JP2019163359A - Radical polymerizable copolymer, curable resin composition and use therefor - Google Patents

Abstract

To provide a radical polymerizable copolymer that can give a cured product having a high development speed and excellent developability, pattern linearity and solvent resistance, and a curable resin composition containing the copolymer.SOLUTION: A radical polymerizable copolymer has an acid radical and an ethylenic unsaturated double bond in a side chain; the radical polymerizable copolymer has an N-substituted maleimide compound-derived structural unit, and a structural unit represented by the following general formula (1); a double bond equivalent is 330-2000 g/equiv.; a glass transition temperature is less than 50°C; a content of a styrene or an alkyl substituted styrene is 5 mass% or less relative to 100 mass% of all the structural units of the copolymer; and an interval of the acid radical to the main chain is 6 or less in atom number (where Ris a hydrogen atom or a methyl group. Ris a C4-20 linear or branched hydrocarbon group).SELECTED DRAWING: None

Description

The present invention relates to a radically polymerizable copolymer. More specifically, it has a radically polymerizable copolymer, a curable resin composition, and a cured product of the curable resin composition, which are excellent in developability and can give a cured product having excellent pattern linearity and solvent resistance. The present invention relates to a laminate, a color filter, and a display device.

Curable resin compositions that can be cured by heat or active energy rays include, for example, color filters, inks, printing plates, printed wiring boards, semiconductor elements, and photoresists used in liquid crystal display devices and solid-state imaging devices. Various applications for various uses such as optical members and electrical / electronic devices have been studied, and curable resin compositions having excellent characteristics required for each use have been developed. Among these applications, the color filter is a main member that constitutes a liquid crystal display device, a solid-state imaging device, and the like, and is generally a substrate, and at least three primary colors (red (R), green (G), and blue (B)). In addition to the pixel and the resin black matrix (BM) and black column spacer (BCS) that divide the pixel, the pixel and the resin black matrix are covered and protected, and a protective film provided for flattening the unevenness thereof It is composed.

Usually, when forming a pixel of a color filter using a curable resin composition, for each pixel color, (1) an application process for applying the curable resin composition to the entire surface of the substrate, and (2) an application process. The resist film is exposed to a pattern through a photomask to cure the exposed portion, and then the exposure step in which the cured portion is insolubilized. (3) The unexposed portion is removed with a developer and then exposed by baking (baking). A method of performing a development / baking (baking) treatment step for further curing the part and repeating the same step for each color is adopted. In consideration of application to such uses of color filters, the curable resin composition has various properties such as curability, solvent resistance after curing, adhesion to a substrate (base material), heat resistance and transparency. It is required to have physical properties. In recent years, optical members, electric devices, electronic devices, and the like have been reduced in size, thickness, and energy saving, and accordingly, members such as color filters to be used are required to have high quality performance.

Various curable resin compositions used for color filters and the like have been proposed so far.
For example, Patent Document 1 describes a photosensitive resin composition for a color filter including a carboxyl group-containing radical polymerizable copolymer, and the copolymer includes a monomer unit derived from an N-substituted maleimide compound. And the resin composition which has a carboxyl group and an ethylenically unsaturated double bond, and whose Tg (glass transition temperature) of the said copolymer is 20 degrees C or less is described.
Further, for example, in Patent Document 2, a carboxyl group is arranged in a side chain separated from the main chain by 7 or more elements, and further has a radical polymerizable double bond in the side chain, so that it has excellent flexibility and alkali A carboxyl group-containing radical copolymer having improved remaining film properties without reducing developability and a photosensitive resin composition containing the carboxyl group-containing radical copolymer are described.

JP 2012-32772 A JP 2012-193219 A

However, in the conventional photosensitive resin composition, the photosensitive resin is used together with the color material as a color filter raw material, but there is a problem that the color material is eluted from the raw material into the cleaning solvent during the production of the color filter. There has been a need for improved resistance to solvents.

Furthermore, in recent years, with an increase in demand for color filters, improvement in quality and productivity is demanded, and there is also a demand for good development in a short time. For example, in the production of a color filter, it is necessary to remove the unexposed portion with a developer after exposure in a short time after the exposure. It is also important that after the unexposed part is removed, the pattern edge of the formed exposed part is sharp and linear. Although such developability has been studied so far, further improvement is required as the performance required for color filters and the like increases.

In view of the above situation, the present invention provides a radical polymerizable copolymer capable of providing a cured product having a high development speed, excellent developability, and excellent pattern linearity and solvent resistance, and the radical polymerizable copolymer. It aims at providing the curable resin composition containing coalescence. Another object of the present invention is to provide a laminate having a cured product of such a curable resin composition, a color filter using the cured product, and a display device.

In order to solve the above-mentioned problems, the present inventor has made various studies on copolymers that can be used in color filter applications, and has an acid group and an ethylenically unsaturated double bond (carbon-carbon double bond) in the side chain. A radical polymerizable copolymer, wherein the radical polymerizable copolymer has a structural unit derived from an N-substituted maleimide compound and a specific structural unit, and a double bond equivalent and a glass transition temperature are within a specific range, By using a copolymer with the content ratio of other specific structural units in a specific range and the position of acid groups in a specific range, a cured product with high development speed and excellent pattern linearity and solvent resistance Found that you can get. Further, the present inventors have found that a curable resin composition containing such a radical polymerizable copolymer is particularly suitable as a resin composition for forming a member for use such as a color filter. The invention has been completed.

That is, the present invention is a radical polymerizable copolymer having an acid group and an ethylenically unsaturated double bond in the side chain, the radical polymerizable copolymer is a structural unit derived from an N-substituted maleimide compound, And having a structural unit represented by the following general formula (1), having a double bond equivalent of 330 to 2000 g / equivalent, a glass transition temperature of less than 50 ° C., and represented by the following general formula (2) The content ratio of the structural unit is 5% by mass or less with respect to 100% by mass of all the structural units of the radical polymerizable copolymer, and the acid group has a distance of 6 or less atoms from the main chain. Is a radically polymerizable copolymer characterized by

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms.)

(In the formula, R ³ represents a hydrogen atom or a methyl group.)

The radical polymerizable copolymer preferably has a ring structure in the side chain.

In the radical polymerizable copolymer, the content ratio of the structural unit represented by the general formula (1) is 10% by mass or more with respect to 100% by mass of all the structural units of the radical polymerizable copolymer. Is preferred.

The acid group is preferably a carboxyl group derived from (meth) acrylic acid.

The radical polymerizable copolymer preferably has an acid value of 30 to 200 mgKOH / g.

The present invention is also a curable resin composition comprising the above-mentioned radical polymerizable copolymer and a polymerizable compound.

This invention is also a laminated body characterized by having the hardened | cured material of the above-mentioned curable resin composition on a board | substrate.

This invention is also a color filter characterized by having the hardened | cured material of the above-mentioned curable resin composition on a board | substrate.

The present invention is also a display device including the color filter described above.

The radical-polymerizable copolymer and curable resin composition of the present invention can provide a cured product having a high development speed, excellent developability, and excellent pattern linearity and solvent resistance. Such radically polymerizable copolymer and curable resin composition of the present invention include color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists and the like used for liquid crystal display devices and solid-state imaging devices. It can be suitably used for various applications such as optical members, electric machines and electronic devices.

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.
In the present specification, “(meth) acrylate” means “acrylate and / or methacrylate”, and “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”.

1. Radical polymerizable copolymer The radical polymerizable copolymer of the present invention is a radical polymerizable copolymer having an acid group and an ethylenically unsaturated double bond in the side chain, and the radical polymerizable copolymer is , A structural unit derived from an N-substituted maleimide compound, and a structural unit represented by the following general formula (1), a double bond equivalent is 330 to 2000 g / equivalent, and a glass transition temperature is less than 50 ° C. Yes, the content ratio of the structural unit represented by the following general formula (2) is 5% by mass or less with respect to 100% by mass of all the structural units of the radical polymerizable copolymer, and the acid group has a main chain. Is a radically polymerizable copolymer characterized by having an interval of 6 or less.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms.)

(In the formula, R ³ represents a hydrogen atom or a methyl group.)
Since the radically polymerizable copolymer of the present invention has the above-described configuration, it can give a cured product having a high development speed, excellent developability, and excellent pattern linearity and solvent resistance. The radically polymerizable copolymer of the present invention is excellent in developability because it has a structural unit derived from an N-substituted maleimide compound and a structural unit represented by the above general formula (1), and has a glass transition in a specific range. By having a temperature, it is presumed that the developer easily penetrates into the film formed using the above copolymer during development. In addition, the pattern linearity is excellent because the structural unit represented by the general formula (1) has hydrophobicity, so that it is possible to prevent the resin from passing through the cured portion (exposed portion) during development and generate a residue. This is presumably because the edges of the pattern are uniformly developed. Furthermore, it is presumed that the solvent resistance is excellent because the hydrophobicity of the copolymer is improved by having the above-described specific structural unit and having a specific range of double bond equivalents.

