.

x is preferably an integer of 1 to 3, preferably 1 or 2, and preferably 1. y and z are each preferably an integer of 0 to 2, preferably 0 or 1, and preferably 0.

If x, y, and z are the above values, the effect of increasing the refractive index is good, and the monomer that gives the unit (a1) is easy to obtain or synthesize.

Suitable specific examples of (meth)acrylate giving the unit represented by formula (a) include (4'-cyano-1,1'-biphenyl-4-yl) acrylate, (4'-cyano-1) ,1'-biphenyl-4-yl) methacrylate, (3'-cyano-1,1'-biphenyl-4-yl) methacrylate, and (2'-cyano-1,1' -Biphenyl-4-yl) methacrylate, etc. can be mentioned.

Among these, (4'-cyano-1,1'-biphenyl-4-yl) acrylate and (4'-cyano-1,1'-biphenyl-4-yl) methacrylate are desirable.

The ratio of the number of moles of the unit (a1) to the number of moles of all units of the resin (A) is not particularly limited as long as the desired effect is not impaired. The ratio of the number of moles of the unit (a1) to the number of moles of all units of the resin (A) is preferably 30 mol% or more and 70 mol% or less, and more preferably 35 mol% or more and 65 mol% or less.

In addition, the ratio of the mass of unit (a1) to the total mass of solids contained in the curable resin composition is preferably 30% by mass or more and 80% by mass or less, and more preferably 35% by mass or more and 70% by mass or less. desirable.

The unit (a1) may exist in the resin (A) in a block shape or may exist randomly.

[Unit with epoxy group (a2a)]

Examples of the unit (a2a) having an epoxy group include a unit represented by the following formula (a2-1).

(In formula (a2-1), R ^a21 represents a hydrogen atom or a methyl group, R ^a22 represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ^a23 represents 2 or more carbon atoms. Indicates an epoxy group-containing group of 30 or less.)

The number of carbon atoms of the alkylene group as R ^a22 is 1 to 5, preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2. Specific examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, and the like.

As R ^a23 , oxiran-2-yl group, 3,4-epoxy cyclohexyl group, and 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ] decan-1-yl group are preferable.

The group represented by -R ^a22 -R ^a23 includes glycidyl group (oxiran-2-yl methyl group), 3,4-epoxy cyclohexyl methyl group, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ] decane- Preferred are the 1-yl, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decan-8-yl group, and the 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decan-9-yl group.

Suitable specific examples of (meth)acrylate giving a unit represented by formula (a2-1) include glycidyl acrylate, glycidyl methacrylate, and (3,4-epoxycyclohexan-1-yl) acrylate. , (3,4-epoxycyclohexan-1-yl) methacrylate, (3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-1-yl) acrylate, (3,4-epoxytri Cyclo[5.2.1.0 ^2,6 ]decan-1-yl) methacrylate, (3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl) acrylate, (3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decan-8-yl) methacrylate, (3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl) acrylate, and (3,4 -Epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl) methacrylate, etc. can be mentioned.

Among these, glycidyl acrylate and glycidyl methacrylate are preferred.

The content of unit (a2a) in the resin (A) is not particularly limited as long as the curable resin composition cures well.

Curable resin relative to the sum of the number of moles of all units of resin (A), the number of moles of epoxy groups of components other than resin (A), and the number of moles of functional groups that react and crosslink with the epoxy groups of components other than resin (A) The ratio of the total number of moles of epoxy groups contained in all components contained in the composition and the total number of moles of functional groups that react and crosslink with the epoxy groups contained in all components contained in the curable resin composition is preferably 30 mol% or more, and is preferably 35 mol%. It is more preferable that it is 40 mol% or more, and it is especially preferable that it is 50 mol% or more.

When the above ratio is 30 mol% or more, the curable resin composition is likely to be well cured by reaction between an epoxy group and a functional group that reacts with and crosslinks the epoxy group.

The ratio between the number of moles of epoxy groups (M _E ) of all components contained in the curable resin composition and the number of moles of functional groups that react and crosslink with the epoxy groups of all components contained in the curable resin composition (M _HI ) is as M _E :M _HI 30:70 to 70:30 is preferable, 40:60 to 60:40 is more preferable, and 45:55 to 55:45 is still more preferable.

[Unit (a2b) having a functional group that reacts with an epoxy group and crosslinks]

The functional group that reacts with and crosslinks the epoxy group in unit (a2b) is not particularly limited as long as the functional group has reactivity with the epoxy group. Examples of the organic group include an organic group having a phenolic hydroxyl group, a primary amino group, a secondary amino group, a dicarboxylic anhydride group, or a carboxyl group.

When the resin (A) is an acrylic resin, the unit (a2b) is preferably a unit represented by the following formula (a2-2).

(In formula (a2-2), R ^a24 is a hydrogen atom or a methyl group, and R ^a25 is an oil having a phenolic hydroxyl group, a primary amino group, a secondary amino group, a mercapto group, a carboxy group, or a dicarboxylic acid anhydride group. It is a device.)

The organic group as R ^a25 may have two or more groups selected from a phenolic hydroxyl group, a primary amino group, a secondary amino group, a mercapto group, a carboxy group, and a dicarboxylic anhydride group. The organic group as R ^a25 preferably has 1 to 4 groups selected from phenolic hydroxyl groups, primary amino groups, secondary amino groups, mercapto groups, carboxyl groups, and dicarboxylic acid anhydride groups, and has 1 or 2 groups. It is more preferable to have one, and it is even more preferable to have one.

Preferred organic groups as R ^a25 include organic groups having a phenolic hydroxyl group or a primary amino group.

Specific examples of organic groups having phenolic hydroxyl groups include 4-hydroxyphenyl group, 3-hydroxyphenyl group, 2-hydroxyphenyl group, 4-hydroxynaphthalen-1-yl group, 6-hydroxynaphthalen-2-yl group, and and 7-hydroxynaphthalene-2-yl group.

Among these, 4-hydroxyphenyl group and 3-hydroxyphenyl group are preferable, and 4-hydroxyphenyl group is more preferable.

Specific examples of organic groups having a primary amino group include amino methyl group, 2-amino ethyl group, 3-amino propyl group, 4-amino phenyl group, 3-amino phenyl group, 2-amino phenyl group, 4-amino phenyl methyl group, 3-amino Phenyl methyl group, 2-amino phenyl methyl group, etc. are mentioned.

The content of unit (a2b) in resin (A) is not particularly limited as long as the curable resin composition cures well.

Curable resin relative to the sum of the number of moles of all units of resin (A), the number of moles of epoxy groups of components other than resin (A), and the number of moles of functional groups that react and crosslink with the epoxy groups of components other than resin (A) The ratio of the total number of moles of epoxy groups of all components contained in the composition and the total number of moles of functional groups that react and crosslink with the epoxy groups of all components contained in the curable resin composition is preferably 30 mol% or more, and more preferably 35 mol% or more. It is preferable, it is more preferable that it is 40 mol% or more, and it is especially preferable that it is 50 mol% or more.

When the above ratio is 30 mol% or more, the curable resin composition is likely to be well cured by reaction between an epoxy group and a functional group that reacts with and crosslinks the epoxy group.

The ratio between the number of moles of epoxy groups (M _E ) of all components contained in the curable resin composition and the number of moles of functional groups that react and crosslink with the epoxy groups of all components contained in the curable resin composition (M _HI ) is as M _E :M _HI 30:70 to 70:30 is preferable, 40:60 to 60:40 is more preferable, and 45:55 to 55:45 is still more preferable.

[Unit (a3a) having a block isocyanate group]

When the resin (A) is an acrylic resin, the block isocyanate group-containing unit (a3a) is preferably a unit derived from an acrylic acid ester having a block isocyanate group. As a unit derived from an acrylic acid ester having a block isocyanate group, a unit represented by the following formula (a3-1) is preferable.

(In formula (a3-1), R ^a31 is a hydrogen atom or a methyl group, R ^a32 is a single bond or an alkylene group having 1 to 5 carbon atoms, and R ^a33 is a block isocyanate group.)

In formula (a3-1), R ^a32 is a single bond or an alkylene group having 1 to 5 carbon atoms. The alkylene group may be linear or branched, and is preferably linear. Specific examples of the alkylene group as R ^a32 include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, butane- 1,4-diyl group, and pentane-1,5-diyl group.

Among these groups, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group are preferred, and methylene group is preferred. , ethane-1,2-diyl group, and propane-1,3-diyl group are more preferable, and ethane-1,2-diyl group is particularly preferable.

It is a block isocyanate group of unit (a3a). Blocked isocyanate group means a group in which an isocyanate group is blocked by a thermally dissociable protecting group.

