JP2019038984A - Curable resin composition and method for producing (meth)acrylate-based polymer - Google Patents

Abstract

To provide a curable resin composition capable of giving a cured product which is excellent in solvent resistance and thermal coloration resistance and can be suitably used for applications such as a color filter, and to provide a method for producing a (meth)acrylate-based polymer.SOLUTION: The curable resin composition contains a (meth)acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator. The (meth)acrylate-based polymer has a constituent unit represented by general formula (1) and a tertiary carbon-containing (meth)acrylate-based monomer unit. (In the general formula (1), Rrepresents a C1-20 alkyl group; Rrepresents a hydrogen atom or a C1-20 organic residue; Rrepresents a hydrogen atom or a methyl group; and n represents 1 or 2.)SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition and a method for producing a (meth) acrylate polymer. Specifically, the present invention relates to a curable resin composition capable of obtaining a cured product excellent in solvent resistance and heat resistant colorability, and a method for producing a (meth) acrylate polymer.

Curable resin compositions that can be cured by heat or active energy rays are variously studied for various applications such as optical members, electrical machinery and electronic equipment, and are excellent in characteristics required for each application. Compositions are being developed. An example of such an application is a color filter.

The color filter is a main member constituting a liquid crystal display device, a solid-state image sensor, and the like. Generally, a substrate, pixels of at least three primary colors (red (R), green (G), blue (B)), and those In addition to the partitioning resin black matrix (BM), the pixel and the resin black matrix are covered and protected, and are formed of a protective film or the like provided for flattening the unevenness thereof. The curable resin composition applied to such a color filter is required to have performance such as curability, solvent resistance after curing, adhesion to a substrate, transparency, and heat resistance.

Various curable resin compositions applied to color filters have been known so far. For example, Patent Document 1 includes a polymer (A) containing a lactone ring structural unit derived from 2- (1-hydroxyalkyl) acrylic acid ester and a polymerizable compound (B), and the polymer ( A curable resin composition in which A) further contains an aromatic ring structure and / or an alicyclic structure is disclosed. For example, Patent Document 2 includes a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, and the (meth) acrylate polymer is a tertiary carbon-containing (meth) acrylate monomer. A curable resin composition having a unit, a monomer unit having a hydroxyl group, and an acrylic acid unit is disclosed.

JP 2004-18836 A JP2015-157909A

By the way, recent color filters tend to increase the concentration of coloring materials such as pigments and dyes in order to further improve luminance. However, when the concentration of the color material is high, there is a problem that the color material is eluted when it is washed with a washing solvent in the manufacturing process of the color filter. In recent years, from the viewpoint of improving luminance, it has also been required that colorants, dispersion resins, and binder resins are excellent in heat-resistant coloration that does not cause discoloration such as fading or yellowing due to heating during the production of a color filter. It is coming. Although suppression of elution of such a color material and improvement of heat resistant colorability of a color filter have been studied so far, they have not been sufficiently solved yet, and there is room for improvement.

In view of the above-mentioned present situation, the present invention provides a curable resin composition that is excellent in solvent resistance and heat-resistant colorability and that can obtain a cured product that can be suitably used for applications such as a color filter. With the goal.

As a result of various studies on curable resin compositions useful for applications such as color filters, the present inventors include a (meth) acrylate polymer having a specific structural unit, a polymerizable compound, and a photopolymerization initiator. It was found that by using a resin composition, a cured product having excellent solvent resistance and heat resistance colorability can be obtained. Further, by using a specific monomer component, it was found that a (meth) acrylate polymer capable of obtaining a cured product having excellent solvent resistance and heat-resistant colorability can be produced, and the present invention has been conceived. .

That is, this invention is curable resin composition containing a (meth) acrylate type polymer, a polymeric compound, and a photoinitiator, Comprising: The said (meth) acrylate type polymer is following General formula (1). And a tertiary carbon-containing (meth) acrylate monomer unit.

(In General Formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and R ³ represents a hydrogen atom or a methyl group. , N represents 1 or 2.)
The present invention is also a method for producing a (meth) acrylate polymer having a ring structure in the main chain, wherein the production method comprises an alkyl 2- (hydroxyalkyl) acrylate represented by the following general formula (2): It is also a method for producing a (meth) acrylate polymer, comprising a step of polymerizing a monomer component containing an ester, a tertiary carbon-containing (meth) acrylate monomer, and (meth) acrylic acid. .

(In General Formula (2), R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and n represents 1 or 2).

Since the curable resin composition of the present invention can obtain a cured product excellent in solvent resistance and heat-resistant colorability, it can be suitably used as a material such as a color filter. Moreover, according to this invention, the (meth) acrylic-type polymer which can obtain the hardened | cured material which has the outstanding solvent resistance and heat-resistant coloring property can be manufactured efficiently.

The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

1. Curable resin composition The curable resin composition of this invention is characterized by including a (meth) acrylate type polymer, a polymeric compound, and a photoinitiator.
Each component will be described below. In the present specification, “(meth) acrylate” means “acrylate and / or methacrylate”.

1-1. (Meth) acrylate polymer The (meth) acrylate polymer in the present invention has a structural unit represented by the following general formula (1) and a tertiary carbon-containing (meth) acrylate monomer unit. By having such a specific structural unit, the hardened | cured material obtained can have the outstanding solvent resistance and heat-resistant coloring property.

（一般式（１）中、Ｒ^１は炭素数１〜２０のアルキル基を表し、Ｒ^２は水素原子又は炭素数１〜２０の有機残基を表し、Ｒ^３は水素原子又はメチル基を表し、ｎは１又は２を表す。）

(In General Formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and R ³ represents a hydrogen atom or a methyl group. , N represents 1 or 2.)

The (meth) acrylate polymer in the present invention has a heat resistant colorability by having a ring structure in the main chain and further not containing a nitrogen atom which is said to cause coloring due to oxidation of the ring structure. Excellent. The (meth) acrylate polymer further has a tertiary carbon-containing (meth) acrylate monomer unit. As will be described later, this monomer unit is involved in the (meth) acrylate polymer. By forming a crosslinked structure in the structure of the polymer, the cured product of the curable resin composition of the present invention has excellent solvent resistance.

The structural unit of the (meth) acrylate polymer in the present invention will be described below.
(I) Structural unit represented by general formula (1) In the general formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched.
R ¹ preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms in terms of the solubility of the monomer.
Specific examples of R ¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, or 2- An ethylhexyl group etc. are mentioned. A methyl group is preferred.

In the general formula (1), ^{R 2} is a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
Examples of the organic residue having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; an unsaturated fat having 1 to 20 carbon atoms such as an ethenyl group and a propenyl group. An aromatic hydrocarbon group having 1 to 20 carbon atoms such as a phenyl group or a naphthyl group; one of the hydrogen atoms in the alkyl group, the unsaturated aliphatic hydrocarbon group and the aromatic hydrocarbon group; Examples thereof include groups substituted with at least one group selected from a hydroxyl group, a carboxyl group, an ether group, and an ester group. R ² is preferably a hydrogen atom from the viewpoint of the hydrophilicity of the lactone ring.
In the above general formula (1), R ³ represents a hydrogen atom or a methyl group.

The (meth) acrylate polymer in the present invention may have only one of the above-described structural units represented by the general formula (1), or may have two or more. Good.

The structural unit represented by the general formula (1) can be formed from, for example, a hydroxyl group-containing monomer unit and a carboxyl group-containing monomer unit. It is preferable that it is a lactone ring structural unit derived from 2- (hydroxyalkyl) acrylic acid alkyl ester and (meth) acrylic acid at the point which property is further excellent.
In the present specification, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”.

Examples of the 2- (hydroxyalkyl) acrylic acid alkyl ester include compounds represented by the following general formula (2).

(In General Formula (2), R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and n represents 1 or 2).

In the general formula (2), R ¹ represents an alkyl group having 1 to 20 carbon atoms, and R ² represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The ^{R 1} and ^{R 2} in the general formula (2) include the same as respectively ^{R 1} and ^{R 2} in the general formula (1) described above.

Examples of the 2- (hydroxyalkyl) acrylic acid alkyl ester include 2- (1-hydroxyalkyl) acrylic acid alkyl ester and 2- (2-hydroxyalkyl) acrylic acid alkyl ester. Specifically, for example, Methyl 2- (1-hydroxymethyl) acrylate, ethyl 2- (1-hydroxymethyl) acrylate, isopropyl 2- (1-hydroxymethyl) acrylate, n-butyl 2- (1-hydroxymethyl) acrylate, Examples include t-butyl 2- (1-hydroxymethyl) acrylate and 2-ethylhexyl 2- (1-hydroxymethyl) acrylate. Of these, methyl 2- (1-hydroxymethyl) acrylate and ethyl 2- (1-hydroxymethyl) acrylate are preferred. These may be used individually by 1 type and may be used in combination of 2 or more type.