Moreover, the radically polymerizable copolymer of the present invention can further provide a cured product having excellent heat resistance. The radically polymerizable copolymer of the present invention is excellent in heat resistance because it has a structural unit derived from an N-substituted maleimide compound, includes a structural unit represented by the general formula (1), and an acid group. Is presumed to be in a specific range of positions.

Moreover, the radically polymerizable copolymer of the present invention can further provide a cured product having excellent dispersibility of pigments and the like and excellent adhesion. It is presumed that the radically polymerizable copolymer of the present invention is excellent in dispersibility of pigments and the like because it has a hydrophobic structure. In particular, the radically polymerizable copolymer of the present invention has a good compatibility with a dispersant having a high amine value, and has a very high pigment dispersibility because it is compatible without forming a salt. Moreover, it is estimated that it is because it has an acid group that the hardened | cured material excellent in adhesiveness can be given.

The radically polymerizable copolymer of the present invention has an acid group and an ethylenically unsaturated double bond in the side chain.
When the radical polymerizable copolymer has an acid group in the side chain, it becomes alkali-soluble and developability can be exhibited. Moreover, in the hardened | cured material of the said radically polymerizable copolymer, adhesiveness can be exhibited.

The acid group has a distance of 6 or less atoms from the main chain. When the acid group is in a specific range, the developability of the radical polymerizable copolymer is improved. In addition, the hydrophobicity and heat resistance of the radical polymerizable copolymer can be suitably exhibited.

Usually, when producing a radically polymerizable copolymer having an acid group at a position relatively far from the main chain, the vinyl monomer is reacted with a compound having an acid group or an acid anhydride to leave the vinyl group. A monomer having an acid group at the selected position is synthesized, and copolymerization is performed using this monomer. For example, a monomer having an acid group at a position away from a vinyl group can be obtained by reacting hydroxyethyl (meth) acrylate with maleic anhydride, and this is produced by copolymerizing this monomer. When the radically polymerizable copolymer is used in the production of a color filter, water is added during the post-curing process (heating process) to desorb the maleic acid part, which becomes a foreign substance, resulting in the heat resistance of the resulting cured product. And transparency may be reduced. On the other hand, when the distance between the acid group and the main chain is 6 or less, it is not necessary to use a monomer obtained by reacting a vinyl monomer with a compound having an acid group or an acid anhydride. In addition, the acid group portion is not detached in the color filter manufacturing process, and the heat resistance and transparency of the radical polymerizable copolymer are not lowered.

Here, in the present invention, the distance from the main chain is 6 or less atoms means that the number of atoms between the main chain atom to which the side chain is bonded and the atom to which the acid group is bonded on the side chain is It means 6 or less. For example, in the structural unit represented by the following (a1), the acid group X is assumed to be 4 atoms apart from the main chain, and in the structural unit represented by the following (a2), the acid group X is Suppose that the distance from the main chain is 6 atoms. When the acid group is directly bonded to the main chain, the distance from the main chain is 0 atoms.

The acid group preferably has a distance from the main chain of 6 or less, more preferably 5 or less, and even more preferably 0.
The acid group is preferably directly bonded to the main chain.

Examples of the acid group include functional groups that neutralize with alkaline water, such as carboxyl groups, phenolic hydroxyl groups, carboxylic anhydride groups, phosphoric acid groups, and sulfonic acid groups. Of these, a carboxyl group or a carboxylic anhydride group is preferable, a carboxyl group is more preferable, and a (meth) acrylic acid group is still more preferable. From the viewpoint of further increasing the development speed, an acrylic acid group is preferred.

Moreover, the said radically polymerizable copolymer has an ethylenically unsaturated double bond in a side chain. Thereby, since heat and a photo-crosslinking reaction are attained, sclerosis | hardenability, image development adhesiveness, solvent resistance, etc. improve. Moreover, the sensitivity with respect to light improves, it can harden | cure with less light, and the mechanical strength of the hardened | cured material after hardening can also be improved.
In the present invention, the ethylenically unsaturated double bond means a polymerizable double bond, that is, a carbon-carbon double bond.

Examples of the ethylenically unsaturated double bond include (meth) acryloyl group, vinyl group, allyl group, methallyl group and the like. The radically polymerizable copolymer of the present invention may have one or more of these. Of these, a (meth) acryloyl group is preferable in terms of reactivity.

The ethylenically unsaturated double bond can be introduced into the radical polymerizable copolymer by using, for example, the epoxy group-containing monomer (X) during the production of the radical polymerizable copolymer.

As said epoxy group containing monomer (X), the compound containing an epoxy group and a polymerizable double bond is mentioned. Examples of the polymerizable double bond are the same as the ethylenically unsaturated double bond described above, and examples thereof include (meth) acryloyl group, vinyl group, allyl group, methallyl group, and the like. What has the above is suitable. Of these, a (meth) acryloyl group is preferable in terms of reactivity.

In this specification, the epoxy group includes an epoxy group in a narrow sense, a group in which an oxirane ring is bonded to carbon such as a glycidyl group, an ether bond or an ester bond such as a glycidyl ether group and a glycidyl ester group. Including groups, epoxycyclohexane rings and the like.

Examples of the epoxy group-containing monomer (X) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether. (Meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide, and the like. Among them, glycidyl (meth) acrylate and / or from the viewpoint that the reactivity is high and the reaction is easy to control and is easily available, and not only radically polymerizable double bonds but also hydroxyl groups can be introduced at the same time. (Meth) acrylic acid 3,4-epoxycyclohexylmethyl is more preferred. More preferred is glycidyl (meth) acrylate (also known as glycidyl (meth) acrylate), and particularly preferred is glycidyl methacrylate.

The radically polymerizable copolymer of the present invention has a structural unit derived from an N-substituted maleimide compound and a structural unit represented by the general formula (1). Each structural unit will be described.

(Structural unit (A) derived from N-substituted maleimide compound)
The radical polymerizable copolymer has a structural unit derived from an N-substituted maleimide compound (hereinafter also referred to as “structural unit (A)”).
By having a structural unit derived from an N-substituted maleimide compound, the hydrophobicity of the radical polymerizable copolymer of the present invention is improved, and a cured product having excellent pattern linearity and solvent resistance can be obtained. Moreover, the heat resistance of hardened | cured material can be improved.

Examples of the monomer that provides the structural unit (A) include N-substituted maleimide compounds. By polymerizing the monomer component containing the N-substituted maleimide compound, a polymer having the structural unit (A) can be obtained.

Examples of N-substituted maleimide compounds include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, and N-benzyl. Maleimide, N-naphthylmaleimide and the like can be mentioned, and one or more of these can be used. Of these, N-benzylmaleimide and N-cyclohexylmaleimide are more preferable, and N-benzylmaleimide is more preferable because heat resistance can be further improved in addition to pattern linearity and solvent resistance.

Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide Halogen-substituted benzylmaleimide such as o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide;

The said radically polymerizable copolymer may have only 1 type as the said structural unit (A), and may have 2 or more types.

The content ratio of the structural unit (A) is 100% by mass of all structural units of the radical polymerizable copolymer, considering the compatibility of developability, pattern linearity, and solvent resistance of the radical polymerizable copolymer. It is preferable that it is 0.5-50 mass% with respect to. The content ratio of the structural unit (A) is more preferably 1% by mass or more, still more preferably 2% by mass or more, and more preferably with respect to 100% by mass of all the structural units of the radical polymerizable copolymer. Is 30% by mass or less, more preferably 20% by mass or less.

(Structural unit (B) represented by general formula (1))
The radically polymerizable copolymer of the present invention also has a structural unit represented by the following general formula (1) (hereinafter also referred to as “structural unit (B)”).

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms.)
When the radically polymerizable copolymer of the present invention has the structural unit (B), the developability is improved, and a cured product excellent in pattern linearity and solvent resistance can be provided.

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. From the viewpoint of development speed, R ¹ is preferably a hydrogen atom.

In the general formula (1), R ² represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms.
Examples of the linear or branched hydrocarbon group having 4 to 20 carbon atoms include n-butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2, 2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,2,2-trimethylpropyl group, 1-ethyl 1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n- Examples include dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-eicosyl group.

