JP7134851B2 - Curable resin composition and use thereof - Google Patents

Description

The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition that can give a cured product with excellent developability and suppressed water unevenness, a laminate, a color filter, and a display device each having a cured product of the curable resin composition.

Curable resin compositions that can be cured by heat or active energy rays are used in various applications such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, and photoresists used in liquid crystal display devices, solid-state imaging devices, and the like. Various applications have been studied for various applications such as optical members and electrical and electronic equipment, and curable resin compositions having excellent properties required for each application have been developed. Among these uses, color filters are the main components that make up liquid crystal display devices, solid-state imaging devices, and the like. In addition to the pixels and the resin black matrix (BM) that separates them, it is composed of a protective film or the like that is provided to cover and protect the pixels and the resin black matrix and to smooth out the unevenness of the pixels and the resin black matrix.

Normally, when forming pixels of a color filter using a curable resin composition, each pixel is formed by (1) a coating step of applying a curable resin composition to the entire surface of the substrate, and (2) a coating step. After pattern exposure is performed on the resist film through a photomask to cure the exposed portion, the exposure step of insolubilizing the cured portion; A developing and baking process for further hardening the part is performed, and the same process is repeated for each color. Considering the application to such color filter applications, the curable resin composition has various properties such as curability, solvent resistance after curing, adhesion to the substrate (base material), heat resistance and transparency. It is required to have physical properties. In recent years, optical members, electrical and electronic devices, etc. have been becoming smaller, thinner, and energy-saving, and along with this, high-quality performance is required for members such as color filters to be used.

Various proposals have been made so far for curable resin compositions suitable for use in color filters.
For example, Patent Document 1 discloses a polymer obtained by polymerizing an N-substituted maleimide monomer and/or a specific ether dimer, vinyltoluene, and a monomer having an acid group as essential components as a monomer component. A photosensitive resin composition is described.
Further, for example, Patent Document 2 discloses a carboxyl group-containing radically polymerizable copolymer in which a carboxyl group is arranged in a side chain separated from the main chain by 7 or more elements and further has a radically polymerizable double bond in the side chain. A photosensitive resin composition comprising

Japanese Patent Application Laid-Open No. 2009-40999 JP 2012-193219 A

However, in conventional curable resin compositions, when developing with a developer after the exposure step, when the developer adheres to the exposed and cured portion (cured portion), the adhered portion becomes cloudy, and the cured portion becomes cloudy. There is a problem that the transparency and colorability of the cured product are lowered due to uneven density (water unevenness).
Further, in recent years, along with an increase in demand for color filters, there is a demand for improved quality and productivity, and it is also desired to be able to develop satisfactorily in a short period of time. 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-mentioned current situation, the present invention aims to provide a curable resin composition that is excellent in developability, can give a cured product with suppressed water unevenness, and can be suitably used for color filters. aim.

In order to solve the above problems, the present inventors have made various studies on a curable resin composition, and found that it has an aromatic vinyl-based monomer unit and an acid group in a side chain portion, and the acid group extends from the main chain. It has been found that by using a polymer having a vinyl-based monomer unit at a position separated by 5 atoms or more, it is possible to obtain a cured product with excellent developability and suppressed water unevenness. In addition, the present inventors have found that a curable resin composition containing such a polymer is particularly suitable as a resin composition for forming members for applications such as color filters, and have completed the present invention. came to.

That is, the present invention provides a vinyl-based monomer having an aromatic vinyl-based monomer unit (A) and an acid group in a side chain portion, wherein the acid group is located at a position separated from the main chain by 5 atoms or more. A curable resin composition characterized by containing a polymer having a unit (B).

The vinyl-based monomer unit (B) is preferably a monomer unit represented by the following general formula (I).

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms. R ³ represents a divalent organic group, X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid anhydride group, or a phosphoric acid group, and m represents the general formula (I). Represents the average number of repeating units of the monomer units that are used, and is a number of 1 or more. n is 0 or 1.)

The above polymer preferably further has an N-substituted maleimide-based monomer unit (C).

The N-substituted maleimide-based monomer units (C) are preferably N-phenylmaleimide monomer units and/or N-cyclohexylmaleimide monomer units.

The polymer further contains a vinyl unit containing a group —COO ^* R ⁴ (R ⁴ is a monovalent organic group and the carbon atom bonded to O ^* is a tertiary carbon atom.). It is preferred to have a mer unit (D).

In the polymer, the content ratio (A)/(B) of the aromatic vinyl-based monomer unit (A) and the vinyl-based monomer unit (B) is 10/60 to 60/ 10 is preferred.

The above polymer preferably has an acid value of 40 to 180 mgKOH/g.

The curable resin composition preferably further contains a polymerizable compound.

The present invention also provides a laminate comprising a substrate and a cured product of the curable resin composition described above.

The present invention also provides a color filter comprising a cured product of the curable resin composition described above on a substrate.

The present invention also provides a display device comprising the color filter described above.

Since the curable resin composition of the present invention has the above-described structure, it can provide a cured product that is excellent in developability and in which water unevenness is suppressed. Such a curable resin composition of the present invention is used for liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. Color filters, black matrices, photospacers, black columns As spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films and other optical members and structural members, it can be suitably used for various applications such as electrical and electronic equipment.

The present invention will be described in detail below.
A combination of two or more of the individual preferred embodiments of the invention described below is also a preferred embodiment of the invention.
Moreover, in this specification, "(meth)acrylate" means "acrylate and/or methacrylate", and "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid".

1. Curable resin composition The curable resin composition of the present invention has an aromatic vinyl-based monomer unit (A) and an acid group in the side chain portion, and the acid group is separated from the main chain by 5 atoms or more. It is characterized by containing a polymer having a vinyl-based monomer unit (B) at the position.
When the curable resin composition of the present invention contains such a specific polymer, it is possible to provide a cured product in which water unevenness is suppressed because the polymer contains an aromatic vinyl monomer unit. This is presumed to be due to the fact that the hydrophobicity of the resulting cured product is increased. Further, the curable resin composition of the present invention is excellent in developability because the polymer has the above-described specific vinyl-based monomer unit (B), and the carboxyl group or the like that exhibits alkali developability. It is presumed that the acid group can be arranged at a position far from the main chain of the highly hydrophobic polymer, thereby increasing the probability of contact with the developer.

In this specification, the term "water unevenness" means that the cured product comes into contact with a water-soluble solution such as a developer, and after the water-soluble solution is removed, a discoloration occurs such that the contact part becomes cloudy, and curing occurs. It means that there is unevenness in the density of an object.
Each component contained in the curable resin composition of the present invention is described below.

<Polymer>
The polymer contained in the curable resin composition of the present invention has an aromatic vinyl-based monomer unit (A) and an acid group in a side chain portion, and the acid group has 5 atoms or more from the main chain. It has a vinyl-based monomer unit (B) at a distant position. The monomer units constituting the polymer are described below. In the present invention, "monomer unit" means a structural unit derived from a monomer.

(Aromatic vinyl-based monomer unit (A))
The polymer has an aromatic vinyl-based monomer unit (hereinafter also referred to as "monomer unit (A)"). Since the polymer has aromatic vinyl-based monomer units, the curable resin composition of the present invention can provide a cured product in which water unevenness is suppressed. In addition, since the polymer has an aromatic vinyl-based monomer unit, the curable resin composition of the present invention can give a cured product excellent in heat color resistance.
In the present invention, the term "heat-resistant coloring resistance" refers to the property that the color of the cured product does not easily turn yellow when heated.
The aromatic vinyl-based monomer unit is a structural unit derived from an aromatic vinyl-based monomer, and preferably includes a structural unit derived from a monomer having an aromatic group and a vinyl group.

Examples of the aromatic group include groups containing a benzene ring, naphthalene ring, etc. Among them, a group containing a benzene ring is preferable.
The aromatic group may have a substituent. Examples of the substituent include alkyl groups having 1 to 5 carbon atoms and alkoxy groups having 1 to 5 carbon atoms.

Specific examples of the aromatic vinyl-based monomer include styrene, vinyltoluene, α-methylstyrene, xylene, methoxystyrene, ethoxystyrene, etc. Among them, thermal decomposition resistance is improved. styrene and vinyltoluene are preferable, and vinyltoluene is more preferable because it has a high dissolution rate in organic solvents and alkalis. A polymer having the monomer unit (A) can be obtained by polymerizing a monomer component containing such an aromatic vinyl monomer.
The polymer may have only one type of aromatic vinyl-based monomer unit, or may have two or more types.