When the 2- (hydroxyalkyl) acrylic acid alkyl ester and (meth) acrylic acid react and cyclize, a lactone ring structure can be formed as the structural unit represented by the general formula (1). As an example, a reaction formula in which methyl 2- (1-hydroxymethyl) acrylate and acrylic acid are cyclized to form a lactone ring structural unit is shown below.

In the case of having the lactone ring structural unit in the (meth) acrylate polymer, the cyclization rate is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably less than 30 mol%, still more preferably. It is 10 to 28 mol%, particularly preferably 15 to 28 mol%. The cyclization rate as used herein refers to the proportion of monomer units actually forming a ring structure among the monomer units used for forming the ring structure of the (meth) acrylate polymer. The cyclization rate (%) can be determined by the method described in Examples described later.

When the cyclization rate is 50 mol% or less, the (meth) acrylate-based polymer has a hydroxyl group-containing monomer unit and a carboxyl group-containing monomer unit that do not form a ring structure in the structure. . Thus, it is one of the preferred embodiments of the present invention that the (meth) acrylate polymer of the present invention has a hydroxyl group-containing monomer unit, and it also has a carboxyl group-containing monomer unit. This is one of the preferred embodiments of the present invention.

When the hydroxyl group-containing monomer unit and the carboxyl group-containing monomer unit that do not form a ring structure are contained in the (meth) acrylate polymer, the curable resin composition of the present invention is heated. When the treatment is added, the remaining hydroxyl group or carboxyl group also undergoes a reaction to form a crosslinked structure together with the cyclization reaction, and the glass transition temperature of the cured product of the resulting curable resin composition is increased, and The cured product is further excellent in solvent resistance. Furthermore, when a coating film containing a coloring material is formed from the curable resin composition of the present invention and the coating film is subjected to heat treatment, the coating film shrinks along with the formation of the crosslinked structure, and thereby the coloring material concentration Therefore, a coating film having a high color material concentration and effectively suppressing the elution of the color material is obtained. The effect obtained due to the formation of such a crosslinked structure is more sufficiently exhibited when the cyclization rate is 50 mol% or less.
The said cyclization rate can be calculated | required by the method as described in the Example mentioned later.

Preferably the content rate of the structural unit shown by the said General formula (1) in the said (meth) acrylate type polymer is 1-15 with respect to 100 mol% of total amounts of all the structural units of the said (meth) acrylate type polymer. It is mol%, More preferably, it is 1-12 mol%, More preferably, it is 1-9 mol%.

(Ii) Tertiary carbon-containing (meth) acrylate monomer unit The tertiary carbon-containing (meth) acrylate monomer unit is a polymerization in a (meth) acrylate monomer having a tertiary carbon atom. The carbon atom is not particularly limited as long as it is a structural unit in which the carbon-carbon double bond (C═C) is a single bond (C—C), but the oxygen atom adjacent to the (meth) acryloyl group is a tertiary carbon atom. Those having a bonded structure are preferred. With such a structure, when the curable resin composition of the present invention is heat-treated, the tertiary carbon atom portion is eliminated to generate a carboxyl group, and the generated carboxyl group is the above-mentioned (meta ) Reacts with the hydroxyl group of the hydroxyl group-containing monomer unit of the acrylate polymer to form a cross-linked structure, the glass transition temperature of the cured product of the resulting curable resin composition of the present invention further increases, The solvent resistance is further improved. Furthermore, when a coating film containing a color material is formed from the curable resin composition of the present invention and the coating film is subjected to a heat treatment, the above-described coating film shrinks more significantly, and the color material concentration is higher. A coating film that is high and in which the elution of the coloring material is more effectively suppressed can be obtained.

The (meth) acrylate monomer having a tertiary carbon atom is preferably the following general formula (a):

(R represents a hydrogen atom or a methyl group. A represents a monovalent organic group including a structure having a tertiary carbon atom on the oxygen atom side).

In the general formula (a), the organic group represented by A can be represented by, for example, —C (R ⁴ ) (R ⁵ ) (R ⁶ ). In this case, R ⁴ , R ⁵ and R ⁶ are the same or different and are preferably a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Moreover, it may have a cyclic structure and may further have a substituent. R ⁴ , R ⁵ and R ⁶ may be linked to each other at a terminal site to form a cyclic structure.

The number of carbon atoms of the organic group represented by A is a tertiary atom in A adjacent to the (meth) acryloyl group (CH ₂ ═C (R) —C (═O) —) and A adjacent thereto. It is preferably 12 or less, and more preferably 9 or less, in that a new compound produced by cleavage of the O—C bond with the carbon atom is likely to volatilize. Moreover, the organic group represented by A may have a branched structure.

Here, in the tertiary carbon-containing (meth) acrylate monomer, the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth) acryloyl group is bonded to a hydrogen atom at least one of the adjacent carbon atoms. It is preferable. For example, a tertiary carbon-containing (meth) acrylate monomer is a compound represented by the above general formula (a), and A is represented by -C (R ⁴ ) (R ⁵ ) (R ⁶ ). It is preferable that at least one of R ⁴ , R ⁵ and R ⁶ contains a carbon atom having one or more hydrogen atoms, and the carbon atom is bonded to a tertiary carbon atom. In such a form, by heating, the O—C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto is cut, and (meth) acrylic acid is generated at the same time. Then, a double bond (C = C) is formed between the tertiary carbon atom and the carbon atom adjacent thereto, and a new compound is generated more stably.

It is preferable that the new compound produced | generated as mentioned above is a thing which volatilizes. In this case, the film thickness of the cured product (cured film) is reduced due to volatilization of the new compound from the cured product, and at the same time, for example, the curable resin composition further includes a color material. In some cases, the colorant concentration increases after heating. Therefore, it is possible to realize a further thinner film, and to achieve higher color purity and higher light blocking ratio of the black matrix. In consideration of this point, R ⁴ , R ⁵ and R ⁶ are preferably the same or different and are each a saturated hydrocarbon group having 1 to 15 carbon atoms. More preferably, it is a C1-C10 saturated hydrocarbon group, More preferably, it is a C1-C5 saturated hydrocarbon group, Most preferably, it is a C1-C3 saturated hydrocarbon group.

As the (meth) acrylate monomer having a tertiary carbon atom, t-butyl (meth) acrylate or t-amyl (meth) acrylate is preferable.

The (meth) acrylate-based polymer in the present invention may have only one of the above-described tertiary carbon-containing (meth) acrylate-based monomer units, or two or more of them. It may be.

The content ratio of the tertiary carbon-containing (meth) acrylate monomer unit in the (meth) acrylate polymer is preferably based on 100 mol% of the total amount of all the structural units of the (meth) acrylate polymer. It is 5-60 mol%, More preferably, it is 10-55 mol%, More preferably, it is 20-55 mol%.

(Iii) Hydroxyl-containing monomer unit The (meth) acrylate polymer is a structural unit in addition to the structural unit represented by the general formula (1) and the tertiary carbon-containing (meth) acrylate monomer unit. It is preferable to further have a hydroxyl group-containing monomer unit. As described above, by having a hydroxyl group-containing monomer unit, a cross-linked structure is formed in the (meth) acrylate polymer, and the solvent resistance and heat resistance coloring property of the curable resin composition of the present invention are further improved. Can be made. Moreover, the development property can be expected to be improved by imparting hydrophilicity.
The hydroxyl group-containing monomer unit of the (meth) acrylate polymer of the present invention may be capable of forming the above-described ring structure or may not be capable of forming a ring structure. Good.

Examples of the hydroxyl group-containing monomer unit include structural units derived from a hydroxyl group-containing monomer. The hydroxyl group-containing monomer is not particularly limited as long as it is a compound having a hydroxyl group and a polymerizable unsaturated double bond in the molecule, but 2- (hydroxyalkyl) acrylic represented by the general formula (2) described above. In addition to acid alkyl esters, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylic Preferred are hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl acid, 4-hydroxybutyl (meth) acrylate, 2,3-hydroxypropyl (meth) acrylate, more preferably 2-hydroxyethyl (meth) acrylate. It is.
The (meth) acrylate polymer in the present invention may have only one of the above-mentioned hydroxyl group-containing monomer units, or may have two or more.

The content ratio of the hydroxyl group-containing monomer unit in the (meth) acrylate polymer is preferably 5 to 50 mol% with respect to a total amount of 100 mol% of all the structural units of the (meth) acrylate polymer. Preferably it is 5-45 mol%, More preferably, it is 10-40 mol%.

(Iv) Monomer unit derived from (meth) acrylic acid The (meth) acrylate polymer preferably further has a monomer unit derived from (meth) acrylic acid as a constituent unit. As described above, since the monomer unit derived from (meth) acrylic acid can form a crosslinked structure, by further having a monomer unit derived from (meth) acrylic acid, the resistance of the cured product to be obtained is improved. Solvent property and heat-resistant colorability can be further improved. Moreover, alkali solubility can be provided.

The content ratio of the monomer unit derived from the (meth) acrylic acid in the (meth) acrylate polymer is preferably 1 to 100 mol% with respect to the total amount of all the structural units of the (meth) acrylate polymer. It is 35 mol%, More preferably, it is 1-30 mol%, More preferably, it is 5-30 mol%.