The linear or branched hydrocarbon group having 4 to 20 carbon atoms is preferably a linear or branched hydrocarbon group having 4 to 18 carbon atoms, and is a linear chain having 4 to 8 carbon atoms. Or it is more preferable that it is a branched hydrocarbon group.

Specific examples of R ² include preferably an n-dodecyl group, an n-butyl group, and a 2-ethylhexyl group, more preferably an n-butyl group and a 2-ethylhexyl group, still more preferably. A 2-ethylhexyl group is mentioned.

Preferred examples of the monomer that gives the structural unit (B) include compounds represented by the following general formula (1-1).
^{_{CH 2 = CR 1 -C (O}} ) -O-R 2 (1-1)
(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms.)
By polymerizing a monomer component containing such a monomer compound, a polymer having the structural unit (B) can be obtained.

The ^{R 1} and ^{R 2} in the general formula (1-1), respectively, are the same as those for ^{R 1} and ^{R 2} in the general formula (1).

Specific examples of the monomer that gives the structural unit (B) are preferably n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-dodecyl (meth) acrylate, and the like. More preferred are n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.

The said radically polymerizable copolymer may have only 1 type as the said structural unit (B), and may have 2 or more types.

The content ratio of the structural unit (B) is 100% by mass of all structural units of the radical polymerizable copolymer, considering the compatibility of developability, pattern linearity, and solvent resistance of the radical polymerizable copolymer. It is preferable that it is 10 mass% or more. The content ratio of the structural unit (B) is more preferably 10.5% by mass or more, still more preferably 11% by mass or more, and preferably 90% by mass or less, with respect to 100% by mass of all the structural units. More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.

(Structural unit derived from acid group-containing monomer (C))
The radical polymerizable copolymer of the present invention preferably further has a structural unit derived from an acid group-containing monomer (hereinafter also referred to as “structural unit (C)”). By having a structural unit (C), the said radically polymerizable copolymer has the acid group mentioned above, and can exhibit developability and adhesiveness.

Examples of the monomer that gives the structural unit (C) include acid group-containing monomers. By polymerizing a monomer component containing an acid group-containing monomer, a polymer having the structural unit (C) can be obtained.
Examples of the acid group of the acid group-containing monomer include the same acid groups as described above.

Examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid Unsaturated unsaturated carboxylic acids such as maleic anhydride and itaconic anhydride; phosphate group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); Among these, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. From the viewpoints of reactivity, heat resistance coloring property, etc., more preferable are unsaturated monocarboxylic acids, and still more preferable is (meth) acrylic acid. Thus, in the radical polymerizable copolymer, the acid group is preferably a carboxyl group derived from (meth) acrylic acid.

The radically polymerizable copolymer may have only one kind as the structural unit (C), or may have two or more kinds, but at least as the structural unit (C), It is preferable to have a structural unit having an acid group in which the distance from the chain is 6 or less. The acid group having 6 or less atoms from the main chain is as described above.

The content ratio of the structural unit (C) is 100% by mass of all structural units of the radical polymerizable copolymer, considering the compatibility of developability, pattern linearity, and solvent resistance of the radical polymerizable copolymer. It is preferable that it is 1-30 mass% with respect to. The content ratio of the structural unit (C) is more preferably 2% by mass or more, further preferably 2.5% by mass or more, and more preferably 25% by mass or less, with respect to 100% by mass of all the structural units. More preferably, it is 20 mass% or less.

(Structural unit (D) having a ring structure in the side chain)
The radically polymerizable copolymer of the present invention preferably has a ring structure in the side chain. That is, the radical polymerizable copolymer preferably has a structural unit having a ring structure in the side chain (hereinafter also referred to as “structural unit (D)”). By having a ring structure in the side chain, the hydrophobicity of the radical polymerizable copolymer can be improved, and the pattern linearity and solvent resistance can be further improved.

Examples of the ring structure include aromatic ring structures such as benzene, and alicyclic structures such as a cyclohexane skeleton, an adamantane skeleton, and a norbornene skeleton.

In order for the radical polymerizable copolymer to have a ring structure in the side chain, a monomer component including an aromatic hydrocarbon group or an alicyclic hydrocarbon group and a monomer having a polymerizable double bond is polymerized. Good.

Examples of the aromatic hydrocarbon group include aryl groups such as benzyl, tolyl, naphthyl, and biphenyl.
As said alicyclic hydrocarbon group, Preferably C3-C20, More preferably, C3-C15 alicyclic hydrocarbon group is mentioned. Specific examples of the alicyclic hydrocarbon group include monocyclic hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, cycloheptyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like; Examples thereof include polycyclic hydrocarbon groups such as pentanyl, dicyclopentenyl, tricyclodecanyl, adamantyl and isobornyl. These may have a substituent.

As said polymerizable double bond, it is the same as that of the ethylenically unsaturated double bond mentioned above, for example, (meth) acryloyl group, a vinyl group, an allyl group, a methallyl group etc. are mentioned. Of these, a (meth) acryloyl group is preferable in terms of reactivity.

Specific examples of the monomer that gives the structural unit (D) include cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (3 , 4-epoxycyclohexyl) methyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol- Alicyclic rings such as tricyclodecane di (meth) acrylate, pentacyclopentadecane dimethanol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, norbornane dimethanol di (meth) acrylate Hydrocarbon group-containing monomer; benzyl (meth) acrylate, aromatic hydrocarbon group-containing monomers such as 1 Moruetokishi phenylphenol acrylate. Especially, an alicyclic hydrocarbon group containing monomer is preferable at the point which can improve hydrophobicity, and a cyclohexyl (meth) acrylate is more preferable.

The content ratio of the structural unit (D) is preferably 1 to 60% by mass and more preferably 3 to 50% by mass with respect to 100% by mass of all the structural units of the radical polymerizable copolymer. Preferably, it is 5-40 mass%.

The said radically polymerizable copolymer may have only 1 type as said structural unit (D), and may have 2 or more types.

However, when the radical polymerizable copolymer has a structural unit represented by the following general formula (2) as the structural unit (D), the content ratio is all structural units of the radical polymerizable copolymer. It is 5 mass% or less with respect to 100 mass%.
The hydrogen atom at the benzyl position represented by the following general formula (2) is cleaved and radicals are easily generated in the main chain, and the heat resistance coloring property of the cured product of the radical polymerizable copolymer is lowered by oxidation of the main chain. There is a fear. In addition, the aromatic ring may absorb light and reduce the transparency of the cured product. Therefore, the content ratio of the structural unit represented by the following general formula (2) is preferably in the above-described range.
The content ratio of the structural unit represented by the following general formula (2) is preferably 3% by mass or less, preferably 1% by mass or less, with respect to 100% by mass of all the structural units of the radical polymerizable copolymer. Is more preferable, and it is still more preferable that it is 0 mass%.

(In the formula, R ³ represents a hydrogen atom or a methyl group.)
Examples of the monomer that gives the structural unit represented by the general formula (2) include styrene and vinyltoluene.

When the structural unit (D) has the structural unit represented by the general formula (2) and other structural units other than the structural unit, the content ratio of the other structural units is a radical polymerizable copolymer. Preferably it is 1-60 mass% with respect to 100 mass% of all the structural units, More preferably, it is 3-50 mass%. The content of the structural unit represented by the general formula (2) is 5% by mass or less, preferably 3% by mass or less, more preferably 100% by mass with respect to 100% by mass of all the structural units of the radical polymerizable copolymer. 1% by mass or less, more preferably 0% by mass.

(Other structural units (E))
The radical polymerizable copolymer may further have other structural units (E) other than the structural units (A) to (D) as necessary.
As said other structural unit (E), (meth) acrylic acid ester-type monomers other than the monomer which gives the said structural unit (B), a hydroxyl-containing monomer, or other copolymerization is possible, for example And structural units derived from various monomers.

Examples of (meth) acrylate monomers other than the monomer that gives the structural unit (B) include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate. , I-propyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylamino (meth) acrylate Ethyl, 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) acryloyloxy Methyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxy-2,2-dimethyl-1,3-dioxolane, and the like.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. And hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2,3-hydroxypropyl (meth) acrylate.

As said other copolymerizable monomer, 1 type (s) or 2 or more types, such as the following compound, are mentioned, for example.
(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; heavy materials such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone and polycaprolactam Macromonomers having a (meth) acryloyl group at one end of the combined molecular chain; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Class: methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl 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, and other vinyl ethers; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole N-vinyl compounds such as N-vinylmorpholine and N-vinylacetamide; Unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate; 2,2 ′-[oxybis (methylene)] bisacryl Acid, dialkyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dialkyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, etc. Dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers; α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl acrylate ethyl, α-allyloxy N-propyl methyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate Α- (unsaturated alkoxy) such as n-amyl α-allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, etc. Alkyl) acrylate monomers and the like.

