JP2019172960A - Curable resin composition and application thereof - Google Patents

Abstract

To provide a curable resin composition capable of obtaining a cured article excellent in developability and having suppressed water irregularity, and capable of being suitable for an application of a color filter.SOLUTION: There is provided a curable resin composition containing a polymer having an aromatic vinyl monomer unit (A), and a vinyl monomer unit (B) having an acid group in a side chain part, in which the acid group is located at 5 atoms or more distance from a main chain.SELECTED DRAWING: None

Description

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

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

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

Various curable resin compositions suitable for color filter applications have been proposed so far.
For example, Patent Document 1 includes a polymer obtained by polymerizing an N-substituted maleimide monomer and / or a specific ether dimer, vinyl toluene, and a monomer having an acid group as an essential component as a monomer component. A photosensitive resin composition is described.
Further, for example, Patent Document 2 discloses a carboxyl group-containing radical 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 radical polymerizable double bond in the side chain. The photosensitive resin composition containing is described.

JP 2009-40999 A JP 2012-193219 A

However, in the case of performing development using a developer after the exposure process in the conventional curable resin composition, if the developer adheres to the exposed and cured part (cured part), the attached part becomes cloudy and the cured part However, there was a problem that unevenness in density (water unevenness) was generated, and transparency and colorability of the cured product were lowered.
In recent years, with an increase in demand for color filters, improvement in quality and productivity has been demanded, and there has been a demand for good development in a short 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 present situation, the present invention provides a curable resin composition that is excellent in developability and capable of obtaining a cured product in which water unevenness is suppressed and that can be suitably used for color filter applications. Objective.

The present inventor made various studies on the curable resin composition in order to solve the above problems. As a result, the aromatic vinyl monomer unit has an acid group in the side chain portion, and the acid group is separated from the main chain. It has been found that by using a polymer having a vinyl monomer unit at a position separated by 5 atoms or more, a cured product having excellent developability and water unevenness can be obtained. Further, the present inventors have found that a curable resin composition containing such a polymer is particularly suitable as a resin composition for forming a member for use such as a color filter, and completed the present invention. It came to do.

That is, the present invention relates to an aromatic vinyl monomer unit (A) and a vinyl monomer having an acid group in the side chain portion and the acid group being located at a position 5 atoms or more away from the main chain. A curable resin composition comprising a polymer having a unit (B).

The vinyl 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 unit, and is a number of 1 or more, and n is 0 or 1.)

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

The N-substituted maleimide monomer unit (C) is preferably an N-phenylmaleimide monomer unit and / or an N-cyclohexylmaleimide monomer unit.

The polymer further includes a vinyl-based single group containing a —COO ^* R ⁴ (R ⁴ is a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom). It is preferable to have a monomer unit (D).

In the polymer, the content ratio (A) / (B) of the aromatic vinyl monomer unit (A) and the vinyl monomer unit (B) is 10/60 to 60 / in molar ratio. 10 is preferable.

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

The curable resin composition preferably further contains a polymerizable compound.

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

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

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

Since the curable resin composition of this invention consists of the above-mentioned structure, it can give the hardened | cured material which was excellent in developability and the water nonuniformity was suppressed. Such a curable resin composition of the present invention includes a color filter, a black matrix, a photo spacer, a black column, which are used for liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, and the like. As optical members and constituent members such as spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, etc., they can be suitably used for various applications such as electrical and electronic equipment.

The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
In the present specification, “(meth) acrylate” means “acrylate and / or methacrylate”, and “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”.

1. Curable resin composition The curable resin composition of the present invention has an aromatic vinyl 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 contains a polymer having a vinyl monomer unit (B) at a different position.
When the curable resin composition of the present invention contains such a specific polymer, a cured product in which water unevenness is suppressed can be provided because the polymer contains an aromatic vinyl monomer unit. By having it, it is estimated that it becomes based on the hydrophobicity of the hardened | cured material obtained becoming high. In addition, the curable resin composition of the present invention is excellent in developability because the polymer has the above-mentioned specific vinyl monomer unit (B), such as a carboxyl group 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 contact probability with the developer.

In this specification, “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, the contacted part becomes discolored, resulting in hardening. This means that unevenness is produced in the object.
Below, each component contained in the curable resin composition of this invention is demonstrated.

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

(Aromatic vinyl monomer unit (A))
The polymer has an aromatic vinyl monomer unit (hereinafter also referred to as “monomer unit (A)”). When the polymer has an aromatic vinyl monomer unit, the curable resin composition of the present invention can provide a cured product in which water unevenness is suppressed. Moreover, when the said polymer has an aromatic vinyl-type monomer unit, the curable resin composition of this invention can give the hardened | cured material excellent also in heat-resistant coloring property.
In addition, in this invention, heat-resistant coloring property means the characteristic that the color of hardened | cured material is hard to yellow at the time of a heating.
The aromatic vinyl monomer unit is a structural unit derived from an aromatic vinyl monomer, and a structural unit derived from a monomer having an aromatic group and a vinyl group is preferred.

As said aromatic group, group containing a benzene ring, a naphthalene ring, etc. is mentioned, Especially, the group containing a benzene ring is preferable.
The aromatic group may have a substituent. As said substituent, a C1-C5 alkyl group, a C1-C5 alkoxy group, etc. are mentioned, for example.