This thermally dissociable protecting group is formed by reacting an isocyanate group with a blocking agent that provides a protecting group.

Examples of such blocking agents include alcohol-based compounds, phenol-based compounds, hydroxyl-containing compounds other than alcohol-based compounds and phenol-based compounds, active methylene-based compounds, amine-based compounds, imine-based compounds, oxime-based compounds, and carbamic acid-based compounds. compounds, urea-based compounds, acid amide-based (lactam-based) compounds, acid imide-based compounds, triazole-based compounds, pyrazole-based compounds, pyrrole-based compounds, mercaptan-based compounds, and bisulfite salts.

Examples of alcohol-based compounds include methanol, ethanol, isopropanol, n-butanol, sec-butanol, 2-ethylhexyl alcohol, 1-octanol, 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2 ,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2-(hydroxymethyl) furan, 2-methoxyethanol, methoxypropanol, 2-2-ethoxyethanol, n-prop Poxyethanol, 2-butoxyethanol, 2-(2-ethoxyethoxy) ethanol, 2-(4-ethoxybutoxy) ethanol, 2-(2-butoxyethoxy) ethanol, N,N-di Butyl-2-hydroxyacetoamide, N-morpholineethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethyl pyridine, furfuryl alcohol , 12-hydroxystearic acid, and 2-hydroxyethyl methacrylate.

Examples of phenolic compounds include phenol, o-cresol, m-cresol, p-cresol, 2-ethyl phenol, 3-ethyl phenol, 4-ethyl phenol, 2-n-propyl phenol, and 3-n-propyl. Phenol, 4-n-propyl phenol, 2-isopropyl phenol, 3-isopropyl phenol, 4-isopropyl phenol, 2-n-butyl phenol, 3-n-butyl phenol, 4-n-butyl phenol, 2- sec-Butyl Phenol, 3-sec-Butyl Phenol, 4-sec-Butyl Phenol, 2-tert-Butyl Phenol, 3-tert-Butyl Phenol, 4-tert-Butyl Phenol, 2-n-hexyl Phenol, 3-n -hexyl phenol, 4-n-hexyl phenol, 2-(2-ethylhexyl) phenol, 3-(2-ethylhexyl) phenol, 4-(2-ethylhexyl) phenol, 2-n-octyl phenol, 3- n-octyl phenol, 4-n-octyl phenol, 2-n-nonyl phenol, 3-n-nonyl phenol, 4-n-nonyl phenol, 2,3-dimethyl phenol, 2,4-dimethyl phenol, 2,5 -Dimethyl phenol, 2,6-dimethyl phenol, 3,4-dimethyl phenol, 3,5-dimethyl phenol, 2,3-di-n-propyl phenol, 2,4-di-n-propyl phenol, 2,5 -di-n-propyl phenol, 2,6-di-n-propyl phenol, 3,4-di-n-propyl phenol, 3,5-di-n-propyl phenol, 2,3-diisopropyl phenol, 2,4-diisopropyl phenol, 2,5-diisopropyl phenol, 2,6-diisopropyl phenol, 3,4-diisopropyl phenol, 3,5-diisopropyl phenol, 3-isopropyl- 2-methyl phenol, 4-isopropyl-2-methyl phenol, 5-isopropyl-2-methyl phenol, 6-isopropyl-2-methyl phenol, 2-isopropyl-3-methyl phenol, 4-isopropyl- 3-methyl phenol, 5-isopropyl-3-methyl phenol, 6-isopropyl-3-methyl phenol, 2-isopropyl-4-methyl phenol, 3-isopropyl-4-methyl phenol, 5-isopropyl- 4-methyl phenol, 6-isopropyl-4-methyl phenol, 2,3-di-n-butyl phenol, 2,4-di-n-butyl phenol, 2,5-di-n-butyl phenol, 2, 6-di-n-butyl phenol, 3,4-di-n-butyl phenol, 3,5-di-n-butyl phenol, 2,3-di-sec-butyl phenol, 2,4-di-sec- Butyl Phenol, 2,5-di-sec-Butyl Phenol, 2,6-di-sec-Butyl Phenol, 3,4-di-sec-Butyl Phenol, 3,5-di-sec-Butyl Phenol, 2,3 -di-tert-butyl phenol, 2,4-di-tert-butyl phenol, 2,5-di-tert-butyl phenol, 2,6-di-tert-butyl phenol, 3,4-di-tert-butyl Phenol, 3,5-di-tert-butyl phenol, 2,3-di-n-octyl phenol, 2,4-di-n-octyl phenol, 2,5-di-n-octyl phenol, 2,6- Di-n-octyl phenol, 3,4-di-n-octyl phenol, 3,5-di-n-octyl phenol, 2,3-di-2-ethylhexyl phenol, 2,4-di-2-ethyl Hexyl phenol, 2,5-di-2-ethylhexyl phenol, 2,6-di-2-ethylhexyl phenol, 3,4-di-2-ethylhexyl phenol, 3,5-di-2-ethylhexyl phenol , 2,3-di-n-nonyl phenol, 2,4-di-n-nonyl phenol, 2,5-di-n-nonyl phenol, 2,6-di-n-nonyl phenol, 3,4-di -n-nonyl phenol, 3,5-di-n-nonyl phenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2-bromo phenol, 3-bromo phenol, 4-bromo phenol 2 -Chloro phenol, 3-chloro phenol, 4-chloro phenol, 2-fluoro phenol, 3-fluoro phenol, 4-fluoro phenol, styrenated phenol (mono-, di-, or tri-formation of phenol by α-methyl benzyl group) substituent), methyl salicylate, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl 4-hydroxybenzoate, 4-[(dimethylamino) methyl] phenol, 4-[(dimethylamino) methyl] Nonyl phenol, bis(4-hydroxyphenyl) acetic acid, 2-hydroxypyridine, 2-hydroxyquinoline, 8-hydroxyquinoline, and 2-chloro-3-pyridinol.

Examples of hydroxyl group-containing compounds other than alcohol-based compounds and phenol-based compounds include N-hydroxysuccinimide and triphenyl silanol.

Active methylene-based compounds include, for example, meldrum acid, dialkyl malonate (e.g., dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-tert-butyl malonate, malonic acid). Di-2-ethylhexyl, methyl n-butyl malonate, ethyl-n-butyl malonate, methyl-sec-butyl malonate, ethyl sec-butyl malonate, methyl tert-butyl malonate, ethyl malonate-tert- butyl, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzyl methyl malonate, ethyl phenyl malonate, tert-butyl phenyl malonate, and isopropylidene malonate, etc.), alkyl acetoacetate (e.g. For example, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, tert-butyl acetoacetate, benzyl acetoacetate, and phenyl acetoacetate, etc.), 2-acetoacetoxyethyl Examples include methacrylate, acetylacetone, and ethyl cyanoacetate.

Amine-based compounds include, for example, dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis(2,2,6,6-tetramethylpiperidinyl)amine, and di-n-propyl. Amine, diisopropylamine, isopropylethylamine, 2,2,4-trimethylhexamethyleneamine, 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis(3 , 5,5-trimethylcyclohexyl) amine, piperidine, 2,6-dimethylpiperidine, tert-butylmethylamine, tert-butylethylamine, tert-butyl-n-propylamine, tert-butyl-n -Butylamine, tert-butylbenzylamine, tert-butylphenylamine, 2,2,6-trimethylpiperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino)-2,2, Examples include 6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6-methyl-2-piperidine, and 6-aminocaproic acid.

Examples of imine compounds include ethyleneimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine, and guanidine.

Examples of oxime-based compounds include formaldoxime, acetoaldoxime, acetooxime, methyl ethyl ketoxime, cyclohexanone oxime, diacetylmonooxime, benzophenone oxime, and 2,2,6,6-tetramethyl cyclo. Hexanone oxime, diisopropyl ketone oxime, methyl tert-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethyl pentyl ketone oxime, methyl 3-ethyl heptyl Ketone oxime, methyl isoamyl ketone oxime, n-amyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4'-dimethoxybenzophenone oxime, and 2- Heptanone oxime, etc. can be mentioned.

Examples of the carbamic acid-based compound include phenyl N-phenylcarbamate.

Examples of urea-based compounds include urea, thiourea, and ethylene urea.

Examples of acid amide-based (lactam-based) compounds include acetoanilide, N-methylacetoamide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5 - Piperazinedione, laurolactam, etc. are mentioned.

Examples of acid imide compounds include succinic acid imide, maleic acid imide, and phthalimide.

Examples of triazole-based compounds include 1,2,4-triazole and benzotriazole.