The content of the monomer unit (A) in the polymer is 5 to 80% by mass with respect to 100% by mass of the total monomer units, considering both excellent water unevenness suppressing effect and developability. Preferably. The content of the monomer unit (A) is more preferably 10% by mass or more with respect to 100% by mass of the total monomer units in that the heat coloring resistance can be further improved. It is more preferably 70% by mass or less, and even more preferably 60% by mass or less.

(Vinyl monomer unit (B))
The polymer has an acid group in the side chain portion, and the acid group is a vinyl-based monomer unit at a position separated by 5 atoms or more from the main chain (hereinafter referred to as "vinyl-based monomer unit (B)"). Also called.). By having such a specific vinyl-based monomer unit, the developability of the curable resin composition of the present invention can be improved.

The vinyl-based monomer unit (B) has an acid group in the side chain portion, and the acid group is located at a distance of 5 atoms or more from the main chain.
Examples of the acid group include functional groups that undergo neutralization reaction with alkaline water, such as carboxyl group, phenolic hydroxyl group, carboxylic anhydride group, phosphoric acid group, and sulfonic acid group. You may have it, and you may have 2 or more types. Among them, the acid group is preferably a carboxyl group or a carboxylic anhydride group, more preferably a carboxyl group.

In the vinyl-based monomer unit (B), the acid group is located at a distance of 5 atoms or more from the main chain. In the present invention, the fact that the acid group is at a position away from the main chain by 5 atoms or more means that the position of the carbon atom on the main chain of the polymer to which the side chain is bonded is 0 (zero), and the side chain from that position The state in which there is an acid group at the position after the 5th atom of Atoms on the side chain may be non-carbon atoms or substituents. Specifically, for example, in the following formula (a1), the acid group X in the formula is located 5 atoms away from the main chain, and in the case of formula (a2), the acid group X is 7 atoms away from the main chain. It can be said that they are located at atomic distances.

Further, the acid groups are preferably separated by 18 atoms or less, more preferably by 16 atoms or less, more preferably by 14 atoms or less, from the viewpoint of maintaining appropriate solubility in the developer. It is more preferable to be in the

As the vinyl-based monomer unit (B), for example, a monomer unit represented by the following general formula (I) is preferable.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms. R ³ represents a divalent organic group, X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid anhydride group, or a phosphoric acid group, and m represents the general formula (I). Represents the average number of repeating units of the monomer units that are used, and is a number of 1 or more. n is 0 or 1.)

By having the monomer unit represented by the general formula (I) in the polymer, the curable resin composition of the present invention provides a cured product having excellent heat coloring resistance in addition to developability. can give. It is not certain that the polymer having the monomer unit represented by the above general formula (I) can give a cured product excellent in heat resistance to coloration, but when the polymer is heated, , Part of the monomer unit represented by the above general formula (I) is eliminated to form a hydroxyl group at the end, and this hydroxyl group captures the radical in the reaction system to reduce the influence of the radical. It is speculated that

In general formula (I) above, R ¹ represents a hydrogen atom or a methyl group. From the viewpoint of copolymerizability with the aromatic vinyl-based monomer, R ¹ is preferably a methyl group.
R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms.
Examples of the divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group include an alkylene group, an arylene group, and a divalent hydrocarbon group having an alicyclic structure. , alkylene groups are preferred. Examples of the alicyclic structure include a cyclohexane skeleton, an adamantane skeleton, and a norbornene skeleton. Moreover, these may have a substituent.

R ² is preferably an alkylene group such as methylene group, ethylene group, propylene group, butylene group, heptylene group, octylene group and dodecylene group; an arylene group such as phenylene group, tolylene group and naphthylene group; A group substituted with a functional group such as a hydroxy group or an alkoxy group; Among them, R ² is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms.

^R3 represents a divalent organic group. The divalent organic group preferably includes a divalent chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. a divalent chain or branched saturated hydrocarbon group or unsaturated hydrocarbon group. The organic group may have a substituent.

Examples of R3 include alkylene groups such as a methylene group ^, ethylene group, propylene group, trimethylene group, butylene group, ethylethylene group, hexylene group, octylene group and dodecylene group; vinylene group, propenylene group and isopropenylene group. , butenylene group, pentenylene group, alkenylene group such as hexenylene group; cycloalkylene group such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, norbornylene group, adamantylene group; phenylene group, tolylene group, naphthylene arylene groups such as groups, fluorene groups; alkyl ether groups such as ethyl ether _groups and propyl ether groups; be done.
Among them, an alkylene group is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 5 carbon atoms is still more preferable, in terms of further excellent developability.

X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group, or a phosphoric acid group. Among them, X is preferably a carboxyl group in terms of further excellent developability.
m represents the average number of repeating units of the monomer units represented by the general formula (I), and is a number of 1 or more.
n is 0 or 1, preferably 1;

As the monomer that provides the vinyl-based monomer unit (B), preferably β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate ) in which the chain between the unsaturated group and the carboxyl group is extended, and more preferably β-carboxyethyl (meth)acrylate and mono(2-acryloyloxyethyl succinate). ), mono(2-methacryloyloxyethyl) succinate, more preferably mono(2-methacryloyloxyethyl) succinate. By polymerizing a monomer component containing such a compound, a polymer having the vinyl-based monomer unit (B) can be obtained.
The polymer may have only one type of the vinyl-based monomer unit (B), or may have two or more types.

The content of the vinyl-based monomer unit (B) in the polymer is 5 to 70% by mass with respect to 100% by mass of the total monomer units, considering both excellent developability and the effect of suppressing water unevenness. %.
The content of the vinyl-based monomer unit (B) is more preferably 10 parts by mass or more with respect to 100% by mass of the total monomer units in that the heat coloring resistance can be further improved. , more preferably 15% by mass or more, particularly preferably 20% by mass or more, more preferably 65% by mass or less, and even more preferably 60% by mass or less.

(N-substituted maleimide-based monomer unit (C))
It is preferable that the polymer further has an N-substituted maleimide-based monomer unit (hereinafter also referred to as "monomer unit (C)"). By having the N-substituted maleimide-based monomer unit in the above polymer, it is possible to provide a cured product having a more excellent effect of suppressing water unevenness, and also to provide a cured product having excellent heat color resistance. .
It is presumed as follows that the effect of suppressing water unevenness is further improved when the polymer further contains an N-substituted maleimide-based monomer unit. That is, when the polymer has an N-substituted maleimide-based monomer unit, the polymer includes N Obtained by polymerizing a substituted maleimide monomer. During this polymerization, the aromatic vinyl-based monomer and the N-substituted maleimide-based monomer that provide the above monomer unit (A) have good alternating copolymerizability, so that they are adjacent to each other in the polymer. easier to introduce. Therefore, in the polymer, the proportion of the hydrophobic monomer unit (A) and the N-substituted maleimide monomer unit (C) is high, and the hydrophilic vinyl monomer unit (B ), it is presumed that the effect of suppressing water unevenness is further exhibited and the developability can be further improved.

Examples of N-substituted maleimide-based monomers that provide the monomer unit (C) include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N- Examples include t-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide and the like, and one or more of these can be used. Among them, N-phenylmaleimide and/or N-cyclohexylmaleimide are more preferable because the effect of suppressing water unevenness becomes more pronounced and the resistance to heat coloring can be improved. Maleimide is more preferred.

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. , o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide and other halogen-substituted benzylmaleimides;

The polymer may have only one type of the monomer unit (C), or may have two or more types of the monomer unit (C).

The content of the monomer unit (C) in the polymer is 5 to 80% by mass with respect to 100% by mass of the total monomer units, considering both excellent developability and the effect of suppressing water unevenness. %.
The content of the monomer unit (C) is more preferably 10% by mass or more with respect to 100% by mass of the total monomer units in that the heat coloring resistance can be further improved. It is more preferably 70% by mass or less, and even more preferably 60% by mass or less.

When the polymer has the monomer unit (C), the total amount of the monomer unit (A) and the monomer unit (C) in the polymer is 100 total monomer units. It is preferably 25 to 75 mol %, more preferably 30 to 70 mol %, relative to mol %. When the total amount of the monomer unit (A) and the monomer unit (C) is within the above range, water unevenness in the resulting cured product can be further suppressed.