(V) Other Structural Units The (meth) acrylate polymer in the present invention further has one or more structural units other than the above-described structural units (i) to (iv) as necessary. You may do it.
As another structural unit, the structural unit derived from the monomer as described in the following (v-1) or (v-2) is mentioned, for example.

(V-1) Acrylic ether dimer Examples of the acrylic ether dimer include compounds represented by the following general formula (b).

(In formula, R < ⁷ > and R <^8> are the same or different, and represent the C1-C25 organic group which may have a hydrogen atom or a substituent.)

In the general formula (b), the organic group having 1 to 25 carbon atoms that can be represented by R ⁷ and R ⁸ is a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. Preferred examples include linear or branched alkyl groups; aryl groups; alicyclic groups; alkyl groups substituted with alkoxy; alkyl groups substituted with aryl groups; Of these, primary or secondary carbon hydrocarbon groups which are difficult to be removed by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl and the like, are preferable in terms of heat resistance. R ⁷ and R ⁸ may be the same organic group or different organic groups.

Among the acrylic ether dimers, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. From the viewpoints of little coloring, dispersibility, industrial availability, and the like, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate is more preferable.

(V-2) α- (Unsaturated alkoxyalkyl) acrylate monomer As the α- (unsaturated alkoxyalkyl) acrylate monomer, for example, alkyl- (α-methallyloxymethyl) acrylate, α -(Allyloxymethyl) acrylate is preferred. Of these, α- (allyloxymethyl) acrylate is more preferable.

Examples of the α- (allyloxymethyl) acrylate include the following general formula (c):

A compound represented by the formula (wherein R ⁹ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms which may have a substituent) is preferable. In the present specification, “α- (allyloxymethyl) acrylate” includes a compound in which R ⁹ is a hydrogen atom (that is, α-allyloxymethylacrylic acid).

R ⁹ in the general formula (c) may be appropriately selected according to the purpose and application, but the organic group having 1 to 30 carbon atoms that R ⁹ may represent may have a substituent. The hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms. Specifically, for example, a chain saturated hydrocarbon group; an alkoxy-substituted chain saturated hydrocarbon group in which a part of the hydrogen atoms of the chain saturated hydrocarbon group is replaced with an alkoxy group; a hydrogen atom of the chain saturated hydrocarbon group A hydroxy-substituted chain saturated hydrocarbon group in which a part of is substituted with a hydroxy group; a halogen-substituted chain saturated hydrocarbon group in which a part of the hydrogen atom of the chain saturated hydrocarbon group is replaced with a halogen; a chain unsaturated hydrocarbon A chain unsaturated hydrocarbon group in which a part of the hydrogen atom is replaced with an alkoxy group, a hydroxy group or a halogen; an alicyclic hydrocarbon group, and a part of the hydrogen atom is an alkoxy group or a hydroxy group And an alicyclic hydrocarbon group substituted with or halogen; an aromatic hydrocarbon group and an aromatic hydrocarbon group in which a part of the hydrogen atom is replaced with an alkoxy group, hydroxy group or halogen; and the like. Moreover, arbitrary substituents may be further bonded to these organic groups.

Specific examples of the α- (allyloxymethyl) acrylate include, for example, α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid. n-propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α- N-amyl allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate , Α-allyloxymethyl acrylate s-hexyl, -N-heptyl allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid 2-ethylhexyl, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate, α -Tridecyl allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-allyloxy Contains chain saturated hydrocarbon groups such as stearyl dimethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, etc. α- (allyloxymethyl) acrylate is preferred. In addition, alkoxyalkyl-α- (allyloxymethyl) acrylate and the like are also suitable. Among these, methyl α-allyloxymethyl acrylate (also referred to as α- (allyloxymethyl) methyl acrylate) is particularly preferable.

The α- (unsaturated alkoxyalkyl) acrylate monomer can be produced by, for example, a production method disclosed in International Publication No. 2010/114077.

When the (meth) acrylate polymer has a structural unit derived from the monomer (v-1) or (v-2), the content is not particularly limited, but the solubility of the structural unit is considered. From 1 to 30 mol%, more preferably from 5 to 30 mol%, based on 100 mol% of the total amount of all the structural units of the (meth) acrylate polymer.

Moreover, monomer units (vi) derived from polymerizable monomers other than those described above can be cited as other structural units other than the above (v-1) or (v-2). Specific examples of the polymerizable monomer include (meth) acrylates other than tertiary carbon-containing (meth) acrylates, aromatic vinyl monomers, and acid group-containing monomers other than (meth) acrylic acid. Examples thereof include monomers and other copolymerizable monomers.

Examples of (meth) acrylates other than the tertiary carbon-containing (meth) acrylate include (meth) acrylic acid ester monomers represented by the following general formula (d).

(In general formula (d), R ¹⁰ is the same or different and represents a hydrogen atom or a methyl group. R ¹¹ is the same or different and has an organic residue having 1 to 20 carbon atoms (having a tertiary carbon). N1 represents a number of 1 or 2.)

In the general formula (d), R ¹¹ is preferably an organic residue having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
Examples of the organic residue having 1 to 20 carbon atoms include linear or branched alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; and carbon numbers 1 such as an ethenyl group and a propenyl group. -20 linear or branched unsaturated aliphatic hydrocarbon group; aromatic hydrocarbon group having 1 to 20 carbon atoms such as phenyl group and naphthyl group; glycidyl group; the above linear or branched alkyl group In the linear or branched unsaturated aliphatic hydrocarbon group and the aromatic hydrocarbon group, one or more of hydrogen atoms are a hydroxyl group; a carboxyl group; a primary to tertiary amino group; an epoxy group; An ether bond-containing group such as a group; an ester group such as an alkyl ester group; a monovalent organic group such as a group substituted by at least one group selected from: a methylene group, an ethylene group, a propylene group, a butylene group; Etc. Alkylene group; a cycloalkylene group; oxyalkylene group; a vinylene group; and the divalent organic group such as; a phenylene group.

Examples of the (meth) acrylate monomer represented by the general formula (d) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth ) I-propyl acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, n- (meth) acrylate Hexyl, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Stearyl acid, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydride (meth) acrylate Furfuryl, N, N-dimethylaminoethyl (meth) acrylate, 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid, (meth) acryloylmorpholine, 4- (meth) acryloyloxymethyl-2 -Methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2 -Cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane and the like. Among them, (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. in that heat resistance, colorant dispersibility, and solvent resolubility are improved. Alkyl is preferred.

Examples of the (meth) acrylic acid ester monomer include cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and (3,4-epoxy). (Cyclohexyl) methyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, pentacyclopentadecanedi Methanol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, norbornane dimethanol di (meth) acrylate, p-menthane-1,8-diol di (meth) acrylate P-menthane-2,8-diol di (meth) acrylate, p-menthane-3,8-diol di (meth) acrylate, bicyclo [2.2.2] -octane-1-methyl-4-isopropyl-5 , 6-dimethylol di (meth) acrylate and other monomers having an alicyclic skeleton. Moreover, alicyclic epoxy compounds, such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and ethyl glycidyl (meth) acrylate, can also be used.

Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, methoxy styrene, and the like. Among these, styrene and / or vinyltoluene are preferable in that the thermal decomposition resistance of the polymer is good.

The acid group-containing monomer other than the (meth) acrylic acid is not particularly limited as long as it is a compound having an acid group and a polymerizable unsaturated double bond in the molecule. Specifically, for example, for example, croton Unsaturated monocarboxylic acids other than (meth) acrylic acid such as acid, cinnamic acid and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl) and other unsaturated monocarboxylic acids in which the chain is extended between an unsaturated group and a carboxyl group; maleic anhydride, itaconic anhydride, etc. Unsaturated acid anhydrides; Phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); and the like. Among these, carboxylic acid monomers (for example, unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) are preferable from the viewpoint of versatility and availability.

Examples of the other copolymerizable monomers include (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; polystyrene, polymethyl (meth) acrylate, and polyethylene oxide. , Polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam, etc., macromonomers having a (meth) acryloyl group at one end of the polymer molecular chain; conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; vinyl acetate Vinyl esters such as vinyl propionate, vinyl butyrate, vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, Vinyl ethers such as uryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl compounds such as N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide, etc .; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate; Can be mentioned.

When the (meth) acrylate polymer has the monomer unit (vi), the content ratio is not particularly limited, but is 100% by mole based on the total amount of all the structural units of the (meth) acrylate polymer. The amount is preferably 1 to 50 mol%, more preferably 1 to 40 mol%.

In the case where the (meth) acrylate polymer has a carboxyl group-containing monomer unit as an acid group-containing monomer other than (meth) acrylic acid among the other monomer units (vi), the above-described case is described above. The total of the monomer units derived from (meth) acrylic acid and the acid group-containing monomers other than the (meth) acrylic acid is 100 mol% with respect to the total amount of all the structural units of the (meth) acrylate polymer. 1 to 50 mol% is preferable. More preferably, it is 5-45 mol%, More preferably, it is 5-40 mol%.