Examples of pyrazole-based compounds include pyrazole, 3,5-dimethylpyrazole, 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, and 3,5-di-tert-butylpyrazole. , 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5 -Phenylpyrazole, etc. can be mentioned.

Examples of pyrrole-based compounds include pyrrole, 2-methylpyrrole, 3-methylpyrrole, and 2,4-dimethylpyrrole.

Examples of mercaptan-based compounds include n-butyl mercaptan, n-dodecyl mercaptan, n-hexyl mercaptan, thiophenol, and pyridine-2-thiol.

Examples of bisulfite include soda bisulfite.

Among the units (a3a) represented by formula (a3-1) explained above, the following formula (a3-1-1) and formula (a3-1-2) are used because the resin is easy to prepare and has good curability. , or the structural unit represented by the formula (a3-1-3) is preferable.

(In formula (a3-1-1), formula (a3-1-2) and formula (a3-1-3), R ^a31 and R ^a32 are the same as in formula (a3-1) above, and R ^a36 is , each independently an organic group having 1 to 12 carbon atoms, R ^a37 each independently a halogen atom or an organic group having 1 to 6 carbon atoms, R ^a38 each independently having 1 or more carbon atoms It is an organic group of 6 or less, and a is an integer of 0 or more and 3 or less.)

In formula (a3-1-1), the organic group as R ^a36 includes an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy alkyl group having 2 to 12 carbon atoms, and a phenyl group. , a phenyl alkyl group having 7 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, etc. Among these groups, an alkyl group is preferable, an alkyl group with 1 to 6 carbon atoms is more preferable, an alkyl group with 1 to 3 carbon atoms is further preferable, and a methyl group or an ethyl group is particularly preferable.

The alkyl group may be linear or branched.

In formula (a3-1-1), the two R ^a36 may be the same or different.

In formula (a3-1-2), R ^a37 is a substituent on the pyrazolyl group, and each independently represents a halogen atom or an organic group having 1 to 6 carbon atoms.

Suitable examples of R ^a37 include a halogen atom, an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, and an aliphatic group with 2 to 6 carbon atoms. Acyl groups, etc. may be mentioned.

R ^a37 is preferably a halogen atom, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, and 1 or more carbon atoms. An alkyl group of 3 or less is more preferred, and a methyl group is particularly preferred.

In formula (a3-1-2), a is an integer of 0 or more and 3 or less, and an integer of 0 or more and 2 or less is preferable.

In formula (a3-1-3), the organic group as R ^a38 includes an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy alkyl group having 2 to 12 carbon atoms, and a phenyl group. , phenyl alkyl groups having 7 to 12 carbon atoms, etc.

In formula (a3-1-3), the two R ^a38 may be the same or different.

The unit (a3a) is introduced into the resin by copolymerizing a (meth)acrylic acid ester represented by the following formula (a3-I) with a monomer that provides another structural unit.

Among the (meth)acrylic acid esters represented by formula (a3-I), (meth)acrylic acid represented by the following formula (a3-I-1), formula (a3-I-2), or formula (a3-I-3) Ester is preferable, and (meth)acrylic acid ester represented by the following formula (a3-I-1a), formula (a3-I-2a), or formula (a3-I-3a) is more preferable.

The unit (a3a) may exist in the resin (A) in a block shape or may exist randomly. Since the isocyanate group formed in the unit (a3a) by heating tends to react favorably, it is preferable that the unit (a3a) exists randomly in the resin (A).

Suitable specific examples of (meth)acrylic acid ester giving unit (a3a) include the following compounds.

Among these, the following (meth)acrylic acid esters are preferable because it is easy to manufacture the resin and it is easy to obtain a resin with good curability.

The content of unit (a3a) in the resin (A) is not particularly limited as long as the curable resin composition cures well.

Regarding the sum of the number of moles of all units of resin (A), the number of moles of block isocyanate groups of components other than resin (A), and the number of moles of functional groups that react and crosslink with the isocyanate groups of components other than resin (A), The ratio of the total number of moles of block isocyanate groups contained in all components contained in the curable resin composition to the number of moles of functional groups that react and crosslink with the isocyanate groups contained in all components contained in the curable resin composition is preferably 30 mol% or more, and is preferably 35 mol%. It is more preferable that it is 40 mol% or more, and it is especially preferable that it is 50 mol% or more.

If the above ratio is 30 mol% or more, the curable resin composition is likely to be well cured by the reaction of the block isocyanate group and the functional group that reacts with the isocyanate group and crosslinks.

The ratio between the number of moles (M _B ) of the block isocyanate group of all the components contained in the curable resin composition and the number of moles (M _H2 ) of the functional group that reacts and crosslinks with the isocyanate group of all the components contained in the curable resin composition is M _B : M As _H2 , 30:70 to 70:30 is preferable, 40:60 to 60:40 is more preferable, and 45:55 to 55:45 is still more preferable.

[Unit (a3b) having a functional group that reacts with an isocyanate group and crosslinks]

In unit (a3b), the functional group that reacts with and crosslinks the isocyanate group includes an organic group containing active hydrogen. Examples of the organic group include organic groups having a hydroxyl group, a primary amino group, a secondary amino group, or a mercapto group.

When the resin (A) is an acrylic resin, the unit (a3b) is preferably a unit represented by the following formula (a3-2).

(In formula (a3-2), R ^a34 is a hydrogen atom or a methyl group, and R ^a35 is an organic group containing a hydroxyl group, a primary amino group, a secondary amino group, or a mercapto group.)

The number of hydroxyl groups, primary amino groups, secondary amino groups, or mercapto groups of the organic group as R ^a35 is not particularly limited as long as the desired effect is not impaired. Typically, the number of hydroxyl groups, primary amino groups, secondary amino groups, or mercapto groups possessed by the organic group as R ^a35 is preferably 1 or more and 4 or less, more preferably 1 or 2, and even more preferably 1. .

Preferred organic groups as R ^a35 include organic groups having a hydroxyl group or a primary amino group, and organic groups having a hydroxyl group are preferable.

When R ^a35 is an organic group having a hydroxyl group, the organic group may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. The number of hydroxyl groups of the organic group having a hydroxyl group as R ^a35 is not particularly limited as long as the desired effect is not impaired. Typically, the number of hydroxyl groups in the organic group having a hydroxyl group as R ^a35 is preferably 1 or more and 4 or less, more preferably 1 or 2, and still more preferably 1.

As R ^a35 , a hydrocarbon group substituted with a hydroxyl group is preferable. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. As the hydrocarbon group, an aliphatic hydrocarbon group is preferable. The aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. As the aliphatic hydrocarbon group, a straight-chain aliphatic hydrocarbon group is preferable.

When R ^a35 is a hydrocarbon group substituted with a hydroxyl group, the number of carbon atoms of the hydrocarbon group substituted with a hydroxyl group is not particularly limited. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms of the hydrocarbon group substituted with a hydroxyl group is preferably 1 to 20, more preferably 2 to 10, and especially preferably 2 to 6.

When the hydrocarbon group in the hydrocarbon group substituted with a hydroxyl group is an aromatic hydrocarbon group or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, the number of carbon atoms in the hydrocarbon group substituted with a hydroxyl group is preferably 6 to 20, and preferably 6 to 12. The following is more preferable.

Specific examples of aliphatic hydrocarbon groups substituted with hydroxyl groups include hydroxymethyl group, 2-hydroxyethyl group, 1-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 1-hydroxypropyl group, 4- Hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, 9-hydroxynonyl group, 10-hydroxydecyl group, 11-hydroxy group Roxyundecyl group, 12-hydroxydodecyl group, 13-hydroxytridecyl group, 14-hydroxytetradecyl group, 15-hydroxypentadecyl group, 16-hydroxyhexadecyl group, 17-hydroxyheptadecyl group , 18-hydroxyoctadecyl group, 19-hydroxynonadecyl group, and 20-hydroxyicosyl group.

Among these, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8 -Hydroxyoctyl group, 9-hydroxynonyl group, 10-hydroxydecyl group, 11-hydroxyundecyl group, 12-hydroxydodecyl group, 13-hydroxytridecyl group, 14-hydroxytetradecyl group, 15-hydroxypentadecyl group, 16-hydroxyhexadecyl group, 17-hydroxyheptadecyl group, 18-hydroxyoctadecyl group, 19-hydroxynonadecyl group, and 20-hydroxyicosyl group are preferred. .

Among these, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8 -Hydroxyoctyl group, 9-hydroxynonyl group, and 10-hydroxydecyl group are more preferable.

Among these, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, and 6-hydroxyhexyl group are more preferable.

Specific examples of aromatic hydrocarbon groups substituted with hydroxyl groups include 4-hydroxyphenyl group, 3-hydroxyphenyl group, 2-hydroxyphenyl group, 4-hydroxynaphthalen-1-yl group, 6-hydroxynaphthalen-2-yl group, and and 7-hydroxynaphthalene-2-yl group.