(Vinyl-based monomer unit (D) containing —COO ^* R ⁴ groups)
The polymer further contains a vinyl unit containing a group —COO ^* R ⁴ (R ⁴ represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom.). It may have a monomer unit (hereinafter also referred to as "vinyl-based monomer unit (D)"). By further having such a vinyl-based monomer unit (D) in the polymer, along with the effect of suppressing water unevenness and developability, the curability of the curable resin composition, the heat resistance of the resulting cured product, Performance such as solvent resistance can be further improved.

In the vinyl-based monomer unit (D), R ⁴ of the —COO ^* R ⁴ group represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom. A tertiary carbon atom means a carbon atom that has three other carbon atoms attached to it.
The monovalent organic group preferably includes a monovalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 91 carbon atoms. The organic group may have a substituent.
The carbon number of R ⁴ is more preferably 1-50, still more preferably 1-35, and particularly preferably 1-20.
R ⁴ is preferably a monovalent organic group similar to A in formula (a) described later.

Examples of the vinyl-based monomer include monomers having a polymerizable carbon-carbon double bond in the molecule, among which (meth)acrylate-based monomers are preferred. That is, the vinyl-based monomer unit (D) is preferably a tertiary carbon-containing (meth)acrylate-based monomer unit.

The tertiary carbon-containing (meth)acrylate monomer preferably has a structure in which an oxygen atom adjacent to a (meth)acryloyl group is bonded to a tertiary carbon atom.

The tertiary carbon-containing (meth)acrylate monomer is a compound having one polymerizable carbon-carbon double bond in the molecule, that is, a (meth)acryloyl group (CH ₂ ═C(R ⁵ ) in the molecule. -C(=O)-) is preferably a compound having one group, for example, the following general formula (a):
_CH2 =C ⁽ R5)-C(=O)-OA (a)
(Wherein, R ⁵ represents a hydrogen atom or a methyl group. A represents a monovalent organic group containing a structure having a tertiary carbon atom on the oxygen atom side.) is a compound represented by is preferred.

In the general formula (a) above, the monovalent organic group represented by A can be represented, for example, by —C(R ⁶ )(R ⁷ )(R ⁸ ). In this case, R ⁶ , R ⁷ and R ⁸ are the same or different and are preferably a hydrocarbon group having 1 to 30 carbon atoms. The above hydrocarbon group may be a saturated hydrocarbon group or , may be an unsaturated hydrocarbon group, may have a cyclic structure, or may have a substituent. Also, R ⁶ , R ⁷ and R ⁸ may be linked to each other at the terminal sites to form a cyclic structure.

The number of carbon atoms in the organic group represented by A above is the oxygen atom adjacent to the (meth)acryloyl group (CH ₂ =C(R ⁵ )-C(=O)-) and the third It is preferably 12 or less, more preferably 9 or less, in that the new compound generated by breaking the O—C bond between the group carbon atoms is likely to volatilize. Moreover, the organic group represented by A may have a branched structure.

Here, in the tertiary carbon-containing (meth)acrylate-based monomer, at least one of the tertiary carbon atoms bonded to the oxygen atoms adjacent to the (meth)acryloyl group is bonded to a hydrogen atom. preferably. For example, the tertiary carbon-containing (meth)acrylate monomer is a compound represented by the general formula (a), and A is represented by -C(R ⁶ )(R ⁷ )(R ⁸ ) is a group, it is preferred that at least one of R ⁶ , R ⁷ and R ⁸ contains a carbon atom having one or more hydrogen atoms, and the carbon atom is bonded to a tertiary carbon atom . In such a form, upon heating, the O—C bond between the oxygen atom adjacent to the (meth)acryloyl group and the tertiary carbon atom adjacent thereto is cleaved to produce (meth)acrylic acid at the same time. , a double bond (C═C) is formed between the tertiary carbon atom and the adjacent carbon atom to form a new compound more stably.

The new compound produced as described above is preferably volatile. In this case, due to volatilization of the new compound from the cured product, the film thickness of the cured product (cured film) is reduced, and at the same time, for example, the curable resin composition further contains a colorant. In some cases, the colorant concentration increases after heating. As a result, it is possible to further reduce the thickness of the film, and it is possible to achieve higher color purity and a higher light shielding rate of the black matrix. Considering this point, R ⁶ , R ⁷ and R ⁸ are preferably the same or different and are saturated hydrocarbon groups having 1 to 15 carbon atoms. A saturated hydrocarbon group having 1 to 10 carbon atoms is more preferred, a saturated hydrocarbon group having 1 to 5 carbon atoms is more preferred, and a saturated hydrocarbon group having 1 to 3 carbon atoms is particularly preferred.

The tertiary carbon-containing (meth)acrylate monomer is preferably t-butyl (meth)acrylate or t-amyl (meth)acrylate.
Further, from the viewpoint of copolymerizability with the above-mentioned aromatic vinyl-based monomer, the tertiary carbon-containing (meth)acrylate-based monomer is preferably a tertiary carbon-containing methacrylate-based monomer, More preferred are t-butyl methacrylate and t-amyl methacrylate.
The polymer may have only one type of the vinyl-based monomer unit (D), or may have two or more types.

The content of the vinyl-based monomer unit (D) in the polymer is preferably 5 to 70% by mass, and preferably 10% by mass or more, relative to 100% by mass of the total monomer units. It is more preferably 15% by mass or more, more preferably 65% by mass or less, and even more preferably 60% by mass or less.

When the polymer has the vinyl-based monomer unit (D), the total amount of the vinyl-based monomer unit (B) and the vinyl-based monomer unit (D) in the polymer is It is preferably 80 mol % or less with respect to 100 mol % of the polymer component. When the total amount is within the above range, the effect of suppressing water unevenness is even more excellent. More preferably, the total amount is 70 mol % or less with respect to 100 mol % of all monomer components. From the viewpoint of developability, the total amount is preferably 20 mol % or more, more preferably 25 mol % or more, based on 100 mol % of the total monomer components.

(Other polymerizable monomer units (E))
The polymer may have other polymerizable monomer units (hereinafter also referred to as "monomer units (E)"), if necessary, in addition to the monomer units described above.
Examples of the other polymerizable monomer units include, for example, an acid group-containing monomer other than the monomer that provides the monomer unit (B), and a monomer that provides the vinyl monomer unit (D). Examples include monomer units derived from (meth)acrylic acid ester-based monomers other than solids, other copolymerizable monomers, and the like.

Examples of the acid group-containing monomer include compounds having an acid group and a polymerizable double bond in the molecule, other than the monomer that gives the monomer unit (B) described above.

Examples of the acid group include functional groups that undergo neutralization reaction with alkaline water, such as carboxyl group, phenolic hydroxyl group, carboxylic anhydride group, phosphoric acid group, and sulfonic acid group. You may have it, and you may have 2 or more types. Among them, a carboxyl group and a carboxylic anhydride group are preferred, and a carboxyl group is more preferred.
Examples of the polymerizable double bond include a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group, and the like.

Specific examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid, Unsaturated polycarboxylic acids such as citraconic acid and mesaconic acid; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; phosphoric acid group-containing unsaturated compounds such as Light Ester P-1M (manufactured by Kyoeisha Chemical); etc. Among these, carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) are preferably used from the viewpoint of versatility, availability, and the like. From the viewpoint of reactivity, effect of suppressing water unevenness, developability, etc., unsaturated monocarboxylic acids are more preferable, (meth)acrylic acid (that is, acrylic acid and/or methacrylic acid) is more preferable, and particularly preferable. methacrylic acid.

Examples of the (meth)acrylic acid ester-based monomer other than the monomer that provides the vinyl-based monomer unit (D) include methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic n-propyl acid, i-propyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, n-amyl (meth)acrylate, s-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic Lauryl acid, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylate Tetrahydrofurfuryl acrylate, N,N-dimethylaminoethyl (meth)acrylate, 1,4-dioxaspiro[4,5]dec-2-yl methacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyl Oxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2 -methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane and the like.

Examples of other copolymerizable monomers include one or more of the following compounds.
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate and 2,3-hydroxypropyl (meth)acrylate; meth)acrylamides; macromonomers having a (meth)acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam; 1, Conjugated dienes such as 3-butadiene, isoprene and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n -Vinyl ethers such as 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; N-vinylpyrrolidone, N - N-vinyl compounds such as vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate; α-allyloxymethyl Acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, n-propyl α-allyloxymethyl acrylate, i-propyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate n-butyl, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, n-amyl α-allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, α- α-(unsaturated acrylic acid) such as t-amyl allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, etc. alkoxyalkyl) acrylate monomers and the like.
The polymer may have only one type of monomer unit (E), or may have two or more types of the monomer unit (E).