Although it does not specifically limit as a weight average molecular weight of the said (meth) acrylate type polymer, 2000-50000 are preferable, 4000-45000 are more preferable, 5000-40000 are still more preferable.
The weight average molecular weight of the (meth) acrylate-based polymer is a value obtained by measuring by the method described in Examples by gel permeation chromatography (GPC).

Although it does not specifically limit as an acid value of the said (meth) acrylate type polymer, Preferably it is 5-200 mgKOH / g, More preferably, it is the point which can improve the solvent resistance and heat-resistant coloring property in hardened | cured material further. -180 mg KOH / g.
The acid value is a value obtained by measurement by a neutralization titration method using a KOH solution.

The amount of hydroxyl groups in the (meth) acrylate polymer is preferable in that it imparts hydrophilicity to the curable resin composition and can serve as a crosslinking point with the carboxylic acid when the curable resin composition is heated. Is 10 to 60 mol%, more preferably 15 to 50 mol%. The amount of hydroxyl groups can be determined by the method [number of moles of hydroxyl group-containing monomer] / [number of moles of all monomer components] × 100.

Method for Producing (Meth) acrylate Polymer As a method for producing the (meth) acrylate polymer used in the present invention, a (meth) acrylate polymer having at least the structural units (i) and (ii) described above is used. The method is not particularly limited as long as it is a method capable of obtaining a monomer, and includes a method of polymerizing a monomer component containing a monomer that can constitute the structural units (i) and (ii) by a known method.

Especially, as a method for producing the (meth) acrylate polymer, the above-mentioned general (meth) acrylate polymer can be efficiently produced in that the solvent-resistant and heat-resistant colorability in the cured product is more excellent. Including a step of polymerizing a monomer component containing 2- (hydroxyalkyl) acrylic acid alkyl ester represented by formula (2), a tertiary carbon-containing (meth) acrylate monomer, and (meth) acrylic acid. Is preferred. Thus, the (meth) acrylate polymer in the present invention is a 2- (hydroxyalkyl) acrylic acid alkyl ester represented by the general formula (2), a tertiary carbon-containing (meth) acrylate monomer, and A copolymer obtained by polymerizing (meth) acrylic acid is preferred. Such a monomer component containing 2- (hydroxyalkyl) acrylic acid alkyl ester represented by the general formula (2), a tertiary carbon-containing (meth) acrylate monomer, and (meth) acrylic acid. A method for producing a (meth) acrylate polymer including a polymerization step is also one aspect of the present invention.

As the 2- (hydroxyalkyl) acrylic acid alkyl ester represented by the general formula (2) and the tertiary carbon-containing (meth) acrylate monomer, the above structural units (i) and (ii) The thing similar to what was described is mentioned.

In the polymerization step, the content of the 2- (hydroxyalkyl) acrylic acid alkyl ester represented by the general formula (2) is preferably 100 to 50% by mass, more preferably 1 to 50% by mass, in 100% by mass of the monomer component. Is 5 to 50% by mass, more preferably 5 to 40% by mass.
The content ratio of the tertiary carbon-containing (meth) acrylate monomer is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, and still more preferably 10 to 50% in 100% by mass of the monomer component. % By mass.
The content ratio of (meth) acrylic acid is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, and further preferably 5 to 30% by mass in 100% by mass of the monomer component.

In addition to the 2- (hydroxyalkyl) acrylic acid alkyl ester represented by the general formula (2), the tertiary carbon-containing (meth) acrylate monomer, and (meth) acrylic acid, Other monomer components may be included as necessary. As said other monomer component, the monomer similar to what was described as a monomer which can comprise structural unit (iii), (v), and (vi) mentioned above is mentioned.
When the monomer component includes a monomer that can constitute the structural units (iii), (v), and (vi) described above, the preferable content ratio of these monomers in the monomer component is as described above. This is the same as the preferred content ratio of these structural units in the (meth) acrylate polymer.

The method for polymerizing the monomer components is not particularly limited, and commonly used techniques such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Of these, solution polymerization is preferred because it is industrially advantageous and allows easy adjustment of the structure such as molecular weight. The polymerization mechanism of the monomer component can be a polymerization method based on mechanisms such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization. A polymerization method based on this is preferred.

The polymerization initiation method in the polymerization reaction may be any method that can supply the monomer component with the energy necessary for initiation of polymerization from an active energy source such as heat, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.) or electron beams. Further, it is preferable to use a polymerization initiator in combination because the energy required for the initiation of polymerization can be greatly reduced and the reaction can be easily controlled. The molecular weight of the polymer obtained by polymerizing the monomer components can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.

When the monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction, the polymerization mechanism, the type and amount of the monomer used, What is necessary is just to set suitably according to superposition | polymerization conditions, such as superposition | polymerization temperature and superposition | polymerization density | concentration. When a solvent is used as a diluent or the like when the curable resin composition is used later, it is efficient and preferable to use a solvent containing the solvent for solution polymerization of the monomer component.

As said solvent, the thing similar to the solvent of Unexamined-Japanese-Patent No. 2015-157909 is mentioned, Those 1 type (s) or 2 or more types can be used. Among these solvents, propylene glycol monomethyl ether from the solubility of the resulting polymer, surface smoothness when forming a coating film, little influence on the human body and the environment, industrial availability, Propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and ethyl lactate are preferably used.

As the usage-amount of the said solvent, Preferably it is 50-1000 mass parts with respect to 100 mass parts of said monomer components, More preferably, 100-500 mass parts is mentioned.

When the monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy. Depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. And may be selected as appropriate. Moreover, you may use together reducing agents, such as transition metal salt and amines, with a polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butylperoxy- 2-ethylhexanoate, azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis ( 2-methylpropionate), hydrogen peroxide, persulfate and the like, and peroxides and azo compounds that are usually used as polymerization initiators. These may be used alone or in combination of two or more.

The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, and the molecular weight of the target polymer. Although it is good, for example with respect to 100 mass parts of said monomer components, Preferably it is 0.1-20 mass parts, More preferably, 0.5-15 mass parts is mentioned.

In the above polymerization, a chain transfer agent may be used as necessary. Preferably, a polymerization initiator and a chain transfer agent are used in combination. When a chain transfer agent is used during polymerization, an increase in molecular weight distribution or gelation tends to be suppressed.

As said chain transfer agent, the thing similar to the solvent of Unexamined-Japanese-Patent No. 2015-157909 is mentioned, Those 1 type (s) or 2 or more types can be used. Among them, mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercaptoalcohols, aromatic mercaptans, mercapto are preferable from the viewpoints of availability, ability to prevent crosslinking, and low degree of decrease in polymerization rate. Compounds having a mercapto group such as isocyanurates can be mentioned, more preferably alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic esters, and still more preferably n-dodecyl mercaptan and mercaptopropionic acid.

The amount of the chain transfer agent used is not particularly limited and may be appropriately set according to the type and amount of the monomer used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, the molecular weight of the target polymer, and the like. For example, in order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts per 100 parts by mass of the monomer component. A mass part is mentioned.

Regarding the polymerization conditions, the polymerization temperature may be appropriately set according to the type and amount of the monomer to be used, the type and amount of the polymerization initiator, and is preferably 50 to 130 ° C, for example, 60 to 120 ° C. is more preferable.

The lactone cyclization rate of the (meth) acrylate polymer obtained in the production method is preferably 50 mol% or less. The effect of the cyclization rate being 50 mol% or less is as described above. The cyclization rate is more preferably 40 mol% or less, still more preferably less than 30 mol%, even more preferably 10 to 28 mol%, and particularly preferably 15 to 28 mol%. The cyclization rate (%) can be determined by the method described in Examples described later.

In the curable resin composition of the present invention, the content ratio of the (meth) acrylate-based polymer is not particularly limited, and may be set as appropriate depending on the use and the blending of other components. 20 mass% or more and 60 mass% or less are preferable with respect to 100 mass% of solid content total amount of a composition. Within such a range, the solvent resistance and heat resistant colorability can be further improved. The content ratio of the (meth) acrylate polymer is more preferably 20 to 55% by mass, and further preferably 25 to 50% by mass with respect to 100% by mass of the total solid content of the curable resin composition.
The “total amount of solids” means the total amount of components that form a cured product (excluding solvents that volatilize during the formation of the cured product).

1-2. Polymerizable compound The curable resin composition of the present invention further contains a polymerizable compound. When the polymerizable compound is contained, when the curable resin composition of the present invention is heat-treated, a cured product obtained by a polymerization reaction of the polymerizable compound has excellent solvent resistance and curability.

The polymerizable compound in the present invention includes a polymerizable unsaturated bond (polymerizable unsaturated group) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.) and electron beams. Low molecular weight compound). For example, the monofunctional compound which has one polymerizable unsaturated group in a molecule | numerator, and the polyfunctional compound which has 2 or more are mentioned.