Among these, 4-hydroxyphenyl group and 3-hydroxyphenyl group are preferable, and 4-hydroxyphenyl group is more preferable.

Suitable specific examples of (meth)acrylic acid esters that give the unit represented by formula (a3-2) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and 3-hyde. Roxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl acrylate, and 3 -Hydroxyphenyl methacrylate, etc. can be mentioned.

Among these, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxyphenyl acrylate, and 4-hydroxyphenyl methacrylate are preferred.

The content of unit (a3b) in resin (A) is not particularly limited as long as the curable resin composition cures well.

Regarding the sum of the number of moles of all units of resin (A), the number of moles of block isocyanate groups of components other than resin (A), and the number of moles of functional groups that react and crosslink with the isocyanate groups of components other than resin (A), The ratio of the total number of moles of block isocyanate groups contained in all components contained in the curable resin composition to the number of moles of functional groups that react and crosslink with the isocyanate groups contained in all components contained in the curable resin composition is preferably 30 mol% or more, and is preferably 35 mol%. It is more preferable that it is 40 mol% or more, and it is especially preferable that it is 50 mol% or more.

If the above ratio is 30 mol% or more, the curable resin composition is likely to be well cured by the reaction of the block isocyanate group and the functional group that reacts with the isocyanate group and crosslinks.

The ratio of the number of moles (M _B ) of the block isocyanate group of all the components contained in the curable resin composition and the number of moles (M _H2 ) of the functional group that reacts and crosslinks with the isocyanate group of all the components contained in the curable resin composition is M _B : M As _H2 , 30:70 to 70:30 is preferable, 40:60 to 60:40 is more preferable, and 45:55 to 55:45 is still more preferable.

[Other units (a4)]

Resin (A) can be used in other units (a4) in addition to the above-described units (a1), (a2a), (a2b), (a3a), and units (a3b), to the extent that the desired effect is not impaired. ) may be included.

Examples of other units (a4) include units derived from (meth)acrylic acid ester. As the (meth)acrylic acid ester, a compound represented by the following formula (a4-1) is preferable.

In the above formula (a4-1), R ^a41 is a hydrogen atom or a methyl group. R ^a42 is an organic group that does not have a group containing active hydrogen and can react with an isocyanate group.

Examples of groups containing active hydrogen include hydroxyl groups, mercapto groups, amino groups, and carboxyl groups. This organic group may contain bonds or substituents other than hydrocarbon groups such as hetero atoms in the organic group. Additionally, the structure of this organic group may be linear, branched, cyclic, or a combination of these structures.

Substituents other than hydrocarbon groups in the organic group of R ^a42 are not particularly limited as long as the effect of the present invention is not impaired, and include a halogen atom, an alkyl thio group, an aryl thio group, a cyano group, a silyl group, an alkoxy group, an alkoxycarbonyl group, Nitro group, nitroso group, acyl group, acyloxy group, alkoxy alkyl group, alkyl thio alkyl group, aryloxy alkyl group, aryl thio alkyl group, N, N-di-substituted amino group (-NRR': R and R' are each independently hydrocarbon (represents a flag), etc. The hydrogen atom included in the substituent may be substituted with a hydrocarbon group. In addition, the structure of the hydrocarbon group included in the above substituent may be linear, branched, cyclic, or a combination of these structures.

As R ^a42 , an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group is preferable. These groups may be substituted with a halogen atom, an alkyl group, or a heterocyclic group. In addition, when 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 to 20, more preferably 1 to 15, and especially preferably 1 to 10. Examples of suitable alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, and sec-pentyl group. , tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and iso Examples include decyl group.

When R ^a42 is an aryl group, suitable examples of the aryl group include phenyl group, naphthalen-1-yl group, naphthalen-2-yl group, 4-phenyl phenyl group, 3-phenyl phenyl group, and 2-phenyl phenyl group.

When R ^a42 is an alicyclic group or a group containing an alicyclic group, suitable alicyclic groups include monocyclic alicyclic groups such as cyclopentyl group and cyclohexyl group, adamantyl group, norbornyl group, isobornyl group, and tricyclo group. Examples include polycyclic alicyclic groups such as nonyl group, tricyclodecyl group, and tetracyclododecyl group.

Monomers other than the above-mentioned (meth)acrylic acid esters that give the unit (a4) include aryl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers can be used individually or in combination of two or more types.

Examples of the aryl compound include aryl esters such as aryl acetate, aryl caproate, aryl caprylate, aryl laurate, aryl palmitate, aryl stearate, aryl benzoate, aryl acetoacetate, and aryl lactate; Aryloxy ethanol; etc. can be mentioned.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, and 1-methyl-2,2-dimethylpropyl vinyl. Alkyl vinyl ethers such as ether, 2-ethylbutyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether; vinylaryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinylnaphthyl ether, and vinylanthranyl ether; etc. can be mentioned.

Examples of vinyl esters include vinyl butyrate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, and vinyl. Examples include phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butylate, vinyl benzoate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

Examples of styrenes include styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene. , alkyl styrene such as acetoxymethyl styrene; Alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro Halostyrenes such as methylstyrene and 4-fluoro-3-trifluoromethylstyrene; etc. can be mentioned.

The content of the other units (a4) in the resin (A) is not particularly limited as long as the desired effect is not impaired. The content of other units (a4) is the sum of the amounts of unit (a1), unit (a2a), unit (a2b), unit (a3a), and unit (a3b) from the amount of all units of resin (A). This is the remaining amount excluding .

[Method for producing resin (A)]

The method for producing the resin (A) described above is not particularly limited. In general, resin (A) can be obtained by polymerizing a monomer mixture. The monomer mixture contains at least one of a monomer that gives the unit (a1), a monomer that gives the unit (a2a), and a monomer that gives the unit (a2b), or It contains a monomer that gives a unit (a3a) and at least one of a monomer that gives a unit (a3b). The monomer mixture contains monomers that provide other units as needed. Resin (A) can be obtained by polymerizing the monomer mixture in a suitable solvent in the presence of a polymerization initiator, for example, in a temperature range of 50°C or more and 120°C or less. Resin (A) can often be obtained as a solution in an organic solvent. Resin (A) obtained as a solution can be blended into the curable resin composition as is, or can be used as it is as a curable resin composition.

The weight average molecular weight of the resin (A) obtained by the above method is preferably 30,000 or more, more preferably 35,000 or more and 100,000 or less, and especially preferably 40,000 or more and 80,000 or less. The weight average molecular weight is the molecular weight in terms of polystyrene measured by GPC. Since the weight average molecular weight of the resin (A) is relatively large, it is easy to form a cured product excellent in solvent resistance and heat decomposition resistance.

The solution of resin (A) obtained as above is mixed with a poor solvent such as hexane, diethyl ether, methanol, and water, the resin (A) is precipitated, and the precipitated resin (A) is recovered. You may use it. The precipitated resin (A) is preferably washed after filtration and then dried under normal pressure or reduced pressure at a temperature that does not decompose the blocked isocyanate group in the unit (a3a). In this way, the powdery individual resin (A) can be recovered. Powdered resin is used by mixing it with a curable resin composition described later.

[Solvent (S)]

The curable resin composition contains a solvent (S) for purposes such as adjusting applicability and viscosity. As the solvent (S), an organic solvent is typically used. The type of organic solvent is not particularly limited as long as it can uniformly dissolve or disperse the components contained in the curable resin composition.

When the curable resin composition contains a component having a blocked isocyanate group, it is preferable that the solvent (S) does not have a group containing active hydrogen that can react with the isocyanate group. Examples of groups containing active hydrogen include hydroxyl groups, primary amino groups, secondary amino groups, and mercapto groups.

Specific examples of the solvent (S) that can be blended in the curable resin composition are:

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol mono-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene. Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (poly)alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether; (poly)alkylene 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. glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactic acid esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethyl 2-hydroxy-2-methylpropionate, 3-methoxymethyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Methyl hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, acetic acid n- Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid. Other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; Nitrogen-containing polar organic solvents such as N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N,N',N'-tetramethylurea, etc. etc. can be mentioned.

Among these, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether in that they do not have a group containing active hydrogen. (poly)alkylene glycol monoalkyl ether acetates such as acetate and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 3-heptanone; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, 3-methyl-3-methoxy butyl acetate, 3-methyl-3- Methoxy butyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl acetate, n-propyl acetate, other esters such as isopropyl acetate, n-butyl acetate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; Nitrogen-containing polar organic solvents such as N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N,N',N'-tetramethylurea, etc. etc. are preferable.