The content of the monomer unit (E) in the polymer is preferably 1 to 60% by mass, preferably 5 to 55% by mass, with respect to 100% by mass of the total monomer units of the polymer. more preferably 10 to 50% by mass.

In the polymer, the content ratio (A)/(B) of the monomer unit (A) and the vinyl monomer unit (B) is 10/60 to 60/10 in terms of molar ratio. is preferred. When the content is within the above range, the effect of suppressing water unevenness and developability are further improved. The content ratio (A)/(B) is more preferably 13/55 to 55/13, and even more preferably 15/50 to 50/15.

When the polymer has the monomer unit (A), the vinyl-based monomer unit (B), and the monomer unit (C), the effect of suppressing water unevenness is sufficient regardless of the other components. from the viewpoint that they can be exhibited in the polymer, the content ratio [(A) + (C)] / (B) in the polymer is preferably 15/60 to 70/10 in terms of molar ratio, and 20/55 to 65 /13 is more preferred, and 25/50 to 60/15 is even more preferred.

When the polymer further has the vinyl-based monomer unit (D), the content ratio of these monomer units in the polymer [(A) + (C)] / [(B) + (D)] is preferably 20/80 to 70/30, more preferably 25/75 to 65/35, even more preferably 30/70 to 60/40 in molar ratio.

The acid value of the polymer is preferably 40 to 180 mgKOH/g, more preferably 50 to 170 mgKOH/g, even more preferably 60 to 160 mgKOH/g.
The above acid value is a value obtained by measuring by a neutralization titration method using a potassium hydroxide solution.

The weight average molecular weight of the polymer is not particularly limited, but is preferably 5,000 to 50,000, more preferably 6,000 to 40,000, and even more preferably 7,000 to 35,000.
The weight-average molecular weight of the polymer is a value obtained by measuring by gel permeation chromatography (GPC) according to the method described in Examples.

<Method for producing polymer>
The method for producing the polymer is not particularly limited as long as it is a method capable of obtaining a polymer having at least the above-described monomer units (A) and vinyl-based monomer units (B). Monomers containing monomers that give the monomer units (A) and (B) described above and monomers that give the monomer units (C), (D) or (E) described above as necessary Examples include a method of polymerizing the body component by a known method.

The method for polymerizing the above monomer component is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization and emulsion polymerization can be used. Among them, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy. In addition, as the polymerization mechanism of the monomer component, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used. is preferred.

The amount of the above-mentioned monomer components to be blended during polymerization is not particularly limited as long as a polymer that gives a cured product with excellent developability and suppressed water unevenness is obtained, and each monomer unit in the polymer may be appropriately designed so that the content of is within the range described above.

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

When the above monomer components are polymerized by a solution polymerization method, the solvent used for polymerization is not particularly limited as long as it is inert to the polymerization reaction. It may be appropriately set according to polymerization conditions such as polymerization temperature and polymerization concentration. When a solvent is used as a diluent or the like when forming the curable resin composition later, it is efficient and preferable to use the solvent containing the solvent for the solution polymerization of the monomer component.

Examples of the solvent include the same solvents as those described in JP-A-2015-157909, and one or more of them can be used. Among these solvents, propylene glycol monomethyl ether and propylene are preferred because of the solubility of the resulting polymer, the smoothness of the surface when forming a coating film, the low impact on the human body and the environment, and the ease of industrial availability. Glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and ethyl lactate are more preferably used.

The amount of the solvent used is preferably 50 to 1000 parts by mass, more preferably 100 to 500 parts by mass, per 100 parts by mass of the monomer component.

When the above monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy. can be selected as appropriate. A reducing agent such as a transition metal salt or amines may be used together with the polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy- 2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis ( 2-methylpropionate), hydrogen peroxide, persulfate, and other peroxides and azo compounds that are usually used as polymerization initiators. These may be used individually by 1 type, or may be used in combination of 2 or more type.

The amount of the polymerization initiator to be used is not particularly limited, and may be appropriately set according to the type and amount of the monomer to be used, the polymerization conditions such as polymerization temperature and polymerization concentration, the molecular weight of the target polymer, and the like. However, for example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the monomer component.

A chain transfer agent may also be used in the above polymerization, if desired. Preferably, a polymerization initiator and a chain transfer agent are used in combination. The use of a chain transfer agent during polymerization tends to suppress an increase in molecular weight distribution and gelation.

Examples of the chain transfer agent include those similar to the solvents described in JP-A-2015-157909, and one or more of them can be used. Among them, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkylmercaptans, mercaptoalcohols, aromatic mercaptans, mercapto Examples include compounds having a mercapto group such as isocyanurates, more preferably alkylmercaptans, mercaptocarboxylic acids and mercaptocarboxylic acid esters, and still more preferably n-dodecylmercaptan and mercaptopropionic acid.

The amount of the chain transfer agent to be used is not particularly limited, and may be appropriately set depending on the type and amount of the monomer to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and the molecular weight of the target polymer. good. For example, in order to obtain a polymer having a weight-average molecular weight of several thousand to several ten thousands, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the monomer component. .

Regarding the conditions for the above polymerization, the polymerization temperature may be appropriately set according to the type and amount of the monomers used, the type and amount of the polymerization initiator, etc. For example, 50 to 150 ° C. 120°C is more preferred. In addition, the polymerization time can be set as appropriate, but is preferably 1 to 5 hours, more preferably 2 to 4 hours, for example.

In the curable resin composition of the present invention, the content of the polymer is not particularly limited, and may be appropriately set according to the application and the blending of other components. It is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, and even more preferably 20 to 50% by mass based on the total amount of 100% by mass.
The term "total solid content" means the total amount of components forming the cured product (excluding the solvent and the like that volatilize during the formation of the cured product).

<Polymerizable compound>
The curable resin composition of the present invention preferably further contains a polymerizable compound. By containing the above-described polymer and polymerizable compound, in addition to the effect of suppressing water unevenness and developability, the curability of the curable resin composition, adhesion to the substrate, surface hardness, heat resistance, solvent resistance It is possible to give a cured product which is more excellent in terms of properties and the like.

The polymerizable compound is a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation of free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), active energy rays such as electron beams, etc. It is a low-molecular-weight compound having Examples thereof include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.

Examples of the monofunctional compounds include N-substituted maleimide-based monomers; (meth)acrylic acid esters; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids; Unsaturated monocarboxylic acids with chain extension between groups; Unsaturated acid anhydrides; Aromatic vinyls; Conjugated dienes; Vinyl esters; Vinyl ethers; 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, glycerin 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 Pentaerythritol tetra(meth)acrylate with ethylene oxide, dipentaerythritol hexa(meth)acrylate with ethylene oxide, trimethylolpropane tri(meth)acrylate with propylene oxide, ditrimethylolpropane tetra(meth)acrylate with propylene oxide, pentaerythritol tetra(meth)acrylate with propylene oxide (Meth)acrylates, 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 (Meth) acrylate, ε-caprolactone-added dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinic acid-modified, pentaerythritol triacrylate succinic acid-modified, dipentaerythritol pentaacrylate phthalic acid-modified, pentaerythritol tri Modified acrylate phthalate, formula:

A trifunctional or higher polyfunctional (meth)acrylate compound such as a modified product of dipentaerythritol hexaacrylate represented by;

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, ditri Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide polyfunctional vinyl ethers such as adduct dipentaerythritol hexavinyl ether;

2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4 (meth) acrylic acid -vinyloxybutyl, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, ( Vinyl ether group-containing (meth)acryl 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 ditrimethylolpropane tetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether;

Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; 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 urethane (meth)acrylates obtained by reaction of polyfunctional isocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; polyfunctional aromatic vinyls such as divinylbenzene; These polymerizable compounds may be used singly or in combination of two or more.

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

As the polyfunctional polymerizable compound, among others, polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, (meth)acryloyl group-containing isocyanates, from the viewpoint of reactivity, economy, availability, etc. A compound having a (meth)acryloyl group such as a nurate compound is preferable, and a polyfunctional (meth)acrylate compound is more preferable. By containing a compound having a (meth)acryloyl group, the curable resin composition becomes more excellent in photosensitivity and curability, and a cured product with higher hardness and higher transparency can be obtained. As the polyfunctional polymerizable compound, it is more preferable to use a trifunctional or higher polyfunctional (meth)acrylate compound.
The polymerizable compounds may be used singly or in combination of two or more.