Specific examples of the aromatic vinyl monomers include styrene, vinyl toluene, α-methyl styrene, xylene, methoxy styrene, ethoxy styrene, and the like. In this respect, styrene and vinyltoluene are preferable, and vinyltoluene is more preferable in that the dissolution rate with respect to an organic solvent or alkali is high. By polymerizing a monomer component containing such an aromatic vinyl monomer, a polymer having the monomer unit (A) can be obtained.
The said polymer may have only 1 type as said aromatic vinyl-type monomer unit, and may have 2 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 all monomer units in consideration of the excellent water unevenness suppressing effect and developability. Preferably there is. 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-resistant coloring property can be further improved. The content is more preferably at least mass%, more preferably at most 70 mass%, still more preferably at most 60 mass%.

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

The vinyl monomer unit (B) has an acid group in the side chain portion, and the acid group is at a position away from the main chain by 5 atoms or more.
Examples of the acid group include a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, and has only one of these. You may have, and you may have 2 or more types. Especially, as said acid group, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable.

In the vinyl monomer unit (B), the acid group is located 5 or more atoms away from the main chain. In the present invention, when the acid group is at a position 5 or more atoms away from the main chain, the position of the carbon atom on the main chain of the polymer to which the side chain is bonded is defined as 0 (zero), and the side chain extends from that position. The state in which there is an acid group at the position after the fifth atom. The atoms on the side chain may be atoms other than carbon or substituents. Specifically, for example, in the case of 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 the formula (a2), the acid group X is 7 from the main chain. It can be said that it is in a position away from the atom.

The acid group is preferably located at a position that is 18 atoms or less away, more preferably located at a position that is 16 atoms or less away, and 14 atoms or less away from the standpoint of maintaining moderate solubility in the developer. More preferably, it is in a different position.

The vinyl monomer unit (B) is preferably, for example, 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 unit, and is a number of 1 or more, and n is 0 or 1.)

When the polymer has the monomer unit represented by the general formula (I), the curable resin composition of the present invention is a cured product having excellent heat resistance colorability in addition to developability. Can be given. Although it is not certain that the polymer having the monomer unit represented by the general formula (I) can give a cured product excellent in heat-resistant colorability, when the polymer is heated, This is because a part of the monomer unit represented by the general formula (I) is eliminated and a hydroxyl group is formed at the terminal, and this hydroxyl group captures a radical in the reaction system to reduce the influence of the radical. It is guessed.

In the above general formula (I), R ¹ represents a hydrogen atom or a methyl group. From the viewpoint of copolymerization with the aromatic vinyl 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. An alkylene group is 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 a methylene group, an ethylene group, a propylene group, a butylene group, a heptylene group, an octylene group or a dodecylene group; an arylene group such as a phenylene group, a tolylene group or a naphthylene group; A group substituted with a functional group such as a hydroxy group or an alkoxy group; Among these, as ^{R 2,} preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms.

R ³ represents a divalent organic group. The divalent organic group is preferably 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. And a divalent chain or branched saturated hydrocarbon group or unsaturated hydrocarbon group. The organic group may have a substituent.

Examples of R ³ include alkylene groups such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, an ethylethylene group, a hexylene group, an octylene group, and a dodecylene group; a vinylene group, a propenylene group, and an isopropenylene group. Alkenylene groups such as butenylene group, pentenylene group, hexenylene group; cycloalkylene groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, norbornylene group, adamantylene group; phenylene group, tolylene group, naphthylene Groups, arylene groups such as fluorene groups; alkyl ether groups such as ethyl ether groups and propyl ether groups; and groups containing bonds such as —O—, —S—, —SO—, and —SO ₂ — with these groups. It is done.
Especially, an alkylene group is preferable at the point which developability is further excellent, A C1-C10 alkylene group is more preferable, A C1-C5 alkylene group is still more preferable.

X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group, or a phosphoric acid group. Especially, it is preferable that X is a carboxyl group at the point which developability is further excellent.
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.
n is 0 or 1, preferably 1.

As the monomer giving the vinyl monomer unit (B), β-carboxyethyl (meth) acrylate, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate is preferable. ) And the like, and unsaturated monocarboxylic acids in which the chain is extended between an unsaturated group and a carboxyl group, and more preferably β-carboxyethyl (meth) acrylate and mono (2-acryloyloxyethyl) succinate. ), Mono (2-methacryloyloxyethyl) succinate, and more preferably mono (2-methacryloyloxyethyl) succinate. By polymerizing a monomer component containing such a compound, a polymer having the vinyl monomer unit (B) can be obtained.
The said polymer may have only 1 type as said vinyl-type monomer unit (B), and may have 2 or more types.

The content of the vinyl monomer unit (B) in the polymer is 5 to 70% by mass with respect to 100% by mass of all monomer units in consideration of both excellent developability and water unevenness suppression effect. % Is preferred.
The content of the vinyl 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 heat resistant colorability can be further improved. 15% by mass or more, more preferably 20% by mass or more, more preferably 65% by mass or less, and still more preferably 60% by mass or less.

(N-substituted maleimide monomer unit (C))
The polymer preferably further has an N-substituted maleimide monomer unit (hereinafter also referred to as “monomer unit (C)”). When the polymer has an N-substituted maleimide-based monomer unit, a cured product having a more excellent water unevenness suppressing effect can be provided, and a cured product having excellent heat-resistant colorability can be provided. .
It is presumed that the effect of suppressing water unevenness is further improved when the polymer further includes an N-substituted maleimide monomer unit as follows. That is, when the polymer has an N-substituted maleimide monomer unit, the polymer includes N monomer together with the above-described monomer unit (A) and vinyl monomer unit (B). Obtained by polymerizing a substituted maleimide monomer. In this polymerization, the aromatic vinyl monomer that gives the monomer unit (A) and the N-substituted maleimide monomer have good alternating copolymerization, so that they are adjacent to each other in the polymer. It becomes easy to be introduced. Therefore, in the polymer, a portion having a large proportion of the monomer unit (A) and the N-substituted maleimide monomer unit (C) that are hydrophobic, and the vinyl monomer unit (B )), It is speculated that the effect of suppressing water unevenness can be further exhibited and the developability can be further improved.