Examples of the monofunctional polymerizable monomer include N-substituted maleimide monomers; (meth) acrylic acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; Unsaturated monocarboxylic acids in which the chain between a saturated group and a carboxyl group is extended; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; Isocyanates; and the like. A monomer having an active methylene group or an active methine group can also be used.

Examples of the polyfunctional polymerizable monomer include the following compounds.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meth) acrylate compounds such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate;

Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Trifunctional or higher polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrile Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethyl Lumpur propane tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, polyfunctional vinyl ethers such as ethylene oxide adduct of dipentaerythritol hexavinyl ether;

(Meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4 -Vinyloxybutyl, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, ( Vinyl ether group-containing (meth) acrylic such as p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, and 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate Acid esters;

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethyl Lumpur propane tetra allyl ether, ethylene oxide adduct of pentaerythritol tetra-allyl ether, polyfunctional allyl ethers such as ethylene oxide adduct of dipentaerythritol hexa-allyl ether;

Allyl group-containing (meth) acrylic acid esters such as (meth) acrylic acid allyl; tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene Polyfunctional (meth) acryloyl group-containing isocyanurates such as oxide-added tri (methacryloyloxyethyl) isocyanurate; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. Polyfunctional isocyanate and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and other hydroxyl-containing (meth) acrylate esters Multifunctional urethane (meth) acrylates obtained by reaction of a; polyfunctional aromatic vinyl compounds such as divinylbenzene; and the like. These polymerizable compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Among the polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further improving the curability of the curable resin composition. The functional number of the polyfunctional polymerizable compound is preferably 3 or more, and more preferably 4 or more. Further, the functional number is preferably 10 or less, and more preferably 8 or less.
The molecular weight of the polymerizable compound is not particularly limited, but is preferably 2000 or less, for example, from the viewpoint of handling.

The polyfunctional polymerizable compound is preferably a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate compound, or a (meth) acryloyl group from the viewpoints of reactivity, economy, availability and the like. The compound which has a (meth) acryloyl group, such as a containing isocyanurate compound, is mentioned, More preferably, a polyfunctional (meth) acrylate compound is mentioned. By including the compound having a (meth) acryloyl group, the resin composition becomes more excellent in photosensitivity and curability, and a hardened and highly transparent cured product can be obtained. As the polyfunctional polymerizable compound, it is more preferable to use a trifunctional or higher polyfunctional (meth) acrylate compound.

In the curable resin composition of the present invention, the content ratio of the polymerizable compound is not particularly limited as long as the effect of the present invention is exerted, and may be appropriately set. From the point which can make it a viscosity, Preferably it is 10-50 mass% with respect to 100 mass% of solid content total amount of the curable resin composition of this invention, More preferably, it is 15-45 mass%.

1-3. Photopolymerization initiator The photopolymerization initiator in the present invention is preferably a radical polymerizable photopolymerization initiator. The radically polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam.

Specific examples of the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE907”, manufactured by BASF), 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ("IRGACURE369", manufactured by BASF), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4 Amino ketone compounds such as -morpholin-4-yl-phenyl) -butan-1-one ("IRGACURE 379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE 651") ”, Manufactured by BASF), phenylglyoxylic acid methyl ester (“ DAROCUR MBF ”, manufactured by BASF) 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (“DAROCUR1173”, BASF) 1)-[4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE2959”, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (“IRGACURE127”, manufactured by BASF), [1-hydroxy-cyclohexyl- Phenyl-ketone + benzophenone] ("IRGACURE500", BASF In addition to the above, alkylphenone compounds; benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethyl, exemplified in paragraphs [0084] to [0086] of JP2013-227485A Triazine compounds; halomethylated oxadiazole compounds; biimidazole compounds; oxime ester compounds; titanocene compounds; benzoate compounds; acridine compounds, etc .; phosphine oxide compounds; oxime ester compounds; Can be mentioned. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

Among the photopolymerization initiators, it is preferable to use at least an aminoketone compound. When the curable resin composition of the present invention further includes the above-described (meth) acrylate polymer and a polymerizable compound, the solvent resistance and heat resistance coloring property of the cured product can be further improved. . Moreover, it can be excellent in internal curability.

The content of the photopolymerization initiator is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately designed. For example, the total solid content of the curable resin composition of the present invention is 100. Preferably it is 5-25 mass% with respect to mass%, More preferably, it is 5-20 mass%.

Moreover, you may use together 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed. Sensitivity and curability are further improved by using a photosensitizer and / or a radical photopolymerization accelerator in combination with the photopolymerization initiator. It does not specifically limit as a photosensitizer and radical photopolymerization promoter, It is good to select suitably from the well-known thing generally used in the curable resin composition.

1-4. Other Components The curable resin composition of the present invention may contain other components as necessary in addition to the above-described (meth) acrylate polymer, photopolymerization initiator, and polymerizable compound. Other components include, for example, solvents; coloring materials (also referred to as colorants); dispersants; heat resistance improvers; leveling agents; development aids; inorganic fine particles such as silica fine particles; silane-based, aluminum-based, titanium-based, etc. Coupling agents; Thermosetting resins such as fillers, epoxy resins, phenolic resins, and polyvinylphenols; Curing aids such as polyfunctional thiol compounds; Plasticizers; Polymerization inhibitors; UV absorbers; Antioxidants; Antifoaming agent; antistatic agent; slip agent; surface modifier; thixotropic agent; thixotropic agent; quinonediazide compound; polyhydric phenol compound; cationic polymerizable compound; These may be used individually by 1 type and may be used in combination of 2 or more type. For example, when using the said curable resin composition for a color filter use, it is preferable that the said curable resin composition contains a coloring material.

(solvent)
The solvent is not particularly limited as long as it dissolves the polymer uniformly and does not react. For example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc. Alcohols; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethyl sulfoxide; It is. These may be used individually by 1 type and may be used in combination of 2 or more type. What is necessary is just to set content of a solvent suitably according to the optimal viscosity at the time of using a curable resin composition.

(Color material)
Examples of the color material include pigments and dyes. As the coloring material, either a pigment or a dye may be used, or a pigment and a dye may be used in combination. For example, when forming red, blue, and green pixels of a color filter, it is preferable to use a known method that exhibits color characteristics obtained by appropriately combining color materials such as blue and purple, green and yellow. Further, when forming a black matrix, a black color material may be used.

Among the color materials, a pigment is preferable from the viewpoint of durability, and a dye is preferable from the viewpoint of improving luminance of a panel or the like. These can be appropriately selected according to required characteristics. In the curable resin composition of this invention, a pigment is preferable at the point which can further improve the solvent resistance and heat-resistant coloring property in hardened | cured material. As the pigment, those described in JP-A-2015-157909 can be used.

As the dye, for example, organic dyes described in JP 2010-9033 A, JP 2010-211198 A, JP 2009-51896 A, and JP 2008-50599 A may be used. it can. Of these, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like are preferable.
These color materials may be used alone or in combination of two or more.

The content of the coloring material is not particularly limited, and can be appropriately set according to the purpose and application, but is preferably 5 to 30% with respect to 100% by mass of the total solid content of the curable resin composition. A mass%, More preferably, 5-25 mass% is mentioned.

(Dispersant)
When the curable resin composition of this invention contains the said color material, it is preferable that a dispersing agent is further included. By including the dispersant, the dispersion of the color material in the dispersion medium can be stabilized. The dispersant is not particularly limited, and examples thereof include known dispersants such as a resin-type dispersant, a surfactant, and a pigment derivative. These may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , Long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide formed by reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, or a salt thereof, (meth) acrylic acid-styrene Copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene oxide adduct, etc. All It is. Examples of commercially available resin-type dispersants include those described in JP-A-2015-157909.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate Surfactants; cationic boundaries such as alkyl quaternary ammonium salts and their ethylene oxide adducts Alkyl betaines such as alkyl dimethylamino acetic acid betaine, and amphoteric surfactants such as alkyl imidazolines; active agents.

The dye derivative is a compound having a structure in which a functional group is introduced into the dye. Examples of the functional group include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, and an amide group. And phthalimide groups. Examples of the structure of the base dye include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, diketopyrrolopyrrole. And the like.

The content of the dispersant may be appropriately set according to the purpose and application, but from the viewpoint of balance of dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency, for example, curing It is preferable that it is 0.01-60 mass% with respect to 100 mass% of solid content total amount of a conductive resin composition. More preferably, it is 0.1-50 mass%, More preferably, it is 0.3-40 mass%.

Preparation of curable resin composition The method for preparing the curable resin composition is not particularly limited, and any known method may be used. For example, each of the above-described components may be mixed using various mixers and dispersers. And mixing and dispersing. The mixing / dispersing step is not particularly limited, and may be performed by a known method. Moreover, the other process normally performed may be further included. In addition, when the said curable resin composition contains a color material, it is preferable to prepare through the dispersion | distribution process process of a color material.