The said radically polymerizable copolymer may have only 1 type as said structural unit (E), and may have 2 or more types.

The content ratio of the structural unit (E) is preferably 0 to 60% by mass, more preferably 0.3 to 50% by mass, with respect to 100% by mass of all the structural units of the radical polymerizable copolymer. More preferably, it is 0.5-40 mass%.

The radical polymerizable copolymer has a glass transition temperature (Tg) of less than 50 ° C. When the glass transition temperature is in the above-described range, the developer is likely to permeate during development, the development speed is high, and the developability is excellent. The glass transition temperature is preferably 30 ° C. or lower, more preferably 10 ° C. or lower, and further preferably 0 ° C. or lower. From the viewpoint of heat resistance, the glass transition temperature is preferably −50 ° C. or higher, and more preferably −25 ° C. or higher.
In the present specification, the glass transition temperature can be determined by the method described in Examples described later.

The double bond equivalent of the radical polymerizable copolymer is 330 to 2000 g / equivalent. When the double bond equivalent is within the above range, the hydrophobicity of the radical polymerizable copolymer is suitable, and the pattern linearity and the solvent resistance are good. Moreover, it is excellent also in developability, sensitivity to light, and the like. The double bond equivalent is preferably 335 g / equivalent or more, more preferably 340 g / equivalent or more, still more preferably 345 g / equivalent or more from the viewpoint of maintaining hydrophobicity and suppressing pattern line thickening. From the viewpoint of linearity or dispersibility, it is preferably 1900 g / equivalent or less, more preferably 1800 g / equivalent or less, still more preferably 1700 g / equivalent or less.

In this specification, the double bond equivalent is a measure of the amount of double bonds contained in a molecule, and means the molecular weight per double bond of a polymer. If the compounds have the same molecular weight, the amount of double bonds introduced decreases as the double bond equivalent value increases.
The double bond equivalent can be calculated from the charged amount of the raw material, and can be determined by dividing the mass (g) of the solid content of the polymer by the double bond amount (mol) of the polymer. Moreover, it can also measure using various analysis, such as titration and elemental analysis, NMR, IR, and a differential scanning calorimeter method.

The radical polymerizable copolymer preferably has a weight average molecular weight of 3000 to 50000. When the weight average molecular weight is in the above range, the solvent resistance is further improved. The weight average molecular weight is more preferably 4000 to 40000, and further preferably 5000 to 35000.
In this specification, a weight average molecular weight can be calculated | required by the method described in the below-mentioned Example.

The acid value of the radical polymerizable copolymer is preferably 30 to 200 mgKOH / g. When the acid value is in the above-mentioned range, not only the alkali solubility is further expressed, but also the solvent resistance is further improved, and the development speed is further appropriate. Further, the leading edge of the resin during development is suppressed, and the pattern linearity is further improved. Further, the dispersibility of the radical polymerizable copolymer is also improved. The acid group is more preferably 31 to 150 mgKOH / g, still more preferably 32 to 100 mgKOH / g.
In this specification, an acid value can be calculated | required by the method described in the below-mentioned Example.

(Method for producing radically polymerizable copolymer)
The method for producing the radical polymerizable copolymer of the present invention will be described.
The method for obtaining the radical polymerizable copolymer is not particularly limited. For example, (1) the monomer (a) that gives the structural unit (A) described above, and the single monomer that gives the structural unit (B) described above. The above-mentioned epoxy group-containing polymer (b) and a polymer obtained by polymerizing the monomer component containing at least the acid group-containing monomer (c) (hereinafter also referred to as “base polymer 1”). A monomer component containing at least the monomer (X) and (2) the monomer (a), the monomer (b), and the epoxy group-containing monomer (X) And a method of reacting the acid group-containing monomer (c) with a polymer obtained by polymerizing (hereinafter also referred to as “base polymer 2”). That is, the radical polymerizable copolymer is a reaction product of the base polymer 1 and the epoxy group-containing monomer (X) or a reaction product of the base polymer 2 and the acid group-containing monomer (c). It is preferable that Especially, it is preferable that it is a reaction material of the base polymer 1 and an epoxy group containing monomer (X) from a viewpoint of the production efficiency with respect to acid group introduction | transduction.
Hereinafter, the synthesis method will be described.

Method (1)
When the radically polymerizable copolymer is obtained by the above method (1), the monomer component giving the base polymer 1 is the monomer (a), the monomer (b), and the acid group-containing monomer. At least the body (c).

The ratio of each monomer shown in the monomer component is not particularly limited as long as a radical polymerizable copolymer excellent in developability, pattern linearity, and solvent resistance is obtained. The content ratio of (a), (b), (c) is 0.5 to 30% by mass of the monomer (a) and 100% by mass of the monomer component giving the base polymer 1. It is preferable that the monomer (b) is 11 to 85% by mass, the monomer (c) is 5 to 85% by mass, the monomer (a) is 1 to 20% by mass, and the monomer (b) 20 is. It is more preferable that they are -80 mass% and the said monomer (c) 10-70 mass%.

Moreover, the monomer component which provides the said base polymer 1 is the monomer which gives the said monomer (a), the said monomer (b), the said monomer (c), and the structural unit (D) mentioned above. When the body (d) is included, the content ratio of each monomer is 0.5 to 30% by mass of the monomer (a) with respect to 100% by mass of the total amount of monomer components giving the base polymer 1. It is preferable that they are monomer (b) 11-85 mass%, said monomer (c) 5-85 mass%, said monomer (d) 1-70 mass%, said monomer (a) It is more preferable that they are 1-20 mass%, the said monomer (b) 20-80 mass%, the said monomer (c) 10-70 mass%, and the said monomer (d) 5-40 mass%. .

The monomer component that provides the base polymer 1 includes the monomer (a), the monomer (b), the monomer (c), the monomer (d), and the structure described above. When the monomer (e) giving the unit (E) is included, the content ratio of each monomer is 0% of the monomer (a) 0 with respect to 100% by mass of the total amount of monomer components giving the base polymer 1. 5-30 mass%, monomer (b) 11-85 mass%, monomer (c) 5-85 mass%, monomer (d) 1-70 mass%, monomer (E) It is preferable that it is 0-70 mass%, the said monomer (a) 1-20 mass%, the said monomer (b) 20-80 mass%, and the said monomer (c) 10-70. It is more preferable that they are the mass%, the said monomer (d) 5-40 mass%, and the said monomer (e) 1-40 mass%.

In the method (1), the method for polymerizing the monomer component is not particularly limited, and commonly used techniques such as bulk polymerization, solution polymerization, and emulsion polymerization can be used, and are appropriately selected according to the purpose and application. do it. Among these, solution polymerization is preferred because it is industrially advantageous and structural adjustments such as molecular weight are easy. The polymerization mechanism of the monomer component may be a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, but the polymerization method based on the radical polymerization mechanism is industrial. Is also preferable. A preferable form of the polymerization reaction is as described in JP-A-2006-29151 [0062] to [0072].

The polymerization initiation method in the above polymerization reaction may be performed by supplying energy necessary for initiation of polymerization to the monomer component from an active energy source such as heat, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.), electron beams, and the like. If an initiator is used in combination, the energy required for initiating polymerization can be greatly reduced, and reaction control is facilitated, which is preferable. 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.

In the method (1), the epoxy group-containing monomer (X) is subjected to an addition reaction with a part of the acid groups contained in the base polymer 1. This reaction method is not particularly limited, and a known method may be adopted as appropriate. For example, the reaction temperature is preferably 60 to 140 ° C. It is also preferable to use a known catalyst such as an amine compound such as triethylamine or dimethylbenzylamine; an ammonium salt such as tetraethylammonium chloride; a phosphonium salt such as tetraphenylphosphonium bromide; an amide compound such as dimethylformamide;

The amount of the epoxy group-containing monomer (X) used is preferably set as appropriate so that the acid value and double bond equivalent are in the desired ranges. For example, the monomer component that gives the base polymer 1 It is preferable to set it as 1-90 mass parts with respect to 100 mass parts of total amounts. As a result, the solvent resistance is further improved, the curability is further increased, and the strength of the cured product is further sufficient. More preferably, it is 3-85 mass parts, More preferably, it is 5-80 mass parts.