Examples of N-substituted maleimide monomers that give the monomer unit (C) include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N- Examples thereof 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 is more preferable because N-phenylmaleimide and / or N-cyclohexylmaleimide are more preferable because the effect of suppressing water unevenness becomes more prominent and heat-resistant colorability can also 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 Halogen-substituted benzylmaleimide such as o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide;

The said polymer may have only 1 type as said monomer unit (C), and may have 2 or more types.

The content of the monomer unit (C) in the polymer is 5 to 80% by mass with respect to 100% by mass of all monomer units, considering both excellent developability and the effect of suppressing water unevenness. % Is preferred.
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 resistant colorability can be further improved. The content is more preferably at least mass%, more preferably at most 70 mass%, still more preferably at most 60 mass%.

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% of all monomer units. It is preferable that it is 25-75 mol% with respect to mol%, and it is more preferable that it is 30-70 mol%. When the total amount of the monomer unit (A) and the monomer unit (C) is in the above range, water unevenness of the obtained cured product can be further suppressed.

(Vinyl monomer unit containing a —COO ^* R ⁴ group (D))
The polymer further includes a vinyl-based single group containing a —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 monomer unit (D)”). When the polymer further has such a vinyl monomer unit (D), the curability of the curable resin composition, the heat resistance of the resulting cured product, together with the water unevenness suppressing effect and developability, Performances such as solvent resistance can be further improved.

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

Examples of the vinyl monomer include monomers having a polymerizable carbon-carbon double bond in the molecule, and (meth) acrylate monomers are particularly preferable. That is, the vinyl monomer unit (D) is preferably a tertiary carbon-containing (meth) acrylate 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. A compound having one -C (= O)-) is preferable. For example, the following general formula (a):
^{_{CH 2 = C (R 5)}} -C (= O) -O-A (a)
(Wherein R ⁵ represents a hydrogen atom or a methyl group. A represents a monovalent organic group including a structure having a tertiary carbon atom on the oxygen atom side). It is preferable.

In the general formula (a), the monovalent organic group represented by A can be represented by, for example, —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 hydrocarbon group may be a saturated hydrocarbon group. , May be an unsaturated hydrocarbon group, may have a cyclic structure, or may have a substituent. R ⁶ , R ⁷ , and R ⁸ may be linked to each other at a terminal site to form a cyclic structure.

The number of carbon atoms of the organic group represented by A is the number of oxygen atoms adjacent to the (meth) acryloyl group (CH ₂ ═C (R ⁵ ) —C (═O) —) and the third in A adjacent to it. It is preferably 12 or less, more preferably 9 or less, in that a new compound produced by cleavage of the O—C bond between the secondary 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 monomer, the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth) acryloyl group is bonded to a hydrogen atom at least one of the adjacent carbon atoms. It is preferable. For example, a tertiary carbon-containing (meth) acrylate monomer is a compound represented by the above general formula (a), and A is represented by -C (R ⁶ ) (R ⁷ ) (R ⁸ ). It is preferable 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, by heating, the O—C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto is cut, and (meth) acrylic acid is generated at the same time. Then, a double bond (C = C) is formed between the tertiary carbon atom and the carbon atom adjacent thereto, and a new compound is generated more stably.

It is preferable that the new compound produced | generated as mentioned above is a thing which volatilizes. In this case, the film thickness of the cured product (cured film) is reduced due to volatilization of the new compound from the cured product, and at the same time, for example, the curable resin composition further includes a color material. In some cases, the colorant concentration increases after heating. Therefore, it is possible to realize a further thinner film, and to achieve higher color purity and higher light blocking ratio of the black matrix. In consideration of this point, R ⁶ , R ⁷ and R ⁸ are preferably the same or different and are each a saturated hydrocarbon group having 1 to 15 carbon atoms. More preferably, it is a C1-C10 saturated hydrocarbon group, More preferably, it is a C1-C5 saturated hydrocarbon group, Most preferably, it is a C1-C3 saturated hydrocarbon group.

The tertiary carbon-containing (meth) acrylate monomer is preferably t-butyl (meth) acrylate or t-amyl (meth) acrylate.
In addition, from the viewpoint of copolymerization with the above aromatic vinyl monomer, the tertiary carbon-containing (meth) acrylate monomer is preferably a tertiary carbon-containing methacrylate monomer, More preferably, it is t-butyl methacrylate or t-amyl methacrylate.
The said polymer may have only 1 type as said vinyl-type monomer unit (D), and may have 2 or more types.

The content of the vinyl monomer unit (D) in the polymer is preferably 5 to 70% by mass and preferably 10% by mass or more with respect to 100% by mass of all monomer units. More preferably, it is more preferably 15% by mass or more, more preferably 65% by mass or less, and further preferably 60% by mass or less.

When the polymer has the vinyl monomer unit (D), the total amount of the vinyl monomer unit (B) and the vinyl monomer unit (D) in the polymer is It is preferable that it is 80 mol% or less with respect to 100 mol% of monomer components. When the total amount is in the above range, the effect of suppressing water unevenness is further improved. The total amount is more preferably 70 mol% or less with respect to 100 mol% of all monomer components. Further, from the viewpoint of developability, the total amount is preferably 20 mol% or more, more preferably 25 mol% or more with respect to 100 mol% of all monomer components.