As the color material dispersion treatment step, for example, first, a predetermined amount of each of a color material (preferably an organic pigment), a dispersant, and a solvent are weighed, and the color material is finely dispersed using a disperser to form a liquid color material A method for obtaining a dispersion (also referred to as a mill base) is mentioned. Examples of the dispersing machine include a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, and a blender. As the dispersion treatment step, preferably, a method of performing a fine dispersion treatment with a media mill such as a bead mill filled with 0.01 to 1 mm beads after a kneading dispersion treatment with a roll mill, a kneader, a blender or the like is mentioned. . A composition containing a (meth) acrylate polymer, a polymerizable monomer, a photopolymerization initiator, and, if necessary, a solvent, a leveling agent, and the like, which are separately stirred and mixed with the obtained mill base. A curable resin composition can be obtained by adding (preferably a transparent liquid) and mixing to obtain a uniform dispersion solution.
In addition, it is preferable that the obtained curable resin composition is filtered with a filter or the like to remove fine dust.

2. Cured product As described above, the curable resin composition of the present invention provides a cured product having excellent solvent resistance and heat-resistant colorability. Moreover, the said hardened | cured material is excellent also in basic performance, such as sclerosis | hardenability, developability, adhesiveness with a base material, heat resistance, and transparency. A cured product obtained by curing such a curable resin composition is also one aspect of the present invention.

When the cured product is a cured film, the film thickness is preferably 0.1 to 20 μm. When the film thickness is in the above-mentioned range, in addition to solvent resistance and heat-resistant colorability, the image forming property and surface smoothness can be excellent. The film thickness is more preferably from 0.5 to 15 μm, still more preferably from 1 to 10 μm.

The method for obtaining a cured product using the curable resin composition of the present invention is not particularly limited, and a known method may be used. For example, the curable resin composition of the present invention is applied on a substrate, Examples include a method for obtaining a cured product by drying and heating the applied material or irradiating it with energy rays such as ultraviolet rays.

The cured product is used for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used in liquid crystal display devices, solid-state imaging devices, etc., and electrical / electronic devices. Are preferably used. Especially, it is preferable to use for a color filter. Thus, the color filter comprising the cured product is also one aspect of the present invention. Hereinafter, the color filter will be described.

3. Color filter The color filter of this invention consists of a form which has the said hardened | cured material on a board | substrate.
In the above color filter, the cured product formed from the curable resin composition of the present invention is particularly suitable as a segment that needs to be colored, such as a black matrix or pixels such as red, green, blue, and yellow. However, it is also suitable as a segment that does not necessarily require coloring such as a photospacer, a protective layer, and an orientation control rib.

Examples of the substrate used in the color filter include glass substrates such as white plate glass, blue plate glass, alkali tempered glass, and silica coated blue plate glass; ring-opening polymers of polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin, and hydrogen thereof. Sheet, film or substrate made of thermoplastic resin such as additive; sheet, film or substrate made of thermosetting resin such as epoxy resin or unsaturated polyester resin; metal substrate such as aluminum plate, copper plate, nickel plate, stainless steel plate A ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member composed of various materials such as a glass substrate (for example, a color filter for LCD) having a color material layer on the surface; Among these, from the viewpoint of heat resistance, a glass substrate, a sheet, a film or a substrate made of a heat resistant resin is preferable. The substrate is preferably a transparent substrate.
Moreover, you may perform the chemical | medical treatment etc. by a corona discharge process, an ozone process, a silane coupling agent, etc. to the said base material as needed.

4). Production method of color filter To obtain the color filter, for example, a step of arranging the curable resin composition on a substrate (also referred to as an arrangement step) for each pixel color (that is, for each pixel of one color), A step of irradiating light to the curable resin composition disposed on the substrate (also referred to as a light irradiation step), a step of developing with a developer (also referred to as a development step), and a step of heating treatment (also referred to as a heating step) It is preferable to employ a manufacturing method that includes the same method as above and to repeat the same method for each color. Note that the order of forming the pixels of each color is not particularly limited.

4-1. Arrangement process (preferably application process)
The arrangement step is preferably performed by coating. Examples of the method of applying the curable resin composition on the substrate include spin coating, slit coating, roll coating, and cast coating, and any method can be preferably used.
In the arranging step, it is preferable that the coating film is dried after the curable resin composition is applied onto the substrate. The coating film can be dried using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but it is usually performed at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds. Is preferred.

4-2. Light irradiation process In the light irradiation process, as the light source of actinic rays used, for example, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, A lamp light source such as a fluorescent lamp, a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser are used. Further, examples of the exposure system include a proximity system, a mirror projection system, and a stepper system, but the proximity system is preferably used.
In the irradiation process of the active energy beam, the active energy beam may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed portion is cured, and the cured portion is insolubilized or hardly soluble in the developer.

4-3. Development Step The development step is a step in which, after the light irradiation step described above, development processing is performed with a developer to remove unexposed portions and form a pattern. Thereby, the patterned cured film can be obtained. The development treatment can be usually performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development.

The developer used in the development step is not particularly limited as long as it dissolves the curable resin composition of the present invention. Usually, an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may be used. . In addition, when using alkaline aqueous solution as a developing solution, it is preferable to wash | clean with water after image development.
Examples of the organic solvent and alkaline aqueous solution include those described in JP-A-2015-157909.

4-4. Heating Step The heating step is a step (also referred to as a post-curing step) in which the exposed portion (cured portion) is further cured by baking after the development step described above. For example, using a light source such as a high-pressure mercury lamp, for example, a step of post-exposure with a light amount of 0.5 to ⁵ J / cm ² , a step of post-heating at a temperature of 60 to 260 ° C. for 10 seconds to 120 minutes, etc. Can be mentioned. By performing such a post-curing step, it becomes possible to further strengthen the hardness and adhesion of the patterned cured film. In addition, as described above, the carboxyl group generated by the elimination of the tertiary carbon-containing site of the structural unit of the (meth) acrylate polymer contained in the curable resin composition by the heating step described above ( It reacts with the hydroxyl group of the hydroxyl group-containing monomer unit of the (meth) acrylate polymer to form a crosslinked structure, and the resulting cured product of the curable resin composition of the present invention is further excellent in solvent resistance and curability. It will be a thing.

The film thickness of the cured film obtained by the heating step (that is, the cured film obtained by thermosetting the curable resin composition) is preferably 0.1 to 20 μm. By using the curable resin composition of the present invention, a cured film having a sufficiently reduced film thickness can be provided. Further, since the film thickness is reduced, the density of the color material per unit volume of the cured film is increased, and the luminance of the color filter can be improved. The film thickness is more preferably 0.5 to 15 μm, still more preferably 1 to 10 μm.
In addition, it is suitable for the film thickness of the coating film (namely, cured film) obtained by the said heating process that it is 90% or less, when the film thickness of the coating film before a heating is 100%. More preferably, it is 80% or less, More preferably, it is 70% or less.

In the heating step, the heating temperature is preferably 150 ° C. or higher. Thereby, the part derived from a part of said tertiary carbon containing (meth) acrylate type monomer is decomposed | disassembled more effectively, and can improve the sclerosis | hardenability and solvent resistance which were mentioned above further. The heating temperature is more preferably 160 ° C. or higher, still more preferably 170 ° C. or higher, and particularly preferably 180 ° C. or higher. Moreover, it is preferable to set it as 260 degrees C or less, More preferably, it is 250 degrees C or less.

Although the heating time in the said heating process is not specifically limited, For example, it is suitable to set it as 5 to 60 minutes. Also, the heating method is not particularly limited, and for example, it can be performed using a heating device such as a hot plate, a convection oven, or a high-frequency heater.

5. Display Device The present invention is also a display device configured using the color filter.
In addition, the display apparatus member and display apparatus which have the hardened | cured material formed with the said curable resin composition are also contained in suitable embodiment of this invention. The cured product (cured film) formed by the curable resin composition is stable, excellent in adhesion to a substrate, etc., and has high hardness, high smoothness, and high transmittance. Therefore, it is particularly suitable as a transparent member, and is also useful as a protective film or insulating film in various display devices.

As the display device, for example, a liquid crystal display device, a solid-state imaging device, a touch panel display device, and the like are suitable.
In addition, when using the said hardened | cured material (cured film) as a member for display apparatuses, the said member may be a film-form single layer or multilayer member comprised from the said cured film, or this single layer or multilayer It may be a member in which another layer is further combined with the above member, or may be a member including the above-mentioned cured film in its constitution.

As described above, the curable resin composition of the present invention can give a cured product excellent in solvent resistance and heat-resistant colorability. Moreover, the hardened | cured material obtained using the curable resin composition of this invention is excellent also in adhesiveness with a board | substrate, heat resistance, transparency, etc. Such a curable resin composition of the present invention is useful for various uses such as a color filter. In addition, a color filter and a display device having a cured product formed from such a curable resin composition are very useful in the optical field, the electric machinery / electronic field, and the like.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

In this example, measurement conditions such as various physical properties are as follows.
(1) Weight average molecular weight (Mw)
Weight average molecular weight was measured by a GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corp.) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corp.) using polystyrene as a standard substance and eluent as tetrahydrofuran.