Moreover, the usage-amount of the said epoxy group containing monomer (X) is 10-95 mol% with respect to 100 mol% of said acid group containing monomers (c) in the monomer component which gives the base polymer 1. It is preferably 15 to 90 mol%, more preferably 20 to 85 mol%.

Method (2)
When the radically polymerizable copolymer is obtained by the method (2), the monomer component that gives the base polymer 2 is the monomer (a), the monomer (b), and the epoxy group-containing monomer. It includes at least the body (X).

The ratio of each monomer in the monomer component is not particularly limited. For example, the content ratio of the monomer (a) is 100% by mass with respect to the total amount of the monomer components giving the base polymer 2. Preferably it is 0.5-30 mass%, More preferably, it is 1-20 mass%, The content rate of the said monomer (b) becomes like this. Preferably it is 15-90 mass%, More preferably, it is 20-80 mass% is there.

The content ratio of the epoxy group-containing monomer (X) is preferably set as appropriate so that the acid value and the double bond equivalent are within the above-described ranges. For example, the monomer component that gives the base polymer 2 It is preferable that it is 3-80 mass% with respect to 100 mass% of total amounts, and it is more preferable that it is 5-75 mass%.

The monomer component that gives the base polymer 2 is the monomer (a), the monomer (b), the epoxy group-containing monomer (X), and the monomer (d). When it contains, the content rate of each monomer is 0.5-30 mass% of said monomers (a) with respect to 100 mass% of total amount of the monomer component which gives the said base polymer 2, and said monomer ( b) 15 to 90% by mass, 3 to 80% by mass of the epoxy group-containing monomer, and 1 to 70% by mass of the monomer (d), preferably 1 to 20% by mass of the monomer (a). %, The monomer (b) 19 to 80% by mass, the epoxy group-containing monomer (X) 5 to 75% by mass, and the monomer (d) 5 to 40% by mass.

The monomer component that provides the base polymer 2 is the monomer (a), the monomer (b), the epoxy group-containing monomer (X), the monomer (d), and When the monomer (e) is included, the content ratio of each monomer is 0.5 to 30 with respect to the monomer (a) with respect to 100% by mass of the total amount of monomer components giving the base polymer 2. % By weight, 15 to 90% by weight of the monomer (b), 3 to 80% by weight of the epoxy group-containing monomer (X), 1 to 70% by weight of the monomer (d), e) It is preferably 0 to 70% by mass, the monomer (a) 0.5 to 20% by mass, the monomer (b) 19 to 80% by mass, the epoxy group-containing monomer (X 5) to 75% by mass, 5 to 40% by mass of the monomer (d), and 0.5 to 40% by mass of the monomer (e).

In the method (2), the method for polymerizing the monomer component is not particularly limited, and is the same as the polymerization method described in the method (1).

In the method (2), the acid group-containing monomer (c) is subjected to an addition reaction with a part of the epoxy groups contained in the base polymer 2. Although this reaction method is not specifically limited, For example, it is preferable that reaction temperature shall be 60 to 140 degreeC. It is also preferable to use a known catalyst such as an amine compound such as triethylamine or dimethylbenzylamine; an ammonium salt such as tetraethylammonium chloride; a phosphonium salt such as tetraphenylphosphonium bromide; an amide compound such as dimethylformamide;

It is preferable that the usage-amount of the said acid group containing monomer (c) shall be 1-60 mass parts with respect to 100 mass parts of total amounts of the monomer component which gives the base polymer 2. FIG. As a result, the solvent resistance is further improved, the curability is further increased, and the strength of the cured product is further sufficient. More preferably, it is 2-50 mass parts, More preferably, it is 3-40 mass parts.

It is also preferable to react a polybasic acid anhydride after the addition reaction of the acid group-containing monomer (c). In this reaction, a polybasic acid anhydride is reacted with a hydroxyl group produced by a reaction between the epoxy group contained in the base polymer 2 and the acid group-containing monomer (c), thereby generating a carboxyl group. By performing this reaction, the acid value can be adjusted to an appropriate amount.

The polybasic acid anhydride is not particularly limited. For example, succinic anhydride (also known as succinic anhydride), maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride And dibasic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, itaconic anhydride; trimellitic anhydride; and the like.

The usage-amount of the said polybasic acid anhydride is not specifically limited, It is preferable to set so that the acid value of the radically polymerizable copolymer obtained may become the range mentioned above.

The radical polymerizable copolymer of the present invention is excellent in alkali developability and can give a cured product excellent in pattern linearity and solvent resistance. Moreover, the hardened | cured material excellent also in heat resistance can be given. Therefore, it is useful for an alkali development type negative resist material for producing colored pixels of a color filter, a black matrix, a black column spacer, an overcoat, a photo spacer, an optical waveguide, and the like. Moreover, since it has favorable color material dispersibility and adhesiveness, it is also useful for colored curable resin compositions for color filters. The radical polymerizable copolymer is particularly preferably used as an alkali-soluble resin for a color resist binder resin or a solder resist resin, and the radical polymerizable copolymer is used as a main component of the photosensitive resin composition. Very useful.

2. Curable resin composition
The radical polymerizable copolymer described above can be made into a curable resin composition by further combining with a polymerizable compound. Since the said curable resin composition contains the said polymer, it can be excellent in alkali developability and can give the hardened | cured material excellent in pattern linearity and solvent resistance. Further, by containing a polymerizable compound, a cured product excellent in various physical properties such as curability of the resin composition, adhesion to a substrate, mechanical strength, and heat resistance can be provided. Such a radical polymerizable copolymer and a curable resin composition containing a polymerizable compound are also one aspect of the present invention.
Moreover, the curable resin composition of this invention can be used suitably as a photosensitive resin composition.

In the curable resin composition of the present invention, the content ratio of the radical polymerizable copolymer is not particularly limited, and may be set as appropriate depending on the use and the blending of other components. For example, the curable resin composition It is preferable that it is 1-90 mass% with respect to 100 mass% of solid content total amount of a thing, It is more preferable that it is 3-80 mass%, It is still more preferable that it is 5-70 mass%.
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).

<Polymerizable compound>
Examples of the polymerizable compound include polymerizable unsaturated bonds (also referred to as polymerizable unsaturated groups) that can be polymerized by irradiation with active radicals such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, and X-rays) and electron beams. ). 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 compound include N-substituted maleimide monomers; (meth) acrylic acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated groups and carboxyls Unsaturated monocarboxylic acids in which the chain is extended; Unsaturated acid anhydrides; Aromatic vinyls; Conjugated dienes; Vinyl esters; Vinyl ethers; N-vinyl compounds; Is mentioned. A monomer having an active methylene group or an active methine group can also be used.

Examples of the polyfunctional compound 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 Hexa (meth) acrylate, dipentaerythritol pentaacrylate modified with succinic acid Trifunctional or more polyfunctional (meth) acrylate compounds such as a product, pentaerythritol triacrylate succinic acid modified product, dipentaerythritol pentaacrylate phthalic acid modified product, pentaerythritol triacrylate phthalic acid modified product;

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.

Among the above polyfunctional polymerizable compounds, polyfunctional (meth) acrylate compounds, polyfunctional urethane (meth) acrylate compounds, (meth) acryloyl group-containing isocyanates are particularly desirable from the viewpoints of reactivity, economy, and availability. A compound having a (meth) acryloyl group such as a nurate compound is preferable, and a polyfunctional (meth) acrylate compound is more preferable. By including the compound having a (meth) acryloyl group, the curable resin composition becomes more excellent in photosensitivity and curability, and a cured product having higher hardness and transparency can be obtained. As the polyfunctional polymerizable compound, it is more preferable to use a trifunctional or higher polyfunctional (meth) acrylate compound.
The said polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.

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 exhibited, and may be set as appropriate, but developability and solvent resistance are good. From the point which is more excellent, Preferably it is 3-90 mass% with respect to 100 mass% of solid content total amount of the curable resin composition of this invention, More preferably, it is 5-80 mass%, More preferably, it is 10-70. % By mass.

<Photopolymerization initiator>
The curable resin composition of the present invention preferably further contains a photopolymerization initiator. By including a photopolymerization initiator, the curability of the curable resin composition can be improved, and the performance of the resulting cured product can be improved.
The photopolymerization initiator used 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.

The photopolymerization initiator is not particularly limited, and examples thereof include alkylphenone compounds, benzophenone compounds, benzoin compounds, thioxanthone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, and biimidazole compounds. Known photopolymerization initiators such as oxime ester compounds, oxime ether compounds, titanocene compounds, benzoate ester compounds, and acridine compounds can be used.