In the curable resin composition of the present invention, the content 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. From the point of being able to have a high viscosity, the total solid content of the curable resin composition of the present invention is preferably 2 to 60% by mass, more preferably 5 to 55% by mass, and still more preferably 10% by mass. ~50% by mass.

<Photoinitiator>
The curable resin composition of the present invention preferably further contains a photopolymerization initiator. By including a photopolymerization initiator, it is possible to improve the curability of the curable resin composition and improve the performance of the obtained cured product.
The photopolymerization initiator used in the present invention is preferably a radically polymerizable photopolymerization initiator. A radically polymerizable photopolymerization initiator is one that generates polymerization initiation radicals upon irradiation with active energy rays such as electromagnetic waves and electron beams.

The photopolymerization initiator is not particularly limited. -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE369", manufactured by BASF), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4 -morpholin-4-yl-phenyl)-butan-1-one ("IRGACURE379", manufactured by BASF) and other alkylphenone compounds; 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE651", manufactured by BASF), benzyl ketal compounds such as phenylglyoxylic acid methyl ester ("DAROCUR MBF", manufactured by BASF); 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", manufactured by BASF) , 2-hydroxy-2-methyl-1-phenyl-propan-1-one (“DAROCUR1173”, manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl -1-propan-1-one (“IRGACURE2959”, manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2- Hydroketone compounds such as methyl-propan-1-one (“IRGACURE 127”, manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone] (“IRGACURE 500”, manufactured by BASF); Alkylphenone compounds exemplified in paragraphs [0084] to [0086] of JP-A-2013-227485; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime)] (“OXE01”, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) ( "OXE02", manufactured by BASF), 1,2-octanedione, 1-[4-(phenylthio)-, 2-, (O-benzoyloxime)], ethanone ("OXE03", manufactured by BASF), 1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-ace oxime ester compounds such as ("OXE04", manufactured by BASF)); benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; titanocene-based compounds; benzoic acid ester-based compounds; acridine-based compounds; phosphine oxide-based compounds; Among them, alkylphenone compounds are preferred.
The photopolymerization initiators may be used singly or in combination of two or more.

The content of the photopolymerization initiator is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately designed. For example, the total solid content of the curable resin composition of the present invention is 100 It is preferably 2 to 35% by mass, more preferably 3 to 30% by mass, and still more preferably 5 to 25% by mass.

Moreover, you may use together 1 type(s) or 2 or more types of a photosensitizer, a photoradical polymerization accelerator, etc. as needed. By using a photosensitizer and/or a photoradical polymerization accelerator together with the photopolymerization initiator, sensitivity and curability are further improved. The photosensitizer and photoradical polymerization accelerator are not particularly limited, and may be appropriately selected from known ones commonly used in curable resin compositions.

Photosensitizers and photoradical polymerization accelerators that may be used in combination with the photopolymerization initiator include, for example, xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, dye compounds such as pyrromethene dyes; 4-dimethylamino dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; and mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole.

When using the above-mentioned photosensitizer and photoradical polymerization accelerator, the content thereof is 100% by mass of the total solid content of the curable resin composition from the viewpoint of the balance of curability, the influence of decomposed products, and economic efficiency. 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 optionally contain other components in addition to the polymer, polymerizable compound, and photopolymerization initiator described above. Other components include, for example, solvents; coloring materials (also referred to as coloring agents); dispersing agents; antioxidants; Coupling agents such as titanium; thermosetting resins such as fillers, epoxy resins, phenolic resins and polyvinylphenol; curing aids such as polyfunctional thiol compounds; plasticizers; antifoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; These may be used individually by 1 type, and may be used in combination of 2 or more type. For example, when the curable resin composition is used for color filters, the curable resin composition preferably contains a colorant.

(solvent)
As the solvent, those commonly used in curable resin compositions can be used, and may be appropriately selected depending on the purpose and application, and is not particularly limited. 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 it should be contained in an amount of 10 to 90% by mass in 100% by mass of the total amount of the curable resin composition. is preferred. More preferably, it is 20 to 80% by mass.

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

Among the coloring materials, pigments are preferred from the standpoint of durability, and dyes are preferred from the standpoint of improving the luminance of panels and the like. These can be appropriately selected according to the properties required. In the curable resin composition of the present invention, pigments are preferred because they can further improve the solvent resistance and heat-resistant coloring resistance of the cured product. Pigments similar to those described in JP-A-2015-157909 can be used.

Examples of the dye include organic dyes described in JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599. can. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable.
These colorants may be used singly or in combination of two or more.

The content of the coloring material is not particularly limited, and can be appropriately set according to the purpose and application. 1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 12% by mass.

(dispersant)
When the curable resin composition of the present invention contains the coloring material, it preferably further contains a dispersant.
The dispersant has a site for interaction with the colorant and a site for interaction with the dispersion medium (for example, solvent or binder resin), and has the function of stabilizing the dispersion of the colorant in the dispersion medium. They are generally classified into resin-type dispersants (eg, polymer dispersants), surfactants (eg, low-molecular-weight dispersants), and pigment derivatives. 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 polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , long-chain polyaminoamide phosphates, hydrogen group-containing polycarboxylic acid esters, amides and salts thereof formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/polypropylene oxide adducts, etc. mentioned. Commercially available products of the resin-type dispersant include those described in JP-A-2015-157909.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, 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 cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazoline;

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 quaternary salts thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, and an amide group. , a phthalimide group, and the like. Examples of the structure of the base dye include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, and diketopyrrolopyrroles. system and the like.

The content of the dispersant may be appropriately set according to the purpose and application. It is preferably 0.01 to 60% by mass with respect to 100% by mass of the total solid content of the resin composition. More preferably 0.1 to 50% by mass, still more preferably 0.3 to 40% by mass.

(Antioxidant)
By containing an antioxidant, the curable resin composition of the present invention can further improve the heat-resistant coloring resistance of the cured product.
The antioxidant that can be used in the present invention is not particularly limited, and a known antioxidant may be appropriately selected and used. agents are preferred. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the antioxidant is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, based on 100% by mass of the solid content of the polymer.

<Preparation of curable resin composition>
The method for preparing the curable resin composition is not particularly limited, and a known method may be used. For example, a method of mixing and dispersing each of the above-described ingredients using various mixers and dispersers may be mentioned. be done. The mixing/dispersing step is not particularly limited, and may be performed by a known method. In addition, other steps that are normally performed may be further included. When the curable resin composition contains a colorant, it is preferably prepared through a colorant dispersion treatment step.

As the above-described colorant dispersion treatment step, for example, first, predetermined amounts of a colorant (preferably an organic pigment), a dispersant, and a solvent are weighed, and the colorant is finely dispersed using a disperser to obtain a liquid colorant. Methods of obtaining dispersions (also called millbases) are included. Examples of the dispersing machine include paint conditioners, bead mills, roll mills, ball mills, jet mills, homogenizers, kneaders and blenders. As the dispersion treatment step, preferably, after kneading and dispersing with a roll mill, a kneader, a blender, etc., fine dispersion treatment is performed with a media mill such as a bead mill filled with beads of 0.01 to 1 mm. . To the obtained mill base, a composition (preferably a transparent liquid) containing a polymer, a polymerizable compound, a photopolymerization initiator, and, if necessary, a solvent, a leveling agent, etc., which has been separately stirred and mixed, is added. A curable resin composition can be obtained by mixing and forming a uniform dispersion solution.
The obtained curable resin composition is preferably filtered using a filter or the like to remove fine dust.

2. Laminate As described above, the curable resin composition of the present invention provides a cured product which is excellent in developability and in which water unevenness is suppressed. In addition, the cured product is excellent in basic properties such as curability, adhesion to substrates, 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 within the above range, a more excellent effect of suppressing water unevenness can be exhibited. In addition, various performances such as adhesion to substrates, heat resistance and transparency can be sufficiently exhibited. The film thickness is more preferably 1 to 15 μm, still more preferably 1 to 10 μm.