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

As said acid group containing monomer, the compound which has an acid group and a polymerizable double bond in a molecule | numerator other than the monomer which gives the monomer unit (B) mentioned above is mentioned.

Examples of the acid group include a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, and has only one of these. You may have, and you may have 2 or more types. Of these, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable.
Examples of the polymerizable double bond include a (meth) acryloyl group, a vinyl group, an allyl group, and a methallyl group.

Specific examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; maleic acid, fumaric acid, itaconic acid, Unsaturated polyhydric carboxylic 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, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. From the viewpoints of reactivity, water unevenness suppression effect, developability, etc., more preferable are unsaturated monocarboxylic acids, still more preferably (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid), particularly preferably. Methacrylic acid.

Examples of (meth) acrylate monomers other than the monomer that gives the vinyl monomer unit (D) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and (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, (meth) a 2-methoxyethyl laurate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 1,4-dioxaspiro [4,5] deca 2-ylmethacrylic acid, (meth) acryloylmorpholine, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl- 2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1, Examples include 3-dioxolane.

As said other copolymerizable monomer, 1 type (s) or 2 or more types, such as the following compound, are mentioned, for example.
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; N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide and the like ( (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; 3- Conjugated dienes such as tadiene, 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-nonyl Vinyl ethers such as 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-vinyl Caprolactam, N-vinylimidazole, N-vinyl morpholine N-vinyl compounds such as N-vinylacetamide; Unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate; α-allyloxymethylacrylic acid, α-allyloxymethylmethylacrylate, α- Allyloxymethyl ethyl acrylate, α-allyloxymethyl acrylate n-propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl , Α-allyloxymethyl acrylate t-butyl, α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl Α- (unsaturated alkoxy) such as neopentyl acrylate Alkyl) acrylate monomers, and the like.
The said polymer may have only 1 type as said monomer unit (E), and may have 2 or more types.

The content of the monomer unit (E) in the polymer is preferably 1 to 60% by mass, and 5 to 55% by mass with respect to 100% by mass of all monomer units of the polymer. More preferably, it is 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 molar ratio. Is preferred. When the content ratio is in the above range, the water unevenness suppressing effect and developability are further improved. The content ratio (A) / (B) is more preferably 13/55 to 55/13, and further preferably 15/50 to 50/15.

When the polymer has the monomer unit (A), the vinyl monomer unit (B), and the monomer unit (C), the effect of suppressing water unevenness is sufficient regardless of other components. The content ratio [(A) + (C)] / (B) in the polymer is preferably 15/60 to 70/10 in molar ratio, and 20/55 to 65. / 13 is more preferable, and 25/50 to 60/15 is even more preferable.

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

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

Although the weight average molecular weight of the said polymer is not specifically limited, 5000-50000 are preferable, 6000-40000 are more preferable, 7000-35000 are still more preferable.
The weight average molecular weight of the polymer is a value obtained by measurement by the method described in Examples by gel permeation chromatography (GPC).

<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 monomer unit (A) and the vinyl monomer unit (B). A monomer comprising the monomer that gives the monomer units (A) and (B) and the monomer that gives the monomer units (C), (D), or (E) as necessary The body component is polymerized by a known method.

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

The blending amount of the monomer component at the time of polymerization is not particularly limited as long as a polymer giving a cured product having excellent developability and suppressed water unevenness can be obtained. Each monomer unit in the polymer What is necessary is just to design suitably so that content of may become the range mentioned above.

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

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

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

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

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

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

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

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

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

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

Regarding the polymerization conditions, the polymerization temperature may be appropriately set according to the type and amount of the monomer to be used, the type and amount of the polymerization initiator, and is preferably 50 to 150 ° C, for example, 70 to 120 ° C. is more preferable. Also, the polymerization time can be appropriately set similarly, but for example, 1 to 5 hours is preferable, and 2 to 4 hours is more preferable.

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 use and the blending of other components. For example, the solid content of the curable resin composition 10-60 mass% is preferable with respect to 100 mass% of total amount, 15-55 mass% is more preferable, and 20-50 mass% is still more preferable.
The “total amount of solids” means the total amount of components that form a cured product (excluding solvents that volatilize during the formation of the cured product).

<Polymerizable compound>
The curable resin composition of the present invention preferably further contains a polymerizable compound. By including the polymer and the polymerizable compound described above, in addition to the water unevenness suppressing effect 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 that is more excellent in terms of properties.

The polymerizable compound can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays), electron beams, etc. (also referred to as polymerizable unsaturated groups). It is a low molecular compound having For example, the monofunctional compound which has one polymerizable unsaturated group in a molecule | numerator, and the polyfunctional compound which has 2 or more are mentioned.

Examples of the monofunctional compound include N-substituted maleimide monomers; (meth) acrylic acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated groups and carboxyls Unsaturated monocarboxylic acids in which the chain is extended; Unsaturated acid anhydrides; Aromatic vinyls; Conjugated dienes; Vinyl esters; Vinyl ethers; N-vinyl compounds; Is mentioned. A monomer having an active methylene group or an active methine group can also be used.