Of these, alkylphenone compounds, oxime ester compounds, and oxime ether compounds are preferably used as the photopolymerization initiator, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro is preferable. Alkylphenones such as pan-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“IRGACURE369”, manufactured by BASF) Compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime)] (“OXE01”, manufactured by BASF), ethanone, 1- [9-ethyl -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxy ("OXE02", manufactured by BASF), 1,2-octanedione, 1- [4- (phenylthio)-, 2-, (O-benzoyloxime)], ethanone ("OXE03", manufactured by BASF), Oxime esters such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (“OXE04” manufactured by BASF) It is more preferable to use
The said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The content ratio 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 0.1-30 mass% with respect to mass%, More preferably, it is 0.5-25 mass%, More preferably, it is 1-20 mass%.

Moreover, you may use together 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed. By using a photosensitizer and / or a photoradical polymerization accelerator together with the photopolymerization initiator, sensitivity and curability are further improved. 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.

Examples of the photosensitizer and photoradical polymerization accelerator that may be used in combination with the photopolymerization initiator include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; 4-dimethylamino Examples thereof include dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole.

In the case of using the photosensitizer and the photo radical polymerization accelerator, the content ratio is 100% by mass of the solid content of the curable resin composition from the viewpoint of balance between curability, the influence of the decomposed product, and economy. On the other hand, it is preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, and still more preferably 0.05 to 10% by mass.

<Other ingredients>
The curable resin composition of the present invention may further contain other components as necessary. Examples of the other components include a solvent, a coloring material, a dispersant, an antioxidant, a heat resistance improver, a leveling agent, a development aid, inorganic fine particles such as silica fine particles, and a silane-based, aluminum-based, titanium-based cup, and the like. Ringing agent; thermosetting resin such as filler, epoxy resin, phenol resin, polyvinylphenol; curing aid such as polyfunctional thiol compound; plasticizer; polymerization inhibitor; UV absorber; matting agent; Inhibitors; slip agents; surface modifiers; thixotropic agents; thixotropic agents; quinonediazide compounds; polyhydric phenol compounds; cationic polymerizable compounds; 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)
As the solvent, those commonly used in the curable resin composition can be used, and may be appropriately selected depending on the purpose and application, and are not particularly limited. For example, described in JP-A-2015-157909 The thing similar to the thing of can be used. These may be used individually by 1 type and may be used in combination of 2 or more type.

The amount of the solvent used may be appropriately set according to the purpose and application, and is not particularly limited, but is 10 to 90% by mass in the total amount of 100% by mass of the curable resin composition. Is preferred. More preferably, it is 20-80 mass%.

(Coloring 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 or a black column spacer, 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 ratio of the color material is not particularly limited, and can be appropriately set according to the purpose and application. Preferably, the content ratio is 2 to 100% by mass relative to the total solid content of the curable resin composition. 80 mass%, More preferably, it is 5-70 mass%, More preferably, 10-60 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.
The above-mentioned dispersant has an interaction site with a color material and an interaction site with a dispersion medium (for example, a solvent or a binder resin), and has a function of stabilizing the dispersion of the color material into the dispersion medium. In general, it is classified into a resin-type dispersant (for example, a polymer dispersant), a surfactant (for example, a low-molecular dispersant), 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 ratio of the dispersant may be appropriately set depending on 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%.

(Antioxidant)
The curable resin composition of this invention can improve the heat-resistant coloring property of hardened | cured material by containing antioxidant.
Antioxidants that can be used in the present invention are not particularly limited, and known antioxidants may be appropriately selected and used. Among them, hindered phenol antioxidants, phosphite ester antioxidants may be used. Agents are preferred. These may be used individually by 1 type and may be used in combination of 2 or more type.

As a content rate of the said antioxidant, 0.01-5 mass% is preferable with respect to 100 mass% of solid content of the said polymer, and 0.05-3 mass% is more preferable.

<Preparation of curable resin composition>
The method for preparing the curable resin composition is not particularly limited, and a known method may be used. Examples thereof include a method of mixing and dispersing each of the above-described components using various mixers and dispersers. It is done. 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 “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. . To the obtained mill base, a composition (preferably a transparent liquid) containing the above-mentioned radical polymerizable copolymer that has been separately stirred and mixed is added and mixed to obtain a uniform dispersion solution to obtain a curable resin composition. Can do.
In addition, it is preferable that the obtained curable resin composition is filtered with a filter or the like to remove fine dust.

3. As described above, the curable resin composition of the present invention provides a cured product having excellent alkali developability and excellent pattern linearity and solvent resistance. Moreover, the said hardened | cured material is excellent also in various performances, such as adhesiveness with a base material, heat resistance, and transparency. Such a laminate having a cured product of the curable resin composition on a substrate (base material) 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 range, the solvent resistance can be further exhibited. In addition, various performances such as adhesion to the substrate, heat resistance and transparency can be sufficiently exhibited. The film thickness is more preferably 0.2 to 15 μm, still more preferably 0.3 to 10 μm.

The method for obtaining the laminate is not particularly limited, and a known method may be used. For example, the above-described curable resin composition is applied on a substrate, and the applied product is dried, heated, or ultraviolet rays. The method of making it harden | cure by irradiating an active energy ray and obtaining hardened | cured material is mentioned.
It does not specifically limit as said board | substrate (base material), What is necessary is just to select suitably according to the objective and use, For example, the base material which consists of various materials, such as a glass plate and a plastic plate, is mentioned.

The laminate 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 the curable resin composition of this invention for a color filter. Thus, the color filter which has the hardened | cured material of the said curable resin composition on a board | substrate is also one of this invention. The color filter will be described below.

4). Color filter The color filter of this invention consists of a form which has the hardened | cured material of the said curable resin composition on a board | substrate.
In the color filter, a cured product formed of the curable resin composition 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. Further, 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-opened 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. The substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, or the like as necessary.

<Color filter manufacturing method>
In order to obtain the color filter, for example, for each pixel color (that is, for each pixel of one color), a step of placing the curable resin composition on the substrate (also referred to as a placement step) and a placement on the substrate A step of irradiating the curable resin composition with light (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 performing a heat treatment (also referred to as a heating step). It is preferable to adopt a manufacturing method that employs a method and repeats the same method for each color. Note that the order of forming the pixels of each color is not particularly limited.

(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.

(Light irradiation process)
In the light irradiation step, the active light source used is, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, etc. Lamp light sources, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, semiconductor lasers, and the like 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.

(Development process)
The development step is a step of developing with a developer after the light irradiation step described above 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 suitable as the developer include an ether solvent and an alcohol solvent. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkyl phenyl ethers, aralkyl phenyl ethers, diaromatic ethers , Isopropanol, benzyl alcohol and the like.

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Examples of the organic solvent in this case include organic solvents suitable as the developer described above.

Examples of the alkali agent include inorganic substances such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. Alkali agents: amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like can be used alone Two or more kinds may be used in combination.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates, alkylnaphthalene sulfonic acids, and the like. Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids, and the like. A combination of the above may also be used.

(Heating process)
The heating step is a step of further curing the exposed portion (cured portion) by baking after the developing step described above (also referred to as a post-curing step). 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.

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. The film thickness is more preferably 0.5 to 10 μm, still more preferably 0.5 to 8 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, 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 270 degrees C or less, More preferably, it is 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 including the color filter described above.
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. A cured product (cured film) formed from the curable resin composition is stable, excellent in adhesion to a substrate and the like, 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 radically polymerizable copolymer of the present invention is excellent in developability and can give a cured product excellent in pattern linearity and solvent resistance. Moreover, the curable resin composition containing the radically polymerizable copolymer of the present invention can provide a cured product that is further excellent in curability and excellent in adhesion to the substrate, transparency, heat resistance, and the like. Such a radically polymerizable copolymer and curable resin composition of the present invention are very useful for various applications in the optical field, electrical machinery and electronic fields, such as color filters.

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”. The analysis of the polymer in each synthesis example was performed as follows.

(1) Weight average molecular weight (Mw)
Tetrahydrofuran (THF) was used as an eluent with GPC (HLC-8220 GPC, manufactured by Tosoh Corporation), TSKgel SuperHZM-N (manufactured by Tosoh Corporation) was used as a column, and the measurement was calculated in terms of standard polystyrene.

(2) Solid content (NV)
About 0.3 g of the copolymer solution prepared in Production Example was weighed into an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Thereafter, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC Corp.), it was dried at 140 ° C. for 3 hours, then allowed to cool in a desiccator, and the weight was measured. From the weight loss, the weight of the solid content (acrylic resin) of the polymer solution was calculated.