Additionally, from the viewpoint of solvent solubility of component (A), ketones such as cyclopentanone or cyclohexanone are preferable.

The solvent (S) can be used individually or in combination of two or more types.

The amount of solvent (S) used is not particularly limited as long as the desired effect is not impaired. From the viewpoint of film forming properties, the solvent (S) is used so that the solid content concentration of the curable resin composition is preferably 1 mass% or more and 50 mass% or less, and more preferably 5 mass% or more and 30 mass% or less.

[Compound (B) having a functional group that reacts with and crosslinks an epoxy group]

The curable resin composition may contain a compound (B) having a functional group that reacts with an epoxy group and crosslinks. The functional group that reacts with and crosslinks the epoxy group in compound (B) is not particularly limited as long as the functional group has reactivity with the epoxy group. Examples of the organic group include an organic group having a phenolic hydroxyl group, a primary amino group, a secondary amino group, a dicarboxylic anhydride group, or a carboxyl group. Compound (B) is not particularly limited as long as the desired effect is not impaired.

Examples of such compounds include amine compounds, compounds having a dicarboxylic anhydride group, aromatic polyol compounds, and polythiol compounds.

Additionally, various compounds commercially available as so-called curing agents for epoxy resins can be used as compound (B).

Examples of amine-based compounds include alkyl amines such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, tri-n-propylamine, and methyl diethylamine; alkanol amines such as ethanol amine, diethanol amine, triethanol amine, dimethyl ethanol amine, and methyl diethanol amine; Hydroxylamine, O-methyl hydroxylamine, O-ethyl hydroxylamine, N-methyl hydroxylamine, N,N-dimethyl hydroxylamine, N,O-dimethyl hydroxylamine, N-ethyl hydroxylamine, N,N-diethyl hydroxylamine, N,O-diethyl hydroxylamine, O,N,N-trimethyl hydroxylamine, N,N-dicarboxyethyl hydroxylamine, and N,N-disulfo Hydroxylamines such as ethyl hydroxylamine; Ethylene diamine, 1,2-propane diamine, 1,3-propane diamine, 1,4-butane diamine, 1,6-hexane diamine, N,N-diethyl ethylene diamine, N-ethyl-ethylene diamine, diethylene triamine Polyamines such as amine, triethylene tetramine, diamino diphenyl methane, diamino diphenyl sulfone, N-amino ethyl piperazine, metaxylylene diamine, dicyan diamide, and bis(paraminocyclohexyl) methane. You can.

Examples of aromatic polyol compounds include benzene diols such as hydroquinone, resorcinol, and catechol; Benzenetriols such as phloroglucinol, pyrogrollol, and 1,2,4-benzenetriol; 1,2-naphthalenediol, 1,3-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 1,5-naphthalenediol, 2 Naphthalenediol, such as 3-naphthalenediol, 2,6-naphthalenediol, and 2,7-naphthalenediol; Naphthalenetriol such as 1,4,5-naphthalenetriol, 1,2,4-naphthalenetriol, 1,3,8-naphthalenetriol, and 1,2,7-naphthalenetriol; Bisphenols such as bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol S, and bisphenol Z; Tetrahydroxybiphenyl such as 3,3',4,4'-tetrahydroxybiphenyl and 3,3',5,5'-tetrahydroxybiphenyl; Calisarane; Novolak resins such as phenol novolak, cresol novolak, and naphthol novolak can be mentioned.

As polythiol compounds, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1 ,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethyl propane-1,3-dithiol, 3 ,4-dimethoxy butane-1,2-dithiol, 2-methylcyclohexane 2,3-dithiol, 1,1-bis(mercaptomethyl) cyclohexane, thiomacidic acid bis(2-mercaptoethyl ester) , 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate) , Diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropylmethyl ether, 2,3-dimercaptopropylmethyl ether, 2,2-bis(mercaptomethyl)-1,3- Propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane bis(2-mercaptoacetate), Trimethylolpropane bis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), tetrakis(mercaptomethyl) methane aliphatic polythiol compounds such as; 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1, 4-bis(mercaptomethyl) benzene, 1,2-bis(mercaptoethyl) benzene, 1,3-bis(mercaptoethyl) benzene, 1,4-bis(mercaptoethyl) benzene, 1,2, 3-trimercapto benzene, 1,2,4-trimercapto benzene, 1,3,5-trimercapto benzene, 1,2,3-tris(mercaptomethyl) benzene, 1,2,4-tris(mercapto) methyl) benzene, 1,3,5-tris(mercaptomethyl) benzene, 1,2,3-tris(mercaptoethyl) benzene, 1,2,4-tris(mercaptoethyl) benzene, 1,3, 5-tris(mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di(p-methoxyphenyl) propane-2,2-dithiol, 1,3 -Diphenyl propane-2,2-dithiol, phenyl methane-1,1-dithiol, 2,4-di(p-mercaptophenyl)pentane, 1,2-bis(mercaptoethylthio)benzene, 1 ,3-bis(mercaptoethylthio) benzene, 1,4-bis(mercaptoethylthio) benzene, 1,2,3-tris(mercaptomethylthio) benzene, 1,2,4-tris(mercapto) methylthio) benzene, 1,3,5-tris(mercaptomethylthio) benzene, 1,2,3-tris(mercaptoethylthio) benzene, 1,2,4-tris(mercaptoethylthio) benzene, aromatic polythiol compounds such as 1,3,5-tris(mercaptoethylthio)benzene, and aromatic polythiol compounds containing sulfur atoms in addition to the mercapto group; Hydroxymethylsulfide bis(2-mercaptoacetate), Hydroxymethylsulfide bis(3-mercaptopropionate), Hydroxyethylsulfide bis(2-mercaptoacetate), Hydroxyethylsulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mer captoacetate), hydroxymethyldisulfide bis(3-mercaptopropionate), hydroxyethyldisulfide bis(2-mercaptoacetate), hydroxyethyldisulfide bis(3-mercaptopropionate), Hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl Ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mer Captopropionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), 4,4-thiodibutyric acid bis(2-mercaptoethyl ester) , dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 4,4-dithiodibutylic acid bis(2-mercaptoethyl ester), thiodiglycolic acid Bis(2,3-dimercaptopropyl ester), bis(2,3-dimercaptopropyl ester) thiodipropionate, bis(2,3-dimercaptopropyl ester) dithioglycolic acid, bis(2,3-dimercaptopropyl ester) dithiodipropionate, 3-dimercaptopropyl ester), 1,1,3,3-tetrakis(mercaptomethylthio) propane, 1,1,2,2-tetrakis(mercaptomethylthio) ethane, 3-mercaptomethyl- 1,5-dimercapto-2,4-dithiapentane, 1,2,5-trimercapto-4-thiapentane, 3,3-dimercaptomethyl-1,5-dimercapto-2,4-dithiapene Tan, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-dimer Captomethyl-1,9-dimercapto-2,5,8-trithianone, 3,7-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianone, 4,6-dimer Captomethyl-1,9-dimercapto-2,5,8-trithianone, 3-mercaptomethyl-1,6-dimercapto-2,5-dithiahexane, 3-mercaptomethylthio-1, 5-dimercapto-2-thiapentane, 1,1,2,2-tetrakis(mercaptomethylthio) ethane, 1,1,3,3-tetrakis(mercaptomethylthio) propane, 1,4, 8,11-tetramercapto-2,6,10-trithiaundecane, 1,4,9,12-tetramercapto-2,6,7,11-tetrathiadodecane, 2,3-dithia -1,4-Butanedithiol, 2,3,5,6-tetrathia-1,7-heptanedithiol, 2,3,5,6,8,9-hexathia-1,10-decanedithiol , 4,5-bis(mercaptomethylthio)-1,3-dithiorane, 4,6-bis(mercaptomethylthio)-1,3-dithian, 2-bis(mercaptomethylthio) methyl- 1,3-dithiethane, 2-(2,2-bis(mercaptomethylthio) ethyl)-1,3-dithiethane, 2-mercaptomethyl-6-mercapto-1,4-dithiacycloheptane aliphatic polythiol compounds containing sulfur atoms in addition to mercapto groups, such as; Heterocyclic compounds containing sulfur atoms in addition to mercapto groups such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole, glycerin di(mercaptoacetate), 2,4- Dimercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, Pentaerythritol Tris (3-mercaptopropionate), Pentaerythritol Bis (3-mercaptopropionate), Pentaerthritol Tris (thioglycolate), Dipentaerthritol Pentakis (3-mercaptopropionate) Compounds containing a hydroxy group in addition to a mercapto group such as mercaptopropionate) and hydroxymethyl tris(mercaptoethylthiomethyl) methane; 2,5-bis(mercaptomethyl)-1,4-dithiane, 2,5-bis(2-mercaptoethyl)-1,4-dithiane, 2,5-bis(3-mercaptopropyl) -1,4-dithiane, 2-(2-mercaptoethyl)-5-mercaptomethyl-1,4-dithiane, 2-(2-mercaptoethyl)-5-(3-mercaptopropyl) -1,4-dithiane, 2-mercaptomethyl-5-(3-mercaptopropyl)-1,4-dithiane, 2,4-bis(mercaptomethyl)-1,3-dithiolane, 2 -Mercaptomethyl-5-mercapto-1,3-dithiolane, 2,2-bis(mercaptomethyl)-1,3-dithiolane, 2-(3-mercaptopropyl)-4-mercaptomethyl -1,3-dithiolane, 2,2-bis(mercaptomethyl)-1,3,5-trithian, 2,4,5-tris(mercaptomethyl)-1,3-dithiolane, 2, 2-bis(mercaptomethyl)-5-mercapto-1,3-dithiolane, 2-(1,2-dimercaptoethyl)-4-mercaptomethyl-1,3-dithiolane, 2-(1 ,2-dimercaptoethyl)-4-mercapto-1,3,5-trithian, 2-(3-mercaptopropyl)-4,5-bis(mercaptomethyl)-1,3-dithiolane, 2,2,4,5-Tetrakis(mercaptomethyl)-1,3-dithiolane, 2-(1,2-dimercaptoethyl)-4,5-bis(mercaptomethyl)-1,3- Cyclic compounds such as dithiorane, etc. can be mentioned.