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

Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Hexa (meth) acrylate, dipentaerythritol pentaacrylate modified with succinic acid Product, pentaerythritol triacrylate succinic acid modified product, dipentaerythritol pentaacrylate phthalic acid modified product, pentaerythritol triacrylate phthalic acid modified product, the following 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, ditrile Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethyl Lumpur propane tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, polyfunctional vinyl ethers such as ethylene oxide adduct of dipentaerythritol hexavinyl ether;

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

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

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

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

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

In the curable resin composition of the present invention, the content 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 which can make it a viscosity, Preferably it is 2-60 mass% with respect to 100 mass% of solid content total amount of the curable resin composition of this invention, More preferably, it is 5-55 mass%, More preferably, it is 10 -50 mass%.

<Photopolymerization initiator>
The curable resin composition of the present invention preferably further contains a photopolymerization initiator. By including a photopolymerization initiator, the curability of the curable resin composition can be improved, and the performance of the resulting cured product can be improved.
The photopolymerization initiator used in the present invention is preferably a radical polymerizable photopolymerization initiator. The radically polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam.

The photopolymerization initiator is not particularly limited. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE907”, manufactured by BASF), 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ("IRGACURE369", manufactured by BASF), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4 Alkylphenone compounds such as -morpholin-4-yl-phenyl) -butan-1-one ("IRGACURE 379" manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one (" IRGACURE 651 ", manufactured by BASF), phenylglyoxylic acid methyl ester (" DAROCUR MBF ", BA Benzyl ketal compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR 1173"). ", 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-methyl-propan-1-one ("IRGACURE127", manufactured by BASF), [1-hydroxy -Cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE500", B In addition to hydroketone compounds such as SF), alkylphenone compounds exemplified in paragraphs [0084] to [0086] of JP2013-227485A; 1,2-octanedione, 1- [ 4- (phenylthio) phenyl]-, 2- (O-benzoyloxime)] (“OXE01”, manufactured by BASF), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 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-acetyl) Oxime) (“OXE04”, manufactured by BASF)), etc .; benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; biimidazole compounds; Examples include titanocene compounds; benzoate compounds; acridine compounds and the like; phosphine oxide compounds. Of these, alkylphenone compounds are preferred.
The said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

In the case of using the photosensitizer and the photo radical polymerization accelerator, the content thereof is 100% by mass of the total solid content of the curable resin composition from the viewpoint of balance between curability, influence of degradation products and economic efficiency. It is preferable that it is 0.001-20 mass% with respect to it, More preferably, it is 0.01-15 mass%, More preferably, it is 0.05-10 mass%.

<Other ingredients>
The curable resin composition of the present invention may contain other components as necessary in addition to the above-described polymer, polymerizable compound, and photopolymerization initiator. Other components include, for example, a solvent, a coloring material (also called a colorant), a dispersant, an antioxidant, a heat resistance improver, a leveling agent, a development aid, an inorganic fine particle such as a silica fine particle, a silane type, an aluminum type, Coupling agents such as titanium; Thermosetting resins such as fillers, epoxy resins, phenol resins, and polyvinylphenols; Curing aids such as polyfunctional thiol compounds; Plasticizers; Polymerization inhibitors; Ultraviolet absorbers; Antifoaming agent; antistatic agent; slip agent; surface modifier; thixotropic agent; thixotropic agent; quinonediazide compound; polyhydric phenol compound; cationic polymerizable compound; These may be used individually by 1 type and may be used in combination of 2 or more type. For example, when using the said curable resin composition for a color filter use, it is preferable that the said curable resin composition contains a coloring material.

(solvent)
As the solvent, those commonly used in the curable resin composition can be used, and may be appropriately selected depending on the purpose and application, and are not particularly limited. For example, described in JP-A-2015-157909 The thing similar to the thing of can be used. These may be used individually by 1 type and may be used in combination of 2 or more type.

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

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

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

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

The content of the coloring material is not particularly limited and can be set as appropriate according to the purpose and application, but is preferably set to 0.1% with respect to 100% by mass of the total solid content of the curable resin composition. 1-20 mass%, More preferably, it is 1-15 mass%, More preferably, 2-12 mass% is mentioned.

(Dispersant)
When the curable resin composition of this invention contains the said color material, it is preferable that a dispersing agent is further included.
The above-mentioned dispersant has an interaction site with a color material and an interaction site with a dispersion medium (for example, a solvent or a binder resin), and has a function of stabilizing the dispersion of the color material into the dispersion medium. In general, it is classified into a resin-type dispersant (for example, a polymer dispersant), a surfactant (for example, a low-molecular dispersant), and a pigment derivative. These may be used individually by 1 type and may be used in combination of 2 or more type.

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

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

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

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

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

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

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

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

2. Laminate The curable resin composition of the present invention provides a cured product having excellent developability and reduced water unevenness as described above. Moreover, the said hardened | cured material is excellent also in basic performance, such as sclerosis | hardenability, adhesiveness with a base material, heat resistance, and transparency. Such a laminate having a cured product of the curable resin composition on a substrate (base material) is also one aspect of the present invention.

When the cured product is a cured film, the film thickness is preferably 0.1 to 20 μm. When the film thickness is in the above-described range, it is possible to exhibit a more excellent water unevenness suppressing effect. In addition, various performances such as adhesion to the substrate, 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 above-described curable resin composition is applied on a substrate, and the applied product is dried, heated, or ultraviolet rays. There is a method of obtaining a cured product by curing by irradiating energy rays.
The base material (substrate) is not particularly limited and may be appropriately selected depending on the purpose and application. Examples thereof include base materials made of various materials such as a glass plate and a plastic plate.