The method for obtaining the laminate is not particularly limited, and a known method may be used. For example, the curable resin composition described above may be applied on a substrate, and the applied product may be dried, heated, or exposed to ultraviolet light or the like. A method of obtaining a cured product by curing by irradiation with an energy ray can be mentioned.
The substrate (substrate) is not particularly limited and may be appropriately selected according to the purpose and application. Examples thereof include substrates made of various materials such as glass plates and plastic plates.

The laminate is, for example, liquid crystal / organic EL / quantum dot / micro LED display device, solid-state image sensor, color filter used for touch panel type display device, black matrix, photo spacer, black column spacer, ink, printing plate, It is preferably used as various optical members and structural members such as printed wiring boards, semiconductor elements, photoresists and insulating films for electrical and electronic equipment. Especially, it is preferable to use it for a color filter and a black column spacer. Such a color filter having a cured product of the curable resin composition on a substrate is also one aspect of the present invention. The color filters are described below.

2-1. Color Filter The color filter of the present invention is a color filter in which a cured resin layer is provided on a substrate, and the resin composition forming the cured resin layer is the curable resin composition of the present invention. The above-mentioned color filter is an optical filter having fine pixels of at least three primary colors and a black matrix separating them on a transparent substrate, which is necessary for colorizing an image. Green (G) and blue (B) are used. Specific examples of members constituting a color filter include three primary color (RGB) pixels, a resin black matrix, a protective film, a columnar spacer, and a black column spacer (BCS). At least one of the members constituting the may be formed by curing the curable resin composition.

Examples of the substrate used in the color filter include glass substrates such as white plate glass, soda plate glass, alkali-strengthened glass, silica-coated soda plate glass; Sheets, films or substrates made of thermoplastic resins such as additives; Sheets, films or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Metal substrates such as aluminum plates, copper plates, nickel plates and stainless steel plates a ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member composed of various materials such as a glass substrate having a coloring material layer on its surface (for example, a color filter for LCD); Among them, a glass substrate and a sheet, film or substrate made of a heat-resistant resin are preferable from the viewpoint of heat resistance. Also, the substrate is preferably a transparent substrate.
If necessary, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a silane coupling agent, or the like.

<Manufacturing method of color filter>
In order to obtain the color filter, for example, for each pixel color (that is, for each pixel of one color), a step of disposing the curable resin composition on a substrate (also referred to as a disposition step), and disposing on the substrate A step of irradiating the cured resin composition with light (also referred to as a light irradiation step), a step of developing with a developer (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step). It is preferable to employ a manufacturing method that employs a technique and repeats the same technique for each color. Note that the order in which the pixels of each color are formed is not particularly limited.

(Placement step (preferably coating step))
The placement step is preferably performed by coating. Examples of the method for applying the curable resin composition on the substrate include spin coating, slit coating, roll coating, casting coating, and the like, and any of these methods can be preferably used.
In the placement step, it is also preferable to dry the coating film after coating the curable resin composition on the substrate. Drying of the coating film can be performed 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 curing component, the film thickness, the performance of the dryer, etc., but usually the drying can be performed at a temperature of 50 to 160° C. for 10 to 300 seconds. preferred.

(Light irradiation step)
In the light irradiation step, the light source of actinic rays used includes, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an extra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a fluorescent lamp, and the like. lamp light sources, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. As for the system of the exposure machine, there are a proximity system, a mirror projection system, and a stepper system, and the proximity system is preferably used.
In addition, in the step of irradiating the active energy beam, depending on the application, the active energy beam may be irradiated through a predetermined mask pattern. In this case, the exposed portion is cured, and the cured portion becomes insoluble or slightly soluble in the developer.

(Development process)
The developing step is a step of developing with a developing solution after the above-described light irradiation step to remove the unexposed portion to form a pattern. Thereby, a patterned cured film can be obtained. Development can be carried out at a development temperature of generally 10 to 50° C. by methods such as immersion development, spray development, brush development and 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, but 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 developer, it is preferable to wash with water after development.

Examples of organic solvents suitable for the developer include ether-based solvents and alcohol-based solvents. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkylphenyl ethers, aralkylphenyl ethers, diaromatic ethers , isopropanol, benzyl alcohol, and the like.

The alkaline aqueous solution may contain surfactants, organic solvents, buffers, dyes, pigments, etc., if necessary, in addition to the alkaline agent. Examples of the organic solvent in this case include organic solvents suitable for the developer described above.

Examples of the alkali agent include inorganic compounds such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, sodium tertiary phosphate, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. alkaline agents; amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., and these may be used alone. , may be used in combination of two or more.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; Anionic surfactants such as salts, alkylsulfates, alkylsulfonates, and sulfosuccinate salts; amphoteric surfactants such as alkylbetaines and amino acids; The above may be used in combination.

(Heating process)
The heating step is a step (also referred to as a post-curing step) of further curing the exposed portion (cured portion) by baking after the above-described developing step. For example, using a light source such as a high-pressure mercury lamp, a step of post-exposure with a light amount of, for example, 0.5 to 5 J/cm ² , a step of post-heating, for example, at a temperature of 60 to 260° C. for 10 seconds to 120 minutes, etc. mentioned. By performing such a post-curing step, it is possible to further increase the hardness and adhesion of the patterned cured film. Further, by this heating step, for example, when the vinyl-based monomer unit (B) contained in the polymer is a monomer unit represented by the general formula (I), the conversion of the monomer unit A hydroxyl group is formed at the end by partial elimination, and the hydroxyl group reacts with the acid group of the monomer unit of general formula (1) that has not been eliminated or the acid group of any other monomer unit. Then, a crosslinked structure is formed, and the curability of the curable resin composition of the present invention and the solvent resistance, heat resistance, etc. of the resulting cured product are further improved. Further, when the polymer has the vinyl-based monomer unit (D), the carboxyl group generated by elimination of the tertiary carbon-containing site reacts with the hydroxyl group to form a crosslinked structure, resulting in curability. and the solvent resistance of the cured product is excellent.

In the heating step, the heating temperature is preferably 150° C. or higher. As a result, when the polymer contains the monomer units represented by the general formula (I) and the vinyl-based monomer units (D), some of these are more effectively decomposed, and the above-described curing is performed. properties, inhibition of coloring of the cured product, solvent resistance, etc. can be further improved. The heating temperature is more preferably 160° C. or higher, still more preferably 170° C. or higher, and particularly preferably 180° C. or higher. Also, the temperature is preferably 270° C. or lower, more preferably 260° C. or lower, and still more preferably 250° C. or lower.

The heating time in the heating step is not particularly limited, but is preferably 5 to 60 minutes, for example. Moreover, the heating method is not particularly limited, either, but for example, it can be performed using a heating device such as a hot plate, a convection oven, or a high-frequency heater.

3. Display Device The present invention is also a display device comprising the color filter described above.
A member for a display device and a display device having a cured product formed from the curable resin composition are also included in the preferred embodiments of the present invention. The cured product (cured film) formed from the curable resin composition is stable, has excellent adhesion to a substrate, etc., has high hardness, exhibits high smoothness, and has high transmittance. Therefore, it is particularly suitable as a transparent member, and is also useful as a protective film or an 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, or the like is suitable.
When the cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multilayer member composed of the cured film, or the single-layer or multilayer It may be a member in which another layer is further combined with the member of (1), or a member including the cured film in its configuration.

As described above, the curable resin composition of the present invention is excellent in developability and can give a cured product in which water unevenness is suppressed. In addition, the cured product obtained using the curable resin composition of the present invention is excellent in heat-resistant color resistance, adhesion to substrates, transparency, heat resistance, and the like. Such a curable resin composition of the present invention is very useful for various applications in the fields of optics, electrical machinery and electronics, such as color filters.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited only to these examples. Unless otherwise specified, "part" means "mass part" and "%" means "mass %". Analysis of the polymer in each synthesis example and each evaluation of the curable resin composition were performed as follows.

(1) weight average molecular weight (Mw)
Using polystyrene as a standard substance and tetrahydrofuran as an eluent, HLC-8220GPC (manufactured by Tosoh Corporation), column: GPC (gel permeation chromatography) using TSKgel SuperHZM-M (manufactured by Tosoh Corporation), the weight average molecular weight of the polymer. was measured.

(2) Solid content (NV)
About 1 g of the polymer solution was precisely weighed in an aluminum cup, and about 2 g of acetone was added to dissolve the polymer solution. After that, it was dried in a vacuum dryer (manufactured by EYELA) at a vacuum of 140° C. for 1.5 hours, then allowed to cool in a desiccator, and the mass of the aluminum cup was measured. The solid content (% by mass) of the polymer solution was calculated from the mass decrease amount.