(3) Acid value (AV)
1.5 g of the copolymer solution prepared in Production Example was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated with a 0.1 N aqueous KOH solution. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of polymer was determined from the solid content concentration (mgKOH / g).

(4) Glass transition temperature (Tg)
The copolymer solution was applied to a 5 cm square glass substrate, spin-coated on a glass substrate, dried at room temperature under reduced pressure for 4 hours, and a volatile component was removed by forming a thin film having a film mass of 30 mg or less. A solid was obtained. As for the solid content, it was confirmed by quantitative determination by gas chromatography that the residual solvent was 0.1 wt% or less. The obtained solid content was measured in accordance with JIS-K7121 at a heating rate of 10 ° C./min in a nitrogen stream using DSC (Differential Scanning Calorimetry, measuring instrument: Netch DSC3500).

(5) Development time (development speed)
The curable resin composition was applied onto a 10 cm square glass substrate with a spin coater and dried in an oven at 90 ° C. for 3 minutes. After drying, by a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON Co., Ltd.) equipped with a 2.0 kW super high pressure mercury lamp with a photomask having a line and space of 15 μm at a distance of 100 μm from the coating film Ultraviolet rays were irradiated at an intensity of 100 mJ / cm ² (in terms of 365 nm illuminance). After UV irradiation, 0.05 mass% potassium hydroxide aqueous solution is sprinkled on the coating film with a spin developing machine to dissolve and remove the unexposed area, and the remaining exposed area is washed with pure water for 10 seconds. Thus, a line and space pattern was formed.
The time required to dissolve and remove the unexposed area was measured, and this was defined as the development time (seconds).

(6) The linearity of the pattern was applied to a 10 cm square glass substrate by a spin coater and dried in an oven at 90 ° C. for 3 minutes. After drying, by a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON Co., Ltd.) equipped with a 2.0 kW super high pressure mercury lamp with a photomask having a line and space of 15 μm at a distance of 100 μm from the coating film Ultraviolet rays were irradiated at an intensity of 100 mJ / cm ² (in terms of 365 nm illuminance). After UV irradiation, 0.05 mass% potassium hydroxide aqueous solution is sprinkled on the coating film with a spin developing machine to dissolve and remove the unexposed area, and the remaining exposed area is washed with pure water for 10 seconds. Then, a line and space pattern was formed, and the edge shape of the pattern was observed with a surface roughness meter (manufactured by Ryoka System Co., Ltd., trade name VertScan 2.0). The evaluation criteria for pattern linearity are as follows.
A: The pattern edge was sharp and the linearity was very good.
◯: Residue remained on a part of the edge of the pattern, but the linearity was good.
X: Residue and line thickening were observed on most of the edges of the pattern, and the linearity was low.

(7) A solvent-resistant curable resin composition was 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 thin film having a thickness of 5 μm was obtained. After that, it was immersed in 20 g of 1-methyl-2-pyrrolidone (N-methylpyrrolidone; also referred to as “NMP”) at 55 ° C. for 5 minutes, and the hue of NMP eluted from the coating film was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) The absorbance at 670 nm was determined.
NMP used for the evaluation of solvent resistance has high polarity and high solubility, and is therefore used as a solvent for various substances mainly in the field of polymer chemistry.

Production Example 1
A separable flask equipped with a cooling tube was prepared as a reaction vessel.
On the other hand, as a monomer composition in the monomer dropping tank, N-benzylmaleimide (BzMI) 5.0 g, acrylic acid (AA) 28.0 g, cyclohexyl methacrylate (CHMA) 31.0 g, methyl methacrylate (MMA) 1 0.0 g, 2-ethylhexyl acrylate (2EHA) 35.0 g, t-butylperoxy-2-ethylhexanoate (trade name “Perbutyl (registered trademark) O”, manufactured by NOF Corporation, hereinafter also referred to as “PBO”) 2.0 g, 17.0 g of propylene glycol methyl ether acetate (PGMEA) and 7.0 g of propylene glycol monomethyl ether (PGME) were added and mixed with stirring.
Further, 2.8 g of dodecyl mercaptan (nDM) and 17.2 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
The reaction vessel was charged with 114.0 g of PGMEA and 56.0 g of PGMEA, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 39.4 g of glycidyl methacrylate (GMA) and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as a polymerization inhibitor (trade name “ANTAGE W400”, manufactured by Kawaguchi Chemical Industry Co., Ltd.) , Hereinafter also referred to as “W400”.) 0.2 g and 0.4 g of triethylamine (TEA) as a catalyst were charged and reacted at 110 ° C. for 1 hour and at 115 ° C. for 10 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-1). Various physical properties are shown in Table 1.

Production Example 2
A separable flask equipped with a cooling tube was prepared as a reaction vessel.
On the other hand, BzMI 5.0 g, AA 35.0 g, CHMA 19.0 g, MMA 1.0 g, 2EHA 40.0 g, PBO 2.0 g, PGMEA 17.0 g and PGME 7.0 g were added to the monomer dropping tank as a monomer composition, and mixed with stirring. did.
In addition, as a chain transfer agent solution, 1.0 g of nDM and 19.0 g of PGMEA were charged into the chain transfer agent dropping tank and mixed with stirring.
The reactor was charged with 110.0 g of PGMEA and 55.0 g of PGMEA and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reactor to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 39.4 g of GMA, 0.2 g of W400 as a polymerization inhibitor, and 0.4 g of TEA were charged into the reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-2). Various physical properties are shown in Table 1.

Production Example 3
A separable flask equipped with a cooling tube was prepared as a reaction vessel.
Meanwhile, 5.0 g of BzMI, 45.0 g of AA, 29.0 g of CHMA, 1.0 g of MMA, 20.0 g of 2EHA, 2.0 g of PBO, 17.0 g of PGMEA and 7.0 g of PGME are added to the monomer dropping tank and stirred and mixed. did.
Moreover, nDM4.0g and PGMEA16.0g were thrown into the chain transfer agent dripping tank as a chain transfer agent solution, and it stirred and mixed.
The reaction vessel was charged with 148.0 g of PGMEA and 70.0 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 69.0 g of GMA, 0.2 g of W400 as a polymerization inhibitor, and 0.4 g of TEA were charged into the reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 10 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-3). Various physical properties are shown in Table 1.

Production Example 4
A separable flask equipped with a cooling tube was prepared as a reaction vessel.
On the other hand, BzMI 5.0 g, AA 17.0 g, CHMA 17.0 g, MMA 1.0 g, 2EHA 60.0 g, PBO 2.0 g, PGMEA 17.0 g and PGME 7.0 g were added to the monomer dropping tank as a monomer composition, and mixed with stirring. did.
Further, 1.5 g of nDM and 18.5 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
After charging 80.0 g of PGMEA and 42.0 g of PGMEA in the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 9.9 g of GMA, 0.2 g of W400 as a polymerization inhibitor, and 0.4 g of TEA were charged into the reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 10 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-4). Various physical properties are shown in Table 1.

Production Example 5
A separable flask equipped with a cooling tube was prepared as a reaction vessel.
On the other hand, BzMI 5.0 g, AA 28.0 g, CHMA 31.0 g, MMA 1.0 g, n-butyl acrylate (BA) 35.0 g, PBO 2.0 g, PGMEA 17.0 g and PGME 7 0.0 g was added and mixed with stirring.
Moreover, nDM2.8g and PGMEA17.2g were thrown into the chain transfer agent dripping tank as a chain transfer agent solution, and it stirred and mixed.
The reaction vessel was charged with 114.0 g of PGMEA and 56.0 g of PGMEA, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 39.4 g of GMA, 0.2 g of W400 as a polymerization inhibitor, and 0.4 g of TEA were charged into the reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 10 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-5). Various physical properties are shown in Table 1.

Production Example 6
A separable flask equipped with a cooling tube was prepared as a reaction vessel.
On the other hand, 5.0 g of BzMI, 18.0 g of AA, 76.0 g of CHMA, 1.0 g of MMA, 2.0 g of PBO, 17.0 g of PGMEA and 7.0 g of PGME were added as a monomer composition to the monomer dropping tank and mixed with stirring.
Moreover, nDM2.0g and PGMEA18.0g were thrown into the chain transfer agent dripping tank as a chain transfer agent solution, and it stirred and mixed.
92.0 g of PGMEA and 47.0 g of PGMA were charged into the reaction vessel, and after the atmosphere was replaced with nitrogen, the reaction vessel was heated to an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 19.7 g of GMA, 0.2 g of W400 as a polymerization inhibitor, and 0.4 g of TEA were charged into the reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 10 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-6). Various physical properties are shown in Table 1.