The laminate is, for example, a color filter, black matrix, photo spacer, black column spacer, ink, printing plate, liquid crystal / organic EL / quantum dot / micro LED display device, solid-state imaging device, touch panel display device, etc. It is preferably used in various applications such as electric and electronic devices as various optical members and components such as printed wiring boards, semiconductor elements, photoresists, insulating films and the like. Especially, it is preferable to use 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 filter will be 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 that becomes the cured resin layer is the curable resin composition of the present invention. The color filter is an optical filter having a fine pixel of at least three primary colors and a black matrix separating them on a transparent substrate, which is necessary for colorization of an image, and the three primary colors are generally red (R). Green (G) and blue (B) are used. Specific examples of members constituting the color filter include three primary color (RGB) pixels, a resin black matrix, a protective film, a columnar spacer, and a black column spacer (BCS). It is sufficient that at least one of the members constituting the material is formed by curing the curable resin composition.

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

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

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

(Light irradiation process)
Examples of the active light source used in the light irradiation step include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, and a fluorescent lamp. Lamp light sources, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, semiconductor lasers, and the like are used. Further, examples of the exposure system include a proximity system, a mirror projection system, and a stepper system, but the proximity system is preferably used.
In the irradiation process of the active energy beam, the active energy beam may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed portion is cured, and the cured portion is insolubilized or hardly soluble in the developer.

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

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

Examples of the organic solvent suitable as the developer include an ether solvent and an alcohol solvent. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkyl phenyl ethers, aralkyl phenyl ethers, diaromatic ethers , Isopropanol, benzyl alcohol and the like.

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

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

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

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

In the heating step, the heating temperature is preferably 150 ° C. or higher. Thereby, when a polymer contains the monomer unit represented by the said general formula (I) and the said vinyl-type monomer unit (D), some of these are decomposed | disassembled more effectively and the hardening mentioned above Property, suppression of coloring of the cured product, solvent resistance, and the like 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. Moreover, it is preferable to set it as 270 degrees C or less, More preferably, it is 260 degrees C or less, More preferably, it is 250 degrees C or less.

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

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

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

As described above, the curable resin composition of the present invention can provide a cured product having excellent developability and suppressed water unevenness. Moreover, the hardened | cured material obtained using the curable resin composition of this invention is excellent also in heat-resistant coloring, and is excellent also in adhesiveness with a board | substrate, transparency, heat resistance, etc. Such a curable resin composition of the present invention is very useful for various applications in the optical field, electrical machinery and electronic fields, such as color filters.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”. 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)
Weight average molecular weight of polymer by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent. Was measured.

(2) Solid content (NV)
About 1 g of the polymer solution was precisely weighed in an aluminum cup, about 2 g of acetone was added and dissolved, and then allowed to stand at room temperature for about 2 hours to be naturally dried. Then, after drying for 1.5 hours at 140 ° C. in a vacuum dryer (manufactured by EYELA), the product was allowed to cool in a desiccator, and the mass of the aluminum cup was measured. The solid content (mass%) of the polymer solution was calculated from the mass reduction amount.

(3) Acid value (AV)
3 g of the polymer solution is precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an aqueous solution of 0.1N potassium hydroxide is used as a titrant. 1700), the acid value of the polymer solution was measured, and the acid value per 1 g of polymer (mgKOH / g) was determined from the acid value of the solution and the solid content.

(4) Evaluation of water unevenness The thickness of the coating film after drying the obtained curable resin composition on a non-alkali glass plate (10 cm × 10 cm, manufactured by Geomat Co.) using a spin coater is 3 μm. And dried on a hot plate at 100 ° C. for 3 minutes, and then irradiated with ultraviolet rays using an ultrahigh pressure mercury lamp so that the irradiation dose was 100 mJ / cm ² . After the exposure, 0.04 mass% potassium hydroxide aqueous solution was sprayed on the coating film for 60 seconds with a spin developing machine to perform shower development. Next, the exposed portion was washed with pure water for 10 seconds, and then water on the glass plate surface was removed by air blowing.
The coating film was observed for water unevenness (darkness unevenness) using an optical microscope (100 times magnification) and evaluated according to the following criteria. On the basis of the following criteria, ○, ○ △, and △ were set to a level having no practical problem.
◯: Water unevenness cannot be confirmed with an optical microscope.
○ Δ: Water unevenness can be confirmed with an optical microscope.
Δ: Water unevenness can be confirmed with the naked eye.
X: A part of coating film is peeled off during development.
XX: All coating films are peeled off during development.

(5) Developability (development time)
The obtained curable resin composition is applied to a glass substrate by a spin coating method, heat-treated (100 ° C. for 3 minutes), and then a line and space opening having a line width of 6 to 100 μm at a distance of 100 μm from the coating film Using a UV aligner (trade name “TME-150RNS” manufactured by TOPCON, Inc.) equipped with a 2.0 kW ultrahigh pressure mercury lamp through a photomask provided with an exposure amount of 60 mJ / cm ² (365 nm illuminance conversion). went. After exposure, a 0.05% aqueous potassium hydroxide solution was sprayed with a spin developing machine (shower pressure 0.15 MPa), and the exposed area was washed with pure water for 10 seconds while dissolving and removing the unexposed area. Water on the glass plate surface was removed by air blowing. By adjusting the time for spraying the potassium hydroxide aqueous solution, the shortest time (Break Time) (seconds) until the development was completed was evaluated.