(3) acid value (AV)
Accurately weigh 3 g of the polymer solution, dissolve it in a mixed solvent of 90 g of acetone and 10 g of water, use a 0.1 N potassium hydroxide aqueous solution as a titrant, and use an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., product: COM- 1700), and the acid value per gram of polymer (mgKOH/g) was determined from the acid value and solid content of the solution.

(4) Evaluation of water unevenness The resulting curable resin composition was dried on a non-alkali glass plate (10 cm x 10 cm, manufactured by Geomatec) using a spin coater so that the thickness of the coating film after drying was 3 μm. and dried on a hot plate at 100° C. for 3 minutes, and then irradiated with ultraviolet rays using an ultra-high pressure mercury lamp so that the irradiation amount was 100 mJ/cm ² . After the exposure, a 0.04% by mass potassium hydroxide aqueous solution was sprayed on the coating film for 60 seconds using a spin developing machine to carry out shower development. Then, the exposed portion was rinsed with pure water for 10 seconds, and the moisture on the surface of the glass plate was removed by blowing air.
Water unevenness (uneven density) of the coating film was observed using an optical microscope (magnification of 100) and evaluated according to the following criteria. 〇, 〇△ and △ were defined as practically acceptable levels according to the following criteria.
◯: Water unevenness cannot be confirmed with an optical microscope.
◯△: Water unevenness can be confirmed with an optical microscope.
Δ: Water unevenness can be confirmed with the naked eye.
x: Part of the coating film is peeled off during development.
XX: The coating film is completely peeled off during development.

(5) developability (development time)
The resulting curable resin composition was applied to a glass substrate by spin coating and heat-treated (100° C. for 3 minutes), and then a line-and-space opening having a line width of 6 to 100 μm was formed at a distance of 100 μm from the coating film. Exposure was performed at an exposure amount of 60 mJ/cm ² (365 nm illuminance conversion) using a UV aligner (manufactured by TOPCON, trade name “TME-150RNS”) equipped with a 2.0 kW ultra-high pressure mercury lamp through a photomask provided with a gone. After exposure, a 0.05% potassium hydroxide aqueous solution was sprayed with a spin developing machine (shower pressure: 0.15 MPa) to dissolve and remove the unexposed areas while washing the exposed areas with pure water for 10 seconds. Moisture on the surface of the glass plate was removed by air blow. By adjusting the time for spraying the aqueous potassium hydroxide solution, the shortest time (Break Time) (seconds) until development was completed was evaluated.

(6) Heat resistance to coloration The obtained curable resin composition was coated with a spin coater (1H-D7, manufactured by Mikasa Co., Ltd.) so that the coating amount was 1.0 to 3.0 mg / cm ² in terms of solid content. It was evenly coated on a 5 cm square glass substrate (soda lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.). At this time, for each curable resin composition, the number of rotations of the spin coater was changed to change the coating amount (in terms of solid content), and two coated plates with different coating amounts were produced. The coating amount on one of the two sheets was always greater than 1.6 mg/cm ² , and the coating amount on the other sheet was always less than 1.6 mg/cm ² .
These coated plates were dried at 140° C. for 1 hour and further dried at 180° C. for 1 hour to obtain a laminate having a coating film formed on a glass substrate. After removing the resin adhering to the edges of the glass substrate, the obtained laminate was heat-treated at 250° C. for 2 hours using a perfect oven thermostat (manufactured by Espec Co., Ltd.), and then cooled to room temperature. . After cooling, the coating film surface of the laminate was measured using a colorimetric color difference meter ZE6000 (manufactured by Nippon Denshoku Industries Co., Ltd.) to obtain the b ^* value after the heating test. For each coating film, an approximate straight line (calibration curve) of the coating amount (x) and b ^* value (y) is obtained from the measured values of the two coating films prepared as described above, and the coating amount is 1.6 mg / cm. The b ^* value for ² was taken as the result of the heat stain resistance of each coating.

(Synthesis example 1)
Preparation of polymer solution 1 A reactor equipped with a thermometer, a stirrer, a gas inlet pipe, a condenser pipe and a dropping tank inlet is charged with 70 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated to 90°C. heated up. On the other hand, as a dropping tank (A), 20 parts of N-benzylmaleimide (BzMI), 80 parts of propylene glycol monomethyl ether acetate (PGMEA) and t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation) were added to a beaker. 2 parts of Perbutyl O”) are stirred and mixed, and 20 parts of vinyl toluene (VT), 20 parts of t-butyl methacrylate (TBMA), 1-[2-(methacryloyl methacryloyl) succinate are added to the dropping tank (B). Oxy)ethyl](HOMS) 40 parts and n-dodecyl mercaptan 4 parts were stirred and mixed to prepare. After the temperature of the reactor reached 90° C., while maintaining the same temperature, dropping was started from the dropping tank over 3 hours to carry out polymerization. After the dropping was completed, the temperature was maintained at 90° C. for 30 minutes, then the temperature was raised to 115° C., and aging was performed for 90 minutes.
Analysis of the obtained polymer solution 1 revealed that the weight average molecular weight was 9000, the acid value was 98 mgKOH/g, and the solid content was 40% by mass. The monomer composition of the obtained polymer was BzMI/VT/TBMA/HOMS (molar ratio)=18/29/24/29.

(Synthesis example 2)
Polymer solution 2 was prepared in the same manner as in Synthesis Example 1, except that the amounts of the monomers charged were 20 parts of N-cyclohexylmaleimide (CHMI), 20 parts of VT, 20 parts of TBMA, and 40 parts of HOMS. got 2.
Analysis of the resulting polymer solution 2 revealed a weight average molecular weight of 10,000, an acid value of 98 mgKOH/g, and a solid content of 40% by mass. The monomer composition of the obtained polymer was CHMI/VT/TBMA/HOMS (molar ratio)=19/28/24/29.

(Synthesis Example 3)
Preparation of polymer solution 3 The same operation as in Synthesis Example 1 was performed except that the charged amounts of the monomers were 20 parts of N-phenylmaleimide (PMI), 20 parts of VT, 20 parts of TBMA, and 40 parts of HOMS. got 3.
Analysis of the resulting polymer solution 3 revealed a weight average molecular weight of 10,000, an acid value of 98 mgKOH/g, and a solid content of 40% by mass. The monomer composition of the obtained polymer was PMI/VT/TBMA/HOMS (molar ratio)=19/29/23/29.

(Synthesis Example 4)
Preparation of polymer solution 4 Polymer solution 4 was obtained in the same manner as in Synthesis Example 1 except that the amounts of the monomers charged were changed to 10 parts of PMI, 10 parts of VT, 40 parts of TBMA and 40 parts of HOMS.
Analysis of the resulting polymer solution 4 revealed a weight average molecular weight of 11,000, an acid value of 98 mgKOH/g, and a solid content of 40% by mass. The monomer composition of the obtained polymer was PMI/VT/TBMA/HOMS (molar ratio)=10/14/47/29.

(Synthesis Example 5)
Preparation of polymer solution 5 A polymer solution 5 was obtained in the same manner as in Synthesis Example 1 except that the amounts of the monomers charged were changed to 20 parts of PMI, 20 parts of VT, 30 parts of TBMA and 30 parts of HOMS.
Analysis of the resulting polymer solution 5 revealed a weight average molecular weight of 10,000, an acid value of 74 mgKOH/g, and a solid content of 40% by mass. The monomer composition of the obtained polymer was PMI/VT/TBMA/HOMS (molar ratio)=18/27/34/21.

(Synthesis Example 6)
Preparation of polymer solution 6 The amount of monomers charged was 10 parts of BzMI, 35 parts of TBMA, 19.5 parts of methyl methacrylate (MMA), 20 parts of 2-hydroxyethyl methacrylate (HEMA), and 15 parts of acrylic acid (AA). A polymer solution 6 was obtained in the same manner as in Synthesis Example 1 except that the content was changed to 5 parts.
Analysis of the resulting polymer solution 6 revealed a weight average molecular weight of 20,000, an acid value of 120 mgKOH/g, and a solid content of 35% by mass. The monomer composition of the obtained polymer was BzMI/TBMA/MMA/HEMA/AA (molar ratio)=6/29/23/18/24.