Production Example 7
A separable flask equipped with a cooling tube was prepared as a reaction vessel.
On the other hand, as a monomer composition, 1.0 g of BzMI, 79.0 g of AA, 20.0 g of CHMA, 2.0 g of PBO, and 4.0 g of PGME were added to the monomer dropping tank and mixed with stirring. Also, 7.1 g of nDM and 12.9 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
216.0 g of PGME was charged into the reaction vessel and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 124.2 g of GMA, 0.3 g of W400 as a polymerization inhibitor, 0.6 g of TEA, and 126.0 g of PGME were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-7). Various physical properties are shown in Table 1.

Production Example 8
A separable flask equipped with a cooling tube was prepared as a reaction vessel.
On the other hand, 7.0 g of AA, 40.0 g of CHMA, 53.0 g of MMA, and 2.0 g of PBO were added as a monomer composition into the monomer dropping tank and mixed with stirring. In addition, as a chain transfer agent solution, 1.0 g of nDM and 19.0 g of PGMEA were charged into the chain transfer agent dropping tank and mixed with stirring.
After charging 86.0 g of PGMEA and 45.0 g of PGMEA in the reaction tank and replacing with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the mixture was cooled to room temperature to obtain a copolymer solution (A-8). Various physical properties are shown in Table 1.

(Example 1)
8.98 g of the copolymer solution (A-1) (that is, 3.5 g of copolymer), dispersant (manufactured by Big Chemie Japan Co., Ltd., trade name “DISPERBYK-2001”, nonvolatile content 1.3 g; 2.77 g of pigment (expressed as byk2001), pigment as a colorant (manufactured by Clariant, trade name “CI Pigment Violet 23”; hereinafter referred to as PV23) and 1.6 g of dye (manufactured by MP Biomedicals, trade name “ 6.4 g of CI Solvent Blue 35 "; hereinafter referred to as SB35). The obtained mixture was diluted with PGMEA so that the non-volatile content concentration was 20% by mass to obtain Millbase B1.
3.5 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., hereinafter referred to as DPHA), 4.62 g of the copolymer solution (A-1) (that is, 1.8 g of copolymer), and a photopolymerization initiator 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name “IRGACURE (registered trademark) 369” manufactured by BASF Japan Ltd .; hereinafter referred to as Irg369) 1.9 g And PGMEA were mixed to obtain a clear resist B1.
Next, the mill base B1 and the clear resist B1 were mixed and diluted with PGMEA so that the nonvolatile content concentration was 20% by mass to obtain a curable resin composition B1. The obtained curable resin composition B1 was subjected to the evaluations (5) to (6). The results are shown in Table 2.

(Examples 2 to 5)
Instead of the copolymer solution (A-1) contained in the mill base and the clear resist, the curable resin composition B2 to B2 was used in the same manner as in Example 1 except that the copolymer solution shown in Table 2 was used. B5 was obtained. In any of the experimental examples, the copolymer solution contained in the mill base is 3.5 g of the copolymer added to the mill base, and the copolymer solution contained in the clear resist is the copolymer solution added to the clear resist. The polymer was used so that the amount of the polymer was 1.8 g.
Obtained curable resin composition B2-5 was used for said evaluation (5)-(6). The results are shown in Table 2.

(Comparative Examples 1-3)
In place of the copolymer solution (A-1) contained in the mill base and the clear resist, the curable resin composition B6 to B6 were used in the same manner as in Example 1 except that the copolymer solution shown in Table 2 was used. B8 was obtained. In any of the experimental examples, the copolymer solution contained in the mill base is 3.5 g of the copolymer added to the mill base, and the copolymer solution contained in the clear resist is the copolymer weight added to the clear resist. The coalescence was 1.8 g. The obtained curable resin compositions B6 to B8 were subjected to the evaluations (5) to (6). The results are shown in Table 2.

(Example 6)
0.52 g (non-volatile content 0.24 g) of byk 2001 as a dispersant, 1.4 g of a dye (SB35) as a coloring material, and 0.4 g of a pigment (PV23) were mixed. The obtained mixture was diluted with PGMEA so that the non-volatile content concentration was 20% by mass and dispersed for 3 hours with a paint shaker to obtain mill base B9.
4.62 g of the copolymer solution (A-1) (that is, 1.8 g of copolymer), 1.8 g of DPHA, and 2-methyl-1- [4- (methylthio) phenyl] as a photopolymerization initiator A clear resist B9 was obtained by mixing 0.6 g of 2-morpholino-propan-1-one (manufactured by BASF Japan, trade name “IRGACURE (registered trademark) 907”; hereinafter referred to as Irg907)) and PGMEA. Next, mill base B9 and clear resist B9 were mixed and diluted with PGMEA so that the nonvolatile content concentration was 20% by mass to obtain curable resin composition B9. The obtained curable resin composition B9 was subjected to the evaluation (7). The results are shown in Table 3.

(Comparative Example 4)
A curable resin composition B10 was obtained in the same manner as in Example 6 except that the copolymer solution (A-7) was used instead of the copolymer solution (A-1). The copolymer solution contained in the clear resist was used so that the copolymer added to the clear resist was 1.8 g. The obtained curable resin composition B10 was subjected to the evaluation (7). The results are shown in Table 3.

The description in Table 1 represents the following.
BzMI: N-benzylmaleimide AA: CHMA acrylate: cyclohexyl methacrylate MMA: Methyl methacrylate 2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate GMA: glycidyl methacrylate

From Tables 1 to 3, the following matters were confirmed.
Copolymers A-1 to A-5 obtained in Production Examples 1 to 5 correspond to the copolymer of the present invention. On the other hand, the copolymer A-6 obtained in Production Example 6 does not contain the structural unit represented by the general formula (1) and has a glass transition temperature of 50 ° C. or higher. The polymer A-7 does not contain the structural unit represented by the above general formula (1), and the copolymer A-8 obtained in Production Example 8 is the above general one in that the double bond equivalent is less than 330. Copolymer A- does not contain the structural unit represented by formula (1), has a glass transition temperature of 50 ° C. or higher, and does not have a polymerizable double bond (carbon-carbon double bond). 1 to A-5.
Comparing the development speed when used in combination with a color material under such a difference, the copolymer A-1 to the comparative example 1 or comparative example 3 using the copolymer A-6 or A-8. In Examples 1 to 5 using A-5, it was found that the development speed was high (see Table 2). Moreover, with respect to Comparative Examples 1 to 3 using the polymers A-6 to A-8, in Examples 1 to 5 using the copolymers A-1 to A-5, the pattern linearity is good. (See Table 2).

Comparing the solvent resistance when used in combination with the coloring material, it can be seen that the absorbance in Example 6 using the copolymer A-1 is remarkably small as compared with the comparative example 4 using the copolymer A-7. (See Table 3). The greater the elution of the coloring material, the higher the absorbance of the eluate. Therefore, it can be determined that the absorbance is extremely small, that is, the solvent resistance is excellent. Therefore, it was recognized that the copolymer of the present invention is excellent in solvent resistance. The copolymer of the present invention can sufficiently suppress elution even when a color material (pigment, dye) different from the color material used above is used.

Claims (9)

A radically polymerizable copolymer having an acid group and an ethylenically unsaturated double bond in the side chain,
The radical polymerizable copolymer has a structural unit derived from an N-substituted maleimide compound and a structural unit represented by the following general formula (1).
The double bond equivalent is 330-2000 g / equivalent,
The glass transition temperature is less than 50 ° C.,
The content ratio of the structural unit represented by the following general formula (2) is 5% by mass or less with respect to 100% by mass of all the structural units of the radical polymerizable copolymer,
The radical polymerizable copolymer, wherein the acid group has a distance of 6 or less atoms from the main chain.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms.)

(In the formula, R ³ represents a hydrogen atom or a methyl group.) 2. The radical polymerizable copolymer according to claim 1, wherein the side chain has a ring structure. The content ratio of the structural unit represented by the general formula (1) is 10% by mass or more with respect to 100% by mass of all the structural units of the radical polymerizable copolymer. The radically polymerizable copolymer described in 1. The radically polymerizable copolymer according to claim 1, wherein the acid group is a carboxyl group derived from (meth) acrylic acid. The radical-polymerizable copolymer according to any one of claims 1 to 4, wherein the acid value is 30 to 200 mgKOH / g. A curable resin composition comprising the radical polymerizable copolymer according to any one of claims 1 to 5 and a polymerizable compound. A laminate having a cured product of the curable resin composition according to claim 6 on a substrate. A color filter comprising a cured product of the curable resin composition according to claim 6 on a substrate. A display device comprising the color filter according to claim 8.