(6) Heat-resistant coloring property The obtained curable resin composition was applied with a spin coater (manufactured by Mikasa Co., Ltd., 1H-D7) with a coating amount of 1.0 to 3.0 mg / cm ^{2 in} terms of solid content. It was applied uniformly on a 5 cm square glass substrate (soda lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.). Under the present circumstances, about each curable resin composition, the rotation speed of the spin coater was changed and application amount (solid content conversion) was changed, and the 2 application | coating board from which application amount differs was produced. The coating amount of one of the two sheets was always larger than 1.6 mg / cm ^2, and the coating amount of the other sheet was always smaller 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 edge of the glass substrate, the obtained laminate was heat-treated at 250 ° C. for 2 hours using a perfect oven incubator (manufactured by Espec Corp.), 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 a b ^* value after the heating test. An approximate straight line (calibration curve) between the coating amount (x) and the b ^* value (y) was determined from the measured values of the two coating films prepared as described above for each coating film, and the coating amount was 1.6 mg / cm. The b ^* value in the case of ² was adopted as a result of the heat resistance coloring property of each coating film.

(Synthesis Example 1)
Preparation of polymer solution 1 A reactor equipped with a thermometer, stirrer, gas inlet tube, cooling tube and dropping tank inlet was charged with 70 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and heated to 90 ° C. The temperature rose. 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-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation) 2 parts of Perbutyl O ") were prepared by stirring and mixing, and 20 parts of vinyltoluene (VT), 20 parts of t-butyl methacrylate (TBMA), 1- [2- (methacryloyl succinate) were added to the dropping tank (B). A mixture prepared by stirring and mixing 40 parts of (oxy) ethyl] (HOMS) and 4 parts of n-dodecyl mercaptan was prepared. After the temperature of the reaction vessel reached 90 ° C., dropping was started over 3 hours from the dropping vessel while maintaining the same temperature, and polymerization was performed. After maintaining the temperature at 90 ° C. for 30 minutes after completion of the dropping, the temperature was raised to 115 ° C. and aging was performed for 90 minutes.
When the obtained polymer solution 1 was analyzed, the weight average molecular weight was 9000, the acid value was 98 mgKOH / g, and the solid content was 40% by mass. Moreover, the monomer composition of the obtained polymer was BzMI / VT / TBMA / HOMS (molar ratio) = 18/29/24/29.

(Synthesis Example 2)
The polymer solution 2 was prepared in the same manner as in Synthesis Example 1 except that the amount of monomer prepared was 20 parts of N-cyclohexylmaleimide (CHMI), 20 parts of VT, 20 parts of TBMA, and 40 parts of HOMS. 2 was obtained.
When the obtained polymer solution 2 was analyzed, the weight average molecular weight was 10,000, the acid value was 98 mgKOH / g, and the solid content was 40% by mass. Further, 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 procedure as in Synthesis Example 1 was carried out except that the amount of monomer prepared was 20 parts of N-phenylmaleimide (PMI), 20 parts of VT, 20 parts of TBMA, and 40 parts of HOMS. 3 was obtained.
When the obtained polymer solution 3 was analyzed, the weight average molecular weight was 10,000, the acid value was 98 mgKOH / g, and the solid content was 40% by mass. Moreover, 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 amount of monomer charged was 10 parts PMI, 10 parts VT, 40 parts TBMA, and 40 parts HOMS.
When the obtained polymer solution 4 was analyzed, the weight average molecular weight was 11000, the acid value was 98 mgKOH / g, and the solid content was 40% by mass. Moreover, 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 Polymer solution 5 was obtained in the same manner as in Synthesis example 1 except that the amount of monomer prepared was 20 parts PMI, 20 parts VT, 30 parts TBMA, and 30 parts HOMS.
When the obtained polymer solution 5 was analyzed, the weight average molecular weight was 10,000, the acid value was 74 mgKOH / g, and the solid content was 40% by mass. Moreover, the monomer composition of the obtained polymer was PMI / VT / TBMA / HOMS (molar ratio) = 18/27/34/21.

(Synthesis Example 6)
The amount of monomer prepared for polymer solution 6 was 10 parts BzMI, 35 parts TBMA, 19.5 parts methyl methacrylate (MMA), 20 parts 2-hydroxyethyl methacrylate (HEMA), and acrylic acid (AA) 15. A polymer solution 6 was obtained in the same manner as in Synthesis Example 1, except that the amount was 5 parts.
When the obtained polymer solution 6 was analyzed, the weight average molecular weight was 20000, the acid value was 120 mgKOH / g, and the solid content was 35 mass%. Moreover, the monomer composition of the obtained polymer was BzMI / TBMA / MMA / HEMA / AA (molar ratio) = 6/29/23/18/24.

(Synthesis Example 7)
Synthesis Example 1 except that the amount of monomer prepared for Polymer Solution 7 was CHMI 10 parts, TBMA 35 parts, dicyclopentanyl methacrylate (DCPMA) 19.5 parts, HEMA 20 parts, and AA 15.5 parts. The same operation was performed to obtain a polymer solution 7.
When the obtained polymer solution 7 was analyzed, the weight average molecular weight was 21000, the acid value was 120 mgKOH / g, and the solid content was 35 mass%. Moreover, 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 Polymer solution 8 was obtained in the same manner as in Synthesis Example 1 except that the amount of monomer prepared was 20 parts of PMI, 20 parts of CHMA, 20 parts of TBMA, and 40 parts of HOMS.
When the obtained polymer solution 8 was analyzed, the weight average molecular weight was 11000, the acid value was 98 mgKOH / g, and the solid content was 40% by mass. Moreover, 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 polymer solution 1, 50 parts of colorant composition (Blue), 20 parts of dipentaerythritol hexaacrylate as a polymerizable compound, and Irgacure 907 (manufactured by BASF) as a photopolymerization initiator. 10 parts were mixed, and propylene glycol monomethyl ether acetate (PGMEA) was further added as a diluent 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 obtained curable resin composition (1-1) was evaluated. The results are shown in Table 2.