For resin (A), a homopolymer consisting only of the above-mentioned unit (a2b) or a copolymer containing the above-mentioned unit (a2b) but not corresponding to resin (A) can also be used as compound (B).

The amount of compound (B) used is not particularly limited as long as the curable resin composition is cured well.

Curable resin relative to the sum of the number of moles of all units of resin (A), the number of moles of epoxy groups of components other than resin (A), and the number of moles of functional groups that react and crosslink with the epoxy groups of components other than resin (A) The ratio of the total number of moles of epoxy groups of all components contained in the composition and the total number of moles of functional groups that react and crosslink with the epoxy groups of all components contained in the curable resin composition is preferably 30 mol% or more, and more preferably 35 mol% or more. It is preferable, it is more preferable that it is 40 mol% or more, and it is especially preferable that it is 50 mol% or more.

When the above ratio is 30 mol% or more, the curable resin composition is likely to be well cured by reaction between an epoxy group and a functional group that reacts with and crosslinks the epoxy group.

The ratio of the number of moles (M _E ) of the epoxy group of all the components contained in the curable resin composition and the number of moles (M _HI ) of the functional group that reacts and crosslinks with the epoxy group of all the components contained in the curable resin composition is as M _E :M _HI 30:70 to 70:30 is preferable, 40:60 to 60:40 is more preferable, and 45:55 to 55:45 is still more preferable.

[Compound (C) having an epoxy group]

The curable resin composition may contain a compound (C) having an epoxy group. Compound (C) is preferably a compound having two or more epoxy groups. Compound (C) is not particularly limited as long as the desired effect is not impaired.

Examples of compounds having two or more epoxy groups include 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. functional epoxy resin; Glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxy resins such as tetraglycidyl amino diphenylmethane, triglycidyl p-amino phenol, tetraglycidyl metaxylene diamine, and tetraglycidyl bisamino methyl cyclohexane; Heterocyclic epoxy resins such as triglycidyl isocyanurate; Phloroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenyl methane triglycidyl ether, glycerin triglycidyl ether, 2-[4-(2,3-epoxypropoxy) phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy) phenyl]ethyl]phenyl]propane, and 1,3-bis[4-[1-[4-( 2,3-epoxypropoxy) phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy) phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol Tri-functional epoxy resin, etc.; and tetrafunctional epoxy resins such as tetrahydroxyphenyl ethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxy biphenyl.

Regarding the resin (A), a homopolymer consisting only of the above-mentioned unit (a2a) or a copolymer containing the above-mentioned unit (a2a) but not corresponding to the resin (A) can also be used as the compound (C).

The amount of compound (C) used is not particularly limited as long as the curable resin composition is cured well.

Curable resin relative to the sum of the number of moles of all units of resin (A), the number of moles of epoxy groups of components other than resin (A), and the number of moles of functional groups that react and crosslink with the epoxy groups of components other than resin (A) The ratio of the total number of moles of epoxy groups of all components contained in the composition and the total number of moles of functional groups that react and crosslink with the epoxy groups of all components contained in the curable resin composition is preferably 30 mol% or more, and more preferably 35 mol% or more. It is preferable, it is more preferable that it is 40 mol% or more, and it is especially preferable that it is 50 mol% or more.

When the above ratio is 30 mol% or more, the curable resin composition is likely to be well cured by reaction between an epoxy group and a functional group that reacts with and crosslinks the epoxy group.

The ratio of the number of moles (M _E ) of the epoxy group of all the components contained in the curable resin composition and the number of moles (M _HI ) of the functional group that reacts and crosslinks with the epoxy group of all the components contained in the curable resin composition is as M _E :M _HI 30:70 to 70:30 is preferable, 40:60 to 60:40 is more preferable, and 45:55 to 55:45 is still more preferable.

[Compound (D) having a functional group that reacts with an isocyanate group and crosslinks]

The curable resin composition may contain a compound (D) having a functional group that reacts with an isocyanate group and crosslinks. Compound (D) is preferably a compound having two or more active hydrogens. Compound (D) is not particularly limited as long as the desired effect is not impaired.

Functional groups that react and crosslink with isocyanate groups include hydroxyl groups, primary amino groups, secondary amino groups, and mercapto groups. Among these, hydroxyl group and primary amino group are preferable, and hydroxyl group is more preferable.

Examples of the compound (D) include amine-based compounds and polyol-based compounds.

As amine-based compounds, ethylene diamine, 1,2-propane diamine, 1,3-propane diamine, 1,4-butane diamine, 1,6-hexane diamine, N,N-diethyl ethylene diamine, and N-ethyl-ethylene. Diamine, diethylene triamine, triethylene tetramine, diamino diphenyl methane, diamino diphenyl sulfone, N-amino ethyl piperazine, metaxylene diamine, dicyan diamide, and bis(paraminocyclohexyl) methane, etc. of polyamines.

Polyol-based compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, glycerin, diglycerol, pentaerythritol, dipentaerythritol, and trimethyl. aliphatic polyols such as all propane, sorbitol, and sucrose; alkylene oxide adducts of aliphatic polyols, such as ethylene oxide adducts of the above-mentioned aliphatic polyols, propylene oxide adducts of the above-mentioned aliphatic polyols, and ethylene oxide/propylene oxide co-adducts of the above-mentioned aliphatic polyols; benzene diols such as hydroquinone, resorcinol, and catechol; Benzenetriols such as phloroglucinol, pyrogrollol, and 1,2,4-benzenetriol; 1,2-naphthalenediol, 1,3-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 1,5-naphthalenediol, 2 Naphthalenediol, such as 3-naphthalenediol, 2,6-naphthalenediol, and 2,7-naphthalenediol; Naphthalenetriol such as 1,4,5-naphthalenetriol, 1,2,4-naphthalenetriol, 1,3,8-naphthalenetriol, and 1,2,7-naphthalenetriol; Bisphenols such as bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol S, and bisphenol Z; Tetrahydroxybiphenyl such as 3,3',4,4'-tetrahydroxybiphenyl and 3,3',5,5'-tetrahydroxybiphenyl; Calisarane; Novolak resins such as phenol novolak, cresol novolak, and naphthol novolak can be mentioned.

Regarding the resin (A), a homopolymer consisting only of the above-mentioned unit (a3b) or a copolymer containing the above-mentioned unit (a3b) but not corresponding to the resin (A) can also be used as the compound (D).

The amount of compound (D) used is not particularly limited as long as the curable resin composition is cured well.

Regarding the sum of the number of moles of all units of resin (A), the number of moles of block isocyanate groups of components other than resin (A), and the number of moles of functional groups that react and crosslink with the isocyanate groups of components other than resin (A), The ratio of the total number of moles of block isocyanate groups contained in all components contained in the curable resin composition to the number of moles of functional groups that react and crosslink with the isocyanate groups contained in all components contained in the curable resin composition is preferably 30 mol% or more, and is preferably 35 mol%. It is more preferable that it is 40 mol% or more, and it is especially preferable that it is 50 mol% or more.

When the above ratio is 30 mol% or more, the curable resin composition is likely to be well cured by reaction between the block isocyanate group and the functional group that reacts and crosslinks the isocyanate group.