(2) About 1 g of the solid polymer solution was weighed into an aluminum cup, dissolved by adding about 3 g of acetone, and then naturally dried at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC Corp.), it was dried at 140 ° C. for 1.5 hours under vacuum, then allowed to cool in a desiccator, and the mass was measured. From the mass reduction amount, the solid content (% by mass) of the polymer solution was calculated.

(3) Acid value (AV)
3 g of the polymer solution was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1N KOH aqueous solution as a titrant. Titration was performed using an automatic titration apparatus (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and an acid value (mg KOH / g) per gram of solid content was determined from the acid value of the solution and the solid content of the solution.

(4) Amount of hydroxyl groups The amount of hydroxyl groups was determined by the following formula.
Hydroxyl amount (mol%) = [mol number of hydroxyl group-containing monomer] / [mol number of all monomer components] × 100
The above “number of moles of the hydroxyl group-containing monomer” is specifically the total number of moles of methyl 2- (1-hydroxyalkyl) acrylate and 2-hydroxyethyl methacrylate.

(5) Cyclization rate (mol%)
All (meth) acrylic acid units corresponding to the difference between the theoretical acid value and the actually measured acid value calculated in (3) were consumed for lactone ring formation, and the cyclization rate was determined by the following equation.
Cyclization rate (mol%) = [(mole number of (meth) acrylic acid corresponding to difference between theoretical acid value and actual acid value) / (mole number of 2- (hydroxyalkyl) acrylic acid ester)] × 100
The theoretical acid value is a value obtained by a calculation formula of [number of moles of (meth) acrylic acid units] / [total mass of all monomer components] × 56.11.

(6) Heat-resistant coloring copolymer solution 1.5 g of polymer was precisely weighed and spin-coated on a 5 cm square glass substrate, 100 ° C. for 1 hour, 180 ° C. for 1 hour, 250 ° C. for 2 hours. Heat treatment was sequentially performed to obtain a thin film having a thickness of 40 μm. The obtained thin film was measured with a color difference meter ZE6000 (manufactured by Nippon Denshoku Industries Co., Ltd., measurement condition in reflection mode), and after the heat treatment at 100 ° C. for 1 hour and the heat treatment at 250 ° C. for 2 hours, The change in color was evaluated by the difference in each b * value. Note that b * is a chromaticity representing saturation based on the L *, a *, and b * color systems standardized by CIE and adopted in Japan by JIS (JIS Z 8729).

(7) A solvent-resistant curable resin composition is spin-coated on a 5 cm square glass substrate, dried at 90 ° C. for 3 minutes, exposed to 100 mJ with a high-pressure mercury lamp, and heat-treated at 230 ° C. for 30 minutes. A cured film having a thickness of 5 μm was obtained. Then, the cured film was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 25 ° C. for 2 hours and then taken out. The immersion liquid (NMP) after taking out the cured film was measured with a spectrophotometer UV3100 (Shimadzu Corporation). The absorbance at 450 nm was measured. The larger the absorbance value, the more the coloring material was eluted in the immersion liquid, and it was evaluated that the solvent resistance of the curable resin composition was low.

(8) The film-decreasing rate curable resin composition was spin-coated on a 5 cm square glass substrate, dried at 100 ° C. for 3 minutes, and then exposed to 100 mJ with a high-pressure mercury lamp to obtain a cured film. Next, when a part of the center of the cured film was scraped off, the film thickness corresponding to the difference between the glass reference surface and the coating film surface was measured using a surface roughness meter VertScan 2.0 (manufactured by Ryoka System Co., Ltd.). Further, after heat treatment at 230 ° C. for 30 minutes, the film thickness was measured in the same manner, and the film reduction rate (%) was calculated from the film thickness before and after the heat treatment according to the following formula.
Film reduction rate (%) = [(film thickness before heat treatment−film thickness after heat treatment) / film thickness before heat treatment] × 100
By making the cured film thinner after the heat treatment, the amount (concentration) of the color material per volume increases, and as a result, the colorability of the cured product improves.

(Synthesis Example 1)
Preparation of copolymer solution 1 (RHMA-t-BMA-MMA-HEMA-AA copolymer solution) A reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dripping vessel introduction port. Then, 290 parts of propylene glycol monomethyl ether acetate was charged and purged with nitrogen, and then heated to 90 ° C. On the other hand, as a dropping tank (A), 10.0 parts of methyl 2- (1-hydroxymethyl) acrylate, 35.0 parts of t-butyl methacrylate, 19.7 parts of methyl methacrylate, 2-hydroxy methacrylate were added to a beaker. Prepared by stirring and mixing 20.0 parts of ethyl, 15.3 parts of acrylic acid and 2.0 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation), and dropping tank (B) was prepared by stirring and mixing 1.5 parts of n-dodecyl mercaptan and 10 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction vessel reached 90 ° C., dropping was started over 3 hours from the dropping vessel while maintaining the same temperature, and polymerization was performed. After maintaining the temperature at 90 ° C. for 30 minutes after completion of the dropping, the temperature was raised to 115 ° C. and aging was performed for 90 minutes. Then, it cooled to room temperature and obtained the copolymer solution 1. Various physical properties are shown in Table 1.

(Synthesis Example 2)
Preparation of copolymer solution 2 (RHMA-t-BMA-MMA-HEMA-AA copolymer solution) The amount of monomer charged in the dropping tank (A) was 2- (1-hydroxymethyl). Synthesis examples except 5.0 parts methyl acrylate, 35.0 parts t-butyl methacrylate, 24.7 parts methyl methacrylate, 20.0 parts 2-hydroxyethyl methacrylate, and 15.3 parts acrylic acid In the same manner as in Example 1, a copolymer solution 2 was obtained. Various physical properties are shown in Table 1.

(Synthesis Example 3)
Preparation of copolymer solution 3 (RHMA-t-BMA-MMA-HEMA-AA copolymer solution) The amount of monomer charged in the dropping tank (A) was 2- (1-hydroxymethyl). Synthesis examples except 30.0 parts methyl acrylate, 35.0 parts t-butyl methacrylate, 8.0 parts methyl methacrylate, 10.0 parts 2-hydroxyethyl methacrylate, and 17.0 parts acrylic acid 1 was used to obtain a copolymer solution 3. Various physical properties are shown in Table 1.

(Synthesis Example 4)
Preparation of copolymer solution 4 (RHMA-t-BMA-HEMA-AA copolymer solution) The amount of monomer charged in the dropping tank (A) was changed to 2- (1-hydroxymethyl) acrylic acid. Copolymer in the same manner as in Synthesis Example 1 except that 30.0 parts of methyl, 50.0 parts of t-butyl methacrylate, 4.0 parts of 2-hydroxyethyl methacrylate, and 16.0 parts of acrylic acid were used. Solution 4 was obtained. Various physical properties are shown in Table 1.

(Synthesis Example 5)
Preparation of copolymer solution 5 (RHMA-t-BMA-MMA-AA copolymer solution) The amount of monomer charged in the dropping tank (A) was changed to 2- (1-hydroxymethyl) acrylic acid. A copolymer solution 5 was prepared in the same manner as in Synthesis Example 1 except that 30.0 parts of methyl, 35.0 parts of t-butyl methacrylate, 18.0 parts of methyl methacrylate, and 17.0 parts of acrylic acid were used. Obtained. Various physical properties are shown in Table 1.

(Synthesis Example 6)
Preparation of copolymer solution 6 (RHMA-t-BMA-MMA-HEMA-AA copolymer solution) The charging amount of the monomer in the dropping tank (A) was 2- (1-hydroxymethyl). Synthesis examples except 10.0 parts methyl acrylate, 35.0 parts t-butyl methacrylate, 14.3 parts methyl methacrylate, 20.0 parts 2-hydroxyethyl methacrylate, and 20.7 parts acrylic acid 1 was used to obtain a copolymer solution 6. Various physical properties are shown in Table 1.

(Synthesis Example 7)
Preparation of copolymer solution 7 (BzMI-t-BMA-MMA-HEMA-AA copolymer solution) The amount of monomer charged in the dropping tank (A) was 10.0 parts of N-benzylmaleimide. In the same manner as in Synthesis Example 1, except that 35.0 parts of t-butyl methacrylate, 19.5 parts of methyl methacrylate, 20.0 parts of 2-hydroxyethyl methacrylate, and 15.5 parts of acrylic acid were used. A copolymer solution 7 was obtained. Various physical properties are shown in Table 1.

(Synthesis Example 8)
Preparation of copolymer solution 8 (RHMA-BMA-HEMA-AA copolymer solution) The amount of monomer charged in the dropping tank (A) was changed to methyl 2- (1-hydroxymethyl) acrylate 30 A copolymer solution 8 was obtained in the same manner as in Synthesis Example 1, except that 0.0 part, 34.0 parts of butyl methacrylate, 20.0 parts of 2-hydroxyethyl methacrylate, and 16.0 parts of acrylic acid were used. It was. Various physical properties are shown in Table 1.