The color material composition (Blue) was prepared by the following method.
* Preparation of colorant composition (Blue) Dispersion resin solution (resin monomer composition: BzMI / cyclohexyl methacrylate / methyl methacrylate / methacrylic acid = 30/30/30/10 (mass ratio), Mw: 10,000, 8.3 parts by mass of acid value: 65 mg KOH / g, solid content in resin solution: 42%), 2. Dispersant (BIC Chemie Japan, trade name “DISPERBYK-2001”, non-volatile content: 1.3 g) 9 parts by mass and 8.0 parts by mass of pigment (CI Pigment Blue 15: 6) were weighed into a 225 ml container and diluted with PGMEA so that the non-volatile content (solid content concentration) was 20% by mass. To this, 64 g of zirconia beads having a diameter of 1.0 mm was added, and after shaking for 3 hours with a paint shaker, the zirconia beads were removed by decantation to obtain a color material composition (Blue).

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

(Example 6)
In terms of solid content, 45 parts of the polymer solution 1, 20 parts of the above colorant composition (Blue), 25 parts of dipentaerythritol hexaacrylate as a polymerizable compound, and Irgacure 907 (manufactured by BASF) as a photopolymerization initiator 10 parts of was added, 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). Water unevenness of the obtained curable resin composition (1-2) was evaluated. The results are shown in Table 3.

(Examples 7 to 10, Comparative Examples 4 to 6)
Curable resin compositions (2-2) to (8-2) were obtained in the same manner as in Example 6 using polymer solutions 2 to 8 so as to have the composition shown in Table 3. Water unevenness of the obtained curable resin composition was evaluated. The results are shown in Table 3.

The description in Table 1 represents the following.
BzMI: N-benzylmaleimide CHMI: N-cyclohexylmaleimide PMI: N-phenylmaleimide VT: vinyltoluene CHMA: cyclohexyl methacrylate TBMA: t-butyl methacrylate MMA: methyl methacrylate DCPMA: dicyclopentanyl methacrylate HEMA: methacryl Acid 2-hydroxyethyl AA: acrylic acid HOMS: succinic acid mono (2-methacryloyloxyethyl)

From Tables 1-3, the curable resin composition (Examples 1-10) containing the polymer which has a vinyltoluene unit and a succinic acid mono (2-methacryloyloxyethyl) unit as a monomer unit is a vinyltoluene unit. Development time is very short compared with the curable resin composition (Comparative Examples 1-6) containing the polymer which does not have both the succinic acid mono (2-methacryloyloxyethyl) unit, and hardening It was confirmed that the water unevenness of the object was sufficiently suppressed.
Thus, it is clear that the curable resin composition of the present invention has the performance as a binder resin that requires quick developability while maintaining hydrophobicity enough to suppress water unevenness. is there.

(Examples 11-15, Comparative Examples 7-8)
Propylene glycol monomethyl ether acetate (PGMEA) is added to the polymer solutions 1 to 6 and 8 so as to have the composition shown in Table 4, and the curable resin composition (1-3) having a solid content of 35% by mass is added. (6-3) and (8-3) were obtained. About the obtained curable resin composition, heat-resistant coloring property was evaluated. The results are shown in Table 4.

From Table 4, the curable resin composition (Examples 11-15) containing the polymer which has a vinyltoluene unit and a succinic acid mono (2-methacryloyloxyethyl) unit as a monomer unit is a vinyltoluene unit and succinic acid. Compared with the polymer curable resin compositions (Comparative Examples 7 to 8) that do not have both acid mono (2-methacryloyloxyethyl) units, the b ^* value is small, and the heat resistance coloring property is also improved. It was recognized that it was excellent.

Claims (11)

Aromatic vinyl-based monomer unit (A) and a vinyl-based monomer unit (B) having an acid group in the side chain portion and the acid group being at a position 5 atoms or more away from the main chain A curable resin composition comprising a polymer. The curable resin composition according to claim 1, wherein the vinyl monomer unit (B) is 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 unit to be used, and is a number of 1 or more, and n is 0 or 1.) The curable resin composition according to claim 1, wherein the polymer further has an N-substituted maleimide monomer unit (C). The curable resin composition according to claim 3, wherein the N-substituted maleimide monomer unit (C) is an N-phenylmaleimide monomer unit and / or an N-cyclohexylmaleimide monomer unit. object. The polymer further includes a vinyl-based unit containing a —COO ^* R ⁴ (R ⁴ is a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom). It has a monomer unit (D), The curable resin composition in any one of Claims 1-4 characterized by the above-mentioned. In the polymer, the content ratio (A) / (B) of the aromatic vinyl monomer unit (A) and the vinyl monomer unit (B) is 10/60 to 60 / in molar ratio. The curable resin composition according to claim 1, wherein the curable resin composition is 10. The curable resin composition according to any one of claims 1 to 6, wherein the polymer has an acid value of 40 to 180 mgKOH / g. The curable resin composition according to claim 1, further comprising a polymerizable compound. A laminate having a cured product of the curable resin composition according to any one of claims 1 to 8 on a substrate. A color filter comprising a cured product of the curable resin composition according to claim 1 on a substrate. A display device comprising the color filter according to claim 10.