(Synthesis Example 7)
Polymer solution 7 was prepared in the same manner as in Synthesis Example 1 except that the amounts of the monomers charged were CHMI 10 parts, TBMA 35 parts, dicyclopentanyl methacrylate (DCPMA) 19.5 parts, HEMA 20 parts, and AA 15.5 parts. A polymer solution 7 was obtained by performing the same operation.
Analysis of the resulting polymer solution 7 revealed a weight average molecular weight of 21,000, an acid value of 120 mgKOH/g, and a solid content of 35% by mass. The monomer composition of the obtained polymer was CHMI/TBMA/DCPMA/HEMA/AA (molar ratio)=7/32/12/20/29.

(Synthesis Example 8)
Preparation of polymer solution 8 A polymer solution 8 was obtained in the same manner as in Synthesis Example 1 except that the amounts of the monomers charged were changed to 20 parts of PMI, 20 parts of CHMA, 20 parts of TBMA and 40 parts of HOMS.
Analysis of the resulting polymer solution 8 revealed a weight average molecular weight of 11,000, an acid value of 98 mgKOH/g, and a solid content of 40% by mass. The monomer composition of the obtained polymer was PMI/CHMA/TBMA/HOMS (molar ratio)=21/22/26/31.

(Example 1)
In terms of solid content, 20 parts of the polymer solution 1, 50 parts of the colorant composition (Blue), 20 parts of dipentaerythritol hexaacrylate as a polymerizable compound, Irgacure 907 (manufactured by BASF) as a photopolymerization initiator. 10 parts were mixed, and propylene glycol monomethyl ether acetate (PGMEA) was added as a dilution solvent so that the solid content concentration was 20% by mass, followed by stirring to obtain a curable resin composition (1-1). The developability of the resulting curable resin composition (1-1) was evaluated. Table 2 shows the results.

The coloring material composition (Blue) was prepared by the following method.
* Resin solution for preparation and dispersion of colorant composition (Blue) (resin monomer composition: BzMI/cyclohexyl methacrylate/methyl methacrylate/methacrylic acid = 30/30/30/10 (mass ratio), Mw: 10000, Acid value: 65 mg KOH / g, solid content in resin solution: 42%) 8.3 parts by mass, dispersant (manufactured by BYK Chemie Japan, trade name "DISPERBYK-2001", non-volatile content 1.3 g) 2. 9 parts by mass and 8.0 parts by mass of pigment (C.I. Pigment Blue 15:6) were weighed into a 225 ml container and diluted with PGMEA so that the concentration of non-volatile matter (concentration of solid matter) was 20% by weight. To this, 64 g of zirconia beads with a diameter of 1.0 mm were added, and after dispersion treatment by shaking with a paint shaker for 3 hours, the zirconia beads were removed by decantation to obtain a coloring material composition (Blue).

(Examples 2-5, Comparative Examples 1-3)
Polymer solutions 2 to 8 were used so as to have the formulations shown in Table 2, and in the same manner as in Example 1, curable resin compositions (2-1) to (8-1) were obtained. The developability of the obtained curable resin composition was evaluated. Table 2 shows the results.

(Example 6)
In terms of solid content, 45 parts of the polymer solution 1, 20 parts of the colorant composition (Blue), 25 parts of dipentaerythritol hexaacrylate as a polymerizable compound, Irgacure 907 as a photopolymerization initiator (manufactured by BASF) 10 parts of were mixed, and further a diluent solvent (PGMEA) was added so that the solid content concentration was 20% by mass, followed by stirring to obtain a curable resin composition (1-2). The water unevenness of the obtained curable resin composition (1-2) was evaluated. Table 3 shows the results.

(Examples 7-10, Comparative Examples 4-6)
Polymer solutions 2 to 8 were used so as to have the formulations shown in Table 3, and in the same manner as in Example 6, curable resin compositions (2-2) to (8-2) were obtained. The water unevenness of the obtained curable resin composition was evaluated. Table 3 shows the results.

Descriptions in Table 1 represent the following.
BzMI: N-benzylmaleimide CHMI: N-cyclohexylmaleimide PMI: N-phenylmaleimide VT: vinyl toluene CHMA: cyclohexyl methacrylate TBMA: t-butyl methacrylate MMA: methyl methacrylate DCPMA: dicyclopentanyl methacrylate HEMA: methacrylic Acid 2-hydroxyethyl AA: acrylic acid HOMS: mono(2-methacryloyloxyethyl) succinate

From Tables 1 to 3, curable resin compositions containing a polymer having a vinyl toluene unit and a succinic acid mono(2-methacryloyloxyethyl) unit as monomer units (Examples 1 to 10) had a vinyl toluene unit and a succinic acid mono (2-methacryloyloxyethyl) curable resin composition containing a polymer that does not have both units (Comparative Examples 1 to 6), development time is very short, and cure It was confirmed that the water unevenness of the material was sufficiently suppressed.
As described above, it is clear that the curable resin composition of the present invention has performance as a binder resin that requires quick developability while maintaining sufficient hydrophobicity to suppress water unevenness. be.

(Examples 11-15, Comparative Examples 7-8)
Propylene glycol monomethyl ether acetate (PGMEA) was added to polymer solutions 1 to 6 and 8 so as to have the formulations shown in Table 4, and curable resin compositions (1-3) to 35% by mass of solid content were prepared. (6-3) and (8-3) were obtained. The obtained curable resin composition was evaluated for heat color resistance. Table 4 shows the results.

From Table 4, curable resin compositions containing polymers having vinyl toluene units and succinic acid mono(2-methacryloyloxyethyl) units as monomer units (Examples 11 to 15) had vinyl toluene units and succinic acid mono(2-methacryloyloxyethyl) units. Compared to the curable resin compositions of polymers that do not have both acid mono(2-methacryloyloxyethyl) units (Comparative Examples 7 and 8), the b ^* value is a small value, and the heat coloring resistance is also improved. recognized to be excellent.

Claims (9)

aromatic vinyl-based monomer unit (A) , vinyl-based monomer unit (B) having an acid group in the side chain portion and the acid group is located at a position separated from the main chain by 5 atoms or more , N-substituted maleimide System monomer unit (C) and —COO ^* R ⁴ (R ⁴ is a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom.) group containing a polymer having a vinyl-based monomer unit (D) ,
The aromatic vinyl-based monomer unit (A) has a group containing a benzene ring,
The vinyl-based monomer unit (B) is a monomer unit represented by the following general formula (I),
The content of the aromatic vinyl-based monomer unit (A) in the polymer is 5 to 80% by mass with respect to 100% by mass of the total monomer units, and the vinyl-based monomer unit (B) is 5 to 70% by mass with respect to 100% by mass of the total monomer units, and the content of the N-substituted maleimide-based monomer unit (C) is 100% by mass of the total monomer units. 5 to 80% by mass with respect to the total monomer units, and the content of the vinyl-based monomer unit (D) is 5 to 70% by mass with respect to 100% by mass of the total monomer units.
A curable resin composition characterized by:

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms. R ³ represents a divalent chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 10 carbon atoms, X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic represents an acid anhydride group or a phosphate group, m represents the average number of repeating units of the monomer unit represented by the general formula (I), and is a number of 1 or more, and n is 0 or 1; be.) 2. The curable resin composition according to claim 1 , wherein the N-substituted maleimide-based monomer units (C) are N-phenylmaleimide monomer units and/or N-cyclohexylmaleimide monomer units. thing. In the polymer, the content ratio (A)/(B) of the aromatic vinyl-based monomer unit (A) and the vinyl-based monomer unit (B) is 10/60 to 60/ 10, the curable resin composition according to claim 1 or 2 . In the polymer, the aromatic vinyl-based monomer unit (A), the vinyl-based monomer unit (B), the N-substituted maleimide-based monomer unit (C), and the vinyl-based monomer unit ( D) and the content ratio [(A) + (C)]/[(B) + (D)] is 20/80 to 70/30 in terms of molar ratio. A curable resin composition according to any one of the above. The curable resin composition according to any one of claims 1 to 4 , wherein the polymer has an acid value of 40 to 180 mgKOH/g. 6. The curable resin composition according to any one of claims 1 to 5 , further comprising a polymerizable compound. A laminate comprising a substrate and a cured product of the curable resin composition according to any one of claims 1 to 6 on the substrate. A color filter comprising a cured product of the curable resin composition according to any one of claims 1 to 6 on a substrate. A display device comprising the color filter according to claim 8 .