(Synthesis Example 9)
Preparation of copolymer solution 9 (RHMA-t-BMA-MMA-HEMA-MAA copolymer solution) The amount of monomer charged in the dropping tank (A) was 2- (1-hydroxymethyl). Synthesis examples except 10.0 parts methyl acrylate, 35.0 parts t-butyl methacrylate, 16.5 parts methyl methacrylate, 20.0 parts 2-hydroxyethyl methacrylate, and 18.5 parts methacrylic acid 1 was used to obtain a copolymer solution 9. Various physical properties are shown in Table 1.

(Synthesis Example 10)
Preparation of copolymer solution 10 (RHMA-t-BMA-MMA-HEMA-MAA copolymer solution) The amount of monomer charged in the dropping tank (A) was 2- (1-hydroxymethyl). Synthesis example except 15.0 parts methyl acrylate, 35.0 parts t-butyl methacrylate, 11.5 parts methyl methacrylate, 20.0 parts 2-hydroxyethyl methacrylate, and 18.5 parts methacrylic acid 1 was used to obtain a copolymer solution 10. Various physical properties are shown in Table 1.

(Synthesis Example 11)
Preparation of copolymer solution 11 (RHMA-t-BMA-MMA-HEMA-MAA copolymer solution) The amount of monomer charged in the dropping tank (A) was 2- (1-hydroxymethyl). Synthesis examples except 20.0 parts methyl acrylate, 35.0 parts t-butyl methacrylate, 6.5 parts methyl methacrylate, 20.0 parts 2-hydroxyethyl methacrylate, and 18.5 parts methacrylic acid 1 was used to obtain a copolymer solution 11. Various physical properties are shown in Table 1.

(Synthesis Example 12)
Preparation of copolymer solution 12 (RHMA-t-BMA-MMA-HEMA-MAA copolymer solution) The amount of monomer charged in the dropping tank (A) was 2- (1-hydroxymethyl). Synthesis examples except 10.0 parts methyl acrylate, 35.0 parts t-butyl methacrylate, 10.0 parts methyl methacrylate, 20.0 parts 2-hydroxyethyl methacrylate, and 25.0 parts methacrylic acid 1 was used to obtain a copolymer solution 12. Various physical properties are shown in Table 1.

(Synthesis Example 13)
Preparation of copolymer solution 13 (RHMA-t-BMA-HEMA-MAA copolymer solution) The amount of monomer charged in the dropping tank (A) was changed to 2- (1-hydroxymethyl) acrylic acid. Copolymer in the same manner as in Synthesis Example 1, except that 20.0 parts of methyl, 35.0 parts of t-butyl methacrylate, 20.0 parts of 2-hydroxyethyl methacrylate, and 25.0 parts of methacrylic acid were used. Solution 13 was obtained. Various physical properties are shown in Table 1.

(Synthesis Example 14)
Preparation of copolymer solution 14 (BzMI-t-BMA-MMA-HEMA-MAA copolymer solution) The amount of monomer charged in the dropping tank (A) was 10.0 parts of N-benzylmaleimide. In the same manner as in Synthesis Example 1, except that 35.0 parts of t-butyl methacrylate, 17.5 parts of methyl methacrylate, 20.0 parts of 2-hydroxyethyl methacrylate, and 17.5 parts of methacrylic acid were used. A copolymer solution 14 was obtained. Various physical properties are shown in Table 1.

(Synthesis Example 15)
Preparation of copolymer solution 15 (MD-t-BMA-MMA-HEMA-MAA copolymer solution) The amount of monomer charged in the dropping tank (A) was changed to dimethyl-2,2 '-[ Oxybis (methylene)] bis-2-propenoate 10.0 parts, 35.0 parts t-butyl methacrylate, 18.5 parts methyl methacrylate, 20.0 parts 2-hydroxyethyl methacrylate, and 16.5 methacrylic acid A copolymer solution 15 was obtained in the same manner as in Synthesis Example 1 except that the content was 1 part. Various physical properties are shown in Table 1.

The heat resistance colorability was evaluated using the obtained copolymer solutions 1-15. The results are shown in Table 1.

The descriptions in Table 1 are as follows.
RHMA: methyl 2- (1-hydroxymethyl) acrylate BzMI: N-benzylmaleimide MD: dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate t-BMA: t-butyl methacrylate BMA: Butyl methacrylate MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate AA: Acrylic acid MAA: Methacrylic acid

According to Table 1, for example, a (meth) acrylate polymer having a structural unit represented by the general formula (1) and a tertiary carbon-containing (meth) acrylate monomer unit (Synthesis Examples 1 to 6, 9 to 13) showed a tendency to be superior in heat-resistant colorability as compared with (meth) acrylate-based polymers (Synthesis Examples 7, 8, 14 and 15) not having the above structural units.
Further, according to Table 1, the heat resistant colorability is generally higher when methacrylic acid is used than when acrylic acid is used as a monomer component capable of forming the above cyclized structure. Although it becomes more excellent in colorability, it is represented by the above general formula (1) in each of the cases where acrylic acid is used (Synthesis Examples 1 to 8) and methacrylic acid (Synthesis Examples 9 to 15). The (meth) acrylate polymer having a structural unit and a tertiary carbon-containing (meth) acrylate monomer unit was found to have excellent heat resistant colorability.

(Preparation Example 1)
Preparation of Pigment Dispersion 1 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparon DA-7301 as a dispersant, and C.I. I. Pigment Green 58 (2.25 parts) and C.I. I. 1.5 parts of Pigment Yellow 138 was mixed and dispersed for 3 hours with a paint shaker to obtain Pigment Dispersion 1 (solid content 22% by mass).

Example 1
2.0 parts of copolymer solution 1, 0.70 parts of dipentaerythritol hexaacrylate as a radical polymerizable compound, 0.35 parts of Irgacure 369 (manufactured by BASF Japan) as a radical polymerizable photopolymerization initiator, pigment 8.5 parts of Dispersion 1 and 6.57 parts of propylene glycol monomethyl ether acetate as a solvent were mixed to obtain curable resin composition 1.

(Examples 2-11, Comparative Examples 1-4)
Except having set it as the mixing | blending shown in Table 2 and Table 3, it carried out similarly to Example 1, and obtained curable resin composition 2-15.

The resulting curable resin compositions 1 to 15 were evaluated for solvent resistance and film reduction rate. The results are shown in Tables 2 and 3.

According to Tables 2 and 3, the (meth) acrylate polymer having the structural unit represented by the general formula (1) and the tertiary carbon-containing (meth) acrylate monomer unit, a polymerizable compound, and light It was recognized that the curable resin composition of the Example containing a polymerization initiator was superior in solvent resistance of the cured product as compared with the curable resin composition of the comparative example. Moreover, it was recognized that the curable resin composition of an Example has a large film reduction rate value compared with the comparative example, and is excellent also in the coloring property of hardened | cured material.
As mentioned above, it was recognized that the curable resin composition of this invention is excellent in heat-resistant coloring property and solvent resistance, and is excellent in coloring property.

Claims (13)

A curable resin composition comprising a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator,
The said (meth) acrylate type polymer has a structural unit shown by following General formula (1), and a tertiary carbon containing (meth) acrylate type monomer unit, The curable resin composition characterized by the above-mentioned.

(In General Formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and R ³ represents a hydrogen atom or a methyl group. , N represents 1 or 2.) The curing according to claim 1, wherein the tertiary carbon-containing (meth) acrylate monomer unit has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. Resin composition. The curable resin composition according to claim 1, wherein the (meth) acrylate polymer further has a hydroxyl group-containing monomer unit. The said (meth) acrylate type polymer further has a monomer unit derived from (meth) acrylic acid, The curable resin composition in any one of Claims 1-3 characterized by the above-mentioned. The structural unit represented by the general formula (1) is a lactone ring structural unit derived from 2- (hydroxyalkyl) acrylic acid alkyl ester and (meth) acrylic acid. A curable resin composition according to claim 1. The curable resin composition according to claim 5, wherein a cyclization rate of the (meth) acrylate polymer is 50 mol% or less. The weight average molecular weight of the said (meth) acrylate type polymer is 2000-50000, The curable resin composition in any one of Claims 1-6 characterized by the above-mentioned. The curable resin composition according to any one of claims 1 to 7, wherein the acid value of the (meth) acrylate polymer is 5 to 200 mgKOH / g. Hardened | cured material formed by hardening | curing the curable resin composition in any one of Claims 1-8. A color filter comprising the cured product according to claim 9. A display device comprising the color filter according to claim 10. A step of polymerizing a monomer component containing 2- (hydroxyalkyl) acrylic acid alkyl ester represented by the following general formula (2), a tertiary carbon-containing (meth) acrylate monomer, and (meth) acrylic acid. A process for producing a (meth) acrylate polymer, comprising:

(In General Formula (2), R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and n represents 1 or 2). The production method according to claim 12, wherein the cyclization rate of the (meth) acrylate polymer is 50 mol% or less.