The ratio of the number of moles (M _B ) of the block isocyanate group of all the components contained in the curable resin composition and the number of moles (M _H2 ) of the functional group that reacts and crosslinks with the isocyanate group of all the components contained in the curable resin composition is M _B : M As _H2 , 30:70 to 70:30 is preferable, 40:60 to 60:40 is more preferable, and 45:55 to 55:45 is still more preferable.

[Compound (E) having a block isocyanate group]

The curable resin composition may contain compound (E), which is a compound having two or more isocyanate groups blocked by a blocking agent. Compound (E) can be obtained by reacting a blocking agent with a compound having two or more isocyanate groups.

Examples of compounds having two or more isocyanate groups include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; Alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tolylene diisocyanate; Tolylene diisocyanate, 4,4'-diphenyl methane diisocyanate, 2,4'-diphenyl methane diisocyanate, naphthalene diisocyanate, xylene diisocyanate, tricine diisocyanate, p-phenylene diisocyanate, naphthylene diisocyanate Aromatic diisocyanates such as isocyanate; Dicyclohexylmethane-4,4'-diisocyanate, its biuret form, isocyanurate form, adduct form of trimethylolpropane, etc. are mentioned.

The blocking agent is as described above for the unit (a3a) contained in the resin (A).

Regarding the resin (A), a homopolymer consisting only of the above-mentioned unit (a3a) or a copolymer containing the above-mentioned unit (a3a) but not corresponding to the resin (A) can also be used as the compound (E).

The amount of compound (E) used is not particularly limited as long as the curable resin composition is cured well.

Regarding the sum of the number of moles of all units of resin (A), the number of moles of block isocyanate groups of components other than resin (A), and the number of moles of functional groups that react and crosslink with the isocyanate groups of components other than resin (A), The ratio of the total number of moles of block isocyanate groups contained in all components contained in the curable resin composition to the number of moles of functional groups that react and crosslink with the isocyanate groups contained in all components contained in the curable resin composition is preferably 30 mol% or more, and is preferably 35 mol%. It is more preferable that it is 40 mol% or more, and it is especially preferable that it is 50 mol% or more.

When the above ratio is 30 mol% or more, the curable resin composition is likely to be well cured by reaction between the block isocyanate group and the functional group that reacts and crosslinks the isocyanate group.

The ratio of the number of moles (M _B ) of the block isocyanate group of all the components contained in the curable resin composition and the number of moles (M _H2 ) of the functional group that reacts and crosslinks with the isocyanate group of all the components contained in the curable resin composition is M _B : M As _H2 , 30:70 to 70:30 is preferable, 40:60 to 60:40 is more preferable, and 45:55 to 55:45 is still more preferable.

[Other ingredients (F)]

The curable resin composition may contain additives as needed. Examples of such additives include acid generators, stabilizers, adhesion enhancers, cross-linking agents, curing accelerators, surfactants, curing agents, antioxidants, adhesion aids, anti-foaming agents, and polymerization inhibitors such as thermal polymerization inhibitors. These additives may be used individually or may be used in combination of two or more types.

<Hardened product>

A cured product is formed by molding the above curable resin composition into a desired shape and then heating it. This cured product has a high refractive index because the resin (A) contains the unit (a1).

The refractive index of the cured product is preferably 1.60 or more, more preferably 1.61 or more, and even more preferably greater than 1.62. The upper limit of the refractive index is not particularly limited, but is, for example, 1.70 or less.

≪Method for producing hardened product≫

Hereinafter, the method for producing the above-mentioned cured product will be described.

The method for producing the cured product is typically:

A molding process of molding the above curable resin composition into a predetermined shape;

It includes a curing process of curing the molded curable resin composition by heating.

In the molding process, the shape of the curable resin composition after molding or the method of molding the curable resin composition is not particularly limited.

Methods for molding the curable resin composition include, for example, a method of applying the curable resin composition onto a substrate and then removing the solvent (S) from the coating film, or a method of removing the solvent (S) from the coating film after placing the liquid of the curable resin composition on the substrate. Examples include a method of removing (S), and a method of removing the solvent (S) from the curable resin composition in the mold after filling the curable resin composition into a mold having a concave portion of a predetermined shape.

The method of applying the curable resin composition onto the substrate is not particularly limited. For example, the curable resin composition is applied onto the substrate using a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or slit coater, or a non-contact type coating device such as a spinner (rotary coating device) or curtain flow coater. , a coating film can be formed by applying it to a predetermined film thickness.

After molding the curable resin composition by the above method, the curable resin is molded into a predetermined shape by appropriately heat treating (prebake (post apply bake (PAB)) treatment) to remove the solvent (S). The composition can be obtained.

The prebake temperature is appropriately selected in consideration of the boiling point of the solvent (S), etc. The prebaking may be performed at low temperature under reduced pressure to prevent the curable resin composition from curing before the solvent (S) is sufficiently removed.

The prebake method is not particularly limited, and for example, (i) using a hot plate at 80°C or higher and 120°C or lower (preferably 85°C or higher and 100°C or lower, more preferably 85°C or higher and 95°C or lower) (ii) a method of drying at a temperature of 60 seconds to 120 seconds; (ii) a method of leaving the product at room temperature within a range of several hours to several days; (iii) a method of drying in a warm air heater or infrared heater for a period of not less than several tens of minutes but not more than several hours; Any of the methods of inserting the base material and removing the solvent (S) within the range may be used.

By heating (post-baking) the curable resin composition formed as described above, a cured product of the curable resin composition is formed. The curing temperature is not particularly limited as long as curing of the curable resin composition progresses satisfactorily and thermal denaturation or thermal decomposition of the cured product does not occur.

The upper limit of the curing temperature is preferably 250°C or lower, and preferably 230°C or lower, for example. The lower limit of the curing temperature is preferably 120°C or higher, and more preferably 130°C or higher.

In addition, the curable resin composition can be cured at low temperature, for example, curing conditions can be set to 180°C or lower, and curing conditions can be set to 150°C or lower.

By the above method, a cured product of the curable resin composition is produced.

≪Method of manufacturing micro lenses≫

Hereinafter, a method for manufacturing a micro lens using the above resin will be described.

The manufacturing method of the microlens using the above-mentioned curable resin composition is not particularly limited.

Typically, microlenses are:

Forming a coating film made of the above-mentioned curable resin composition,

Heating the coating film to form a cured film,

Forming a mask with a shape according to the shape of the microlens to be formed on the cured film,

It is manufactured by a method that includes forming a micro lens onto which the shape of the mask is transferred by etching the cured film together with the mask.

A coating film is usually formed on a substrate. Examples of the substrate include image elements including photodiodes (organic photodiodes, inorganic photodiodes, etc.), silicon wafers with color filter layers, etc., and, in some cases, substrates such as silicon wafers with additional anti-reflection films.

The method of applying the curable resin composition onto the substrate is not particularly limited. Specific examples of the method of applying the curable resin composition onto the substrate include the method described above for the method of producing the cured product.

The formed coating film may be appropriately heat treated (pre-bake (post-apply bake (PAB))) to remove the solvent in the coating film.

The specific method of prebaking is also as described above for the method of producing the cured product.

The upper limit of the curing temperature of the coating film when forming the cured film is, for example, preferably 250°C or lower, and preferably 230°C or lower. The lower limit of the curing temperature is preferably 120°C or higher, and more preferably 130°C or higher.

From the viewpoint of process construction when using an organic photo diode, the curing conditions may be, for example, 180°C or lower, or 150°C or lower.

The thickness of the cured film is preferably in the range of 100 nm to 4.0 μm, more preferably 400 nm to 2.0 μm.

Next, a mask with a shape corresponding to the shape of the microlens to be formed is formed on the cured film. The method of forming the mask is not particularly limited.

Typically, the mask is

Forming a dot pattern using a photosensitive composition so that the dots are located at positions corresponding to the positions of the microlenses on the cured film,

It is formed by a method that includes deforming the dots into a lens shape by heating.

By etching the cured film together with the mask, a micro lens onto which the shape of the mask is transferred is formed.

The etching method is preferably dry etching. Dry etching is not particularly limited, and examples include dry etching using plasma (oxygen, argon, CF ₄ , etc.), corona discharge, etc.

By going through the above steps and using the above resin, it is possible to form a microlens with a high refractive index and little dimensional change or decrease in transparency when used in a high temperature environment. For this reason, the microlens formed by the above method is suitably used in various applications.

The diameter of the microlens formed is preferably 20 μm or less, more preferably 5 μm or less, and still more preferably 1.5 μm or less. The minimum diameter of the microlens is not particularly limited, but is preferably 0.3 μm or more.

As mentioned above, the present inventor provides the following (1) to (10).

(1) A curable resin composition containing a resin (A) and a solvent (S), which can be cured by heating through a crosslinking reaction of epoxy groups and/or a crosslinking reaction of isocyanate groups,

The resin (A) contains a unit (a1) represented by the following formula (a),

The resin (A) has at least one of a unit (a2a) having an epoxy group and a unit (a2b) having a functional group that reacts with and crosslinks the epoxy group, or reacts with a unit (a3a) having a block isocyanate group and an isocyanate group. A curable resin composition comprising at least one of the units (a3b) having a crosslinking functional group.

(In formula (a), R ¹ is a hydrogen atom or a methyl group, R ² is each independently a halogen atom or an organic group having 1 to 6 carbon atoms, x is an integer of 1 to 5, , y is an integer between 0 and 4, and z is an integer between 0 and 4.)

(2) The balance (A) has units (a1), units (a2a) and units (a2b), or

The resin (A) has a unit (a1) and a unit (a2a), and the curable resin composition further contains a compound (B) having a functional group that reacts with and crosslinks an epoxy group, or

The curable resin composition according to (1), wherein the resin (A) has a unit (a1) and a unit (a2b), and the curable resin composition further contains a compound (C) which has an epoxy group.

(3) The curable resin composition according to (1) or (2), wherein the resin (A) has a unit (a1), a unit (a2a), and a unit (a2b).

(4) The balance (A) has units (a1), units (a3a), and units (a3b), or

The resin (A) has a unit (a1) and a unit (a3a), and the curable resin composition further contains a compound (D) having a functional group that reacts with an isocyanate group and crosslinks, or

The curable resin composition according to (1), wherein the resin (A) has a unit (a1) and a unit (a3b), and the curable resin composition further contains a compound (E) having a blocked isocyanate group.

(5) The curable resin composition according to (1) or (4), wherein the resin (A) has a unit (a1), a unit (a3a), and a unit (a3b).

(6) Curability according to any one of (1) to (5), wherein the mass of unit (a1) represented by formula (a) relative to the total mass of solids contained in the curable resin composition is 30 mass% or more and 80 mass% or less. Resin composition.

(7) A cured product of the curable resin composition according to any one of (1) to (5).

(8) A microlens made of the cured material according to (7).

(9) forming a coating film made of the curable resin composition according to any one of (1) to (5) on a substrate,

Heating the coating film to form a cured film,

Forming a mask with a shape according to the shape of the microlens to be formed on the cured film,

A method of manufacturing a micro lens, comprising forming a micro lens to which the shape of the mask is transferred by etching the cured film together with a mask.

(10) the surface layer of the substrate is composed of a color filter selected from the group consisting of a green color filter, a blue color filter, or a red color filter,

The method for producing a microlens according to (9), which includes forming a coating film on a color filter.

[Example]

Hereinafter, the present invention will be described in more detail by examples and comparative examples. The present invention is not limited to these examples.

[Preparation of curable resin composition]

As the resin (A), a resin consisting of the types and quantities shown in Table 1 was used. The structure of each unit listed in Table 1 is as follows.

Resin (A) used in the examples and comparative examples is as follows. The weight average molecular weight of Resin 1 to Resin 10 measured by GPC in terms of polystyrene was 50,000.

Additionally, the numbers in () are mass%.

As a solvent (S), cyclopentanone and propylene glycol monomethyl ether acetate (PGMEA) were used.

The types of resin (A) shown in Table 2 were dispersed and dissolved in the solvent (S) shown in Table 2, respectively, to prepare a curable resin composition. The solvent (S) was used so that the solid component concentration of the curable resin composition was 15%.

Using the obtained curable resin compositions of each Example and Comparative Example, the items shown in Table 3 were evaluated according to the following method.

<Production of a substrate with a cured film>

The curable resin compositions obtained in each Example and Comparative Example were applied using a spin coater on a 100 mmХ100 mm, 0.7 m thick silicon substrate to form a coating film. For the formed coating film, a prebake at 100°C for 60 seconds and a postbake at 200°C for 5 minutes were performed to obtain a cured film with a film thickness of 1 μm.

<Evaluation of refractive index>

The refractive index of the obtained cured film was measured using a spectroscopic ellipsometer (product name: M-2000, manufactured by J.A. Warram Japan Co., Ltd.) at a temperature of 25°C and a wavelength of 550 nm, and evaluated based on the following criteria. did. The results are shown in Table 1.

A: The refractive index was greater than 1.62.

B: The refractive index was 1.60 or more and 1.62 or less.

C: The refractive index was less than 1.60.

<Evaluation of solvent resistance>

The substrate provided with the cured film was immersed in PGMEA for 10 minutes under room temperature (23°C) conditions.

After PGMEA immersion, rinsing was performed in pure water for 30 seconds. Afterwards, the substrate was heated using a hot plate under conditions of 100°C for 1 minute.

Before and after PGMEA immersion, the film thickness of the cured film was measured. The film thickness before immersion was set to Th1, and the film thickness after immersion was set to Th2.

Based on the measured value of the film thickness, the change rate of the film thickness of the cured film was calculated based on the following formula.

Film thickness change rate (%) = Th2/Th1Х100

Based on the calculated film thickness change value, solvent resistance was evaluated according to the following standards. The results are shown in Table 3.

A: Film thickness change rate is 99% or more and 102% or less.

B: Film thickness change rate is 95% or more and less than 99%, or more than 102% and 105% or less.

C: Film thickness change rate is less than 95% or more than 105%

According to Table 3, it can be seen that the curable resin compositions of Examples 1 to 4 containing the resin (A) containing the unit (a1) provide a cured film with a high refractive index and excellent solvent resistance.

On the other hand, when the curable resin compositions of Comparative Examples 1 to 6 containing resin (A) not containing unit (a1) were used, it was difficult to form a cured film that had both a high refractive index and excellent solvent resistance.

Claims (10)

A curable resin composition comprising a resin (A) and a solvent (S), which can be cured by heating through a crosslinking reaction of epoxy groups and/or a crosslinking reaction of isocyanate groups,
The resin (A) contains a unit (a1) represented by the following formula (a),
The resin (A) has at least one of a unit (a2a) having an epoxy group and a unit (a2b) having a functional group that reacts with and crosslinks the epoxy group, or a unit (a3a) having a block isocyanate group and reacts with an isocyanate group. A curable resin composition comprising at least one of the units (a3b) having a functional group that is crosslinked.
[Tuesday 1]

(In formula (a), R ¹ is a hydrogen atom or a methyl group, R ² is each independently a halogen atom or an organic group having 1 to 6 carbon atoms, x is an integer of 1 to 5, , y is an integer between 0 and 4, and z is an integer between 0 and 4.) In claim 1,
The resin (A) has the unit (a1), the unit (a2a), and the unit (a2b), or
The resin (A) has the unit (a1) and the unit (a2a), and the curable resin composition further contains a compound (B) having a functional group that reacts with and crosslinks an epoxy group, or
A curable resin composition in which the resin (A) has the unit (a1) and the unit (a2b), and the curable resin composition further contains a compound (C) having an epoxy group. In claim 2,
A curable resin composition in which the resin (A) has the unit (a1), the unit (a2a), and the unit (a2b). In claim 1,
The resin (A) has the unit (a1), the unit (a3a), and the unit (a3b), or
The resin (A) has the unit (a1) and the unit (a3a), and the curable resin composition further contains a compound (D) having a functional group that reacts with and crosslinks an isocyanate group, or
A curable resin composition in which the resin (A) has the unit (a1) and the unit (a3b), and the curable resin composition further contains a compound (E) having a blocked isocyanate group. In claim 4,
A curable resin composition in which the resin (A) has the unit (a1), the unit (a3a), and the unit (a3b). The method according to any one of claims 1 to 5,
A curable resin composition in which the mass of the unit (a1) represented by the formula (a) relative to the total mass of solids contained in the curable resin composition is 30 mass% or more and 80 mass% or less. A cured product of the curable resin composition according to any one of claims 1 to 5. A micro lens made of the cured material of claim 7. Forming a coating film made of the curable resin composition according to any one of claims 1 to 5 on a substrate,
Heating the coating film to form a cured film,
Forming a mask with a shape according to the shape of the micro lens to be formed on the cured film,
A method of manufacturing a micro lens, comprising forming a micro lens to which the shape of the mask is transferred by etching the cured film together with the mask. In claim 9,
The surface layer of the substrate is composed of a color filter selected from the group consisting of a green color filter, a blue color filter, or a red color filter,
A method of manufacturing a micro lens, comprising forming the coating film on the color filter.