TWI730272B - Polymer, curable resin composition and its use - Google Patents

Abstract

The present invention provides a polymer that can sufficiently suppress yellowing during heating and can be applied to high coloring, and a curable resin composition containing the polymer. The polymer of the present invention is characterized by having: 10-60% by mass of monomer units represented by the following general formula (I), and containing -COO*R ⁴ (R ⁴ is a monovalent organic group, bonded to O * The carbon atoms are tertiary carbon atoms) 5~80% by mass of vinyl monomer units.

Description

Polymer, curable resin composition and its use

The present invention relates to a novel polymer. More specifically, it relates to a color filter and a display device having a polymer excellent in heat-resistant colorability, a curable resin composition containing the polymer, and a cured product of the curable resin composition.

Polymers that can be hardened by heat or active energy rays are used in various applications according to the characteristics of the polymer. Examples of such applications include, for example, various optical components such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, and photoresists used in liquid crystal display devices or solid-state imaging devices, and electrical and electronic equipment. , Further research on copolymers suitable for these purposes.

In the above-mentioned applications, the color filter constitutes the main component of a liquid crystal display device or a solid-state imaging element. Generally speaking, it is composed of a substrate, pixels of at least three primary colors (red (R), green (G), and blue (B)), and The resin black matrix (BM) that separates these, and the protective film provided for covering and protecting the pixels and the resin black matrix and flattening the unevenness.

Generally, when a curable resin composition is used to form the pixels of a color filter, the following steps are used for one color of the pixel, and the same steps are repeated for each color: (1) Coating Step: Coating a curable resin composition on the entire substrate surface; (2) Exposure step: Through a photomask, pattern exposure is performed on the resist film formed by the coating step to harden the exposed part, and then harden Part insoluble; and (3) development, calcination (baking) processing steps: by displaying After the shadow solution removes the unexposed part, the exposed part is further hardened by firing (baking). Considering the application in the purpose of such a color filter, etc., the resin used or the curable resin composition containing the resin requires curability, solvent resistance after curing, adhesion to the substrate, Various physical properties such as heat resistance and transparency.

So far, various kinds of resins with various physical properties have been proposed.

For example, in Patent Document 1, as a polymer with excellent heat resistance, it is proposed to use N-substituted maleimide and/or specific ether dimers, vinyl toluene, and monomers having acid groups as monomers. It is a polymer made by copolymerization of body components.

However, in a resin composition containing a maleimide-derived polymer, since the maleimide-based polymer contains nitrogen atoms, the polymer may be colored yellow to yellowish brown when heated. Problems such as insufficient transparency of the cured film. In contrast to this, a polymer capable of forming a coating film excellent in heat resistance and transparency has been proposed.

For example, in Patent Document 2, as a polymer that can form a coating film excellent in heat resistance and transparency, it is proposed to make a specific monomer as an ether dimer of 2-(hydroxyalkyl) acrylate, a carboxyl group-containing polymer Unsaturated monomers and hydroxy-containing unsaturated monomers are copolymerized as monomer components.

In addition, Patent Document 3 proposes a curable resin composition that can stably exhibit various physical properties such as curability or solvent resistance after curing, adhesion to the substrate, heat resistance, and transparency. The curable resin The composition contains a (meth)acrylate polymer having a tertiary carbon-containing (meth)acrylate monomer unit and a monomer unit having a hydroxyl group, a polymerizable compound, and a photopolymerization initiator.

In addition, as a curable resin composition suitable for color filter applications, for example, Patent Document 4 describes a photosensitive resin composition containing a carboxyl group arranged in a side chain with 7 or more elements separated from the main chain and having a side chain A carboxyl group-containing radical polymerizable copolymer having a radical polymerizable double bond.

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2009-40999

Patent Document 2: Japanese Patent Laid-Open No. 2012-82317

Patent Document 3: Japanese Patent Laid-Open No. 2015-42697

Patent Document 4: Japanese Patent Laid-Open No. 2012-193219

In recent years, the miniaturization, thinning, and energy-saving of optical components, electrical and electronic equipment, etc. have continued to advance. With this, high-quality performance is required for components such as color filters used. However, it is hard to say that such requirements are fully met, and there is still room for improvement. Especially in the use of color filters, as the quality of color liquid crystal display devices and other applications are increased, there is a strong demand for higher brightness and higher contrast of display panels. The development of the It turns yellow and can be applied to highly colored polymers.

The present invention was completed in view of the above-mentioned current situation, and its object is to provide a polymer that can sufficiently suppress yellowing during heating and can be applied to high coloring, and a curable resin composition containing the polymer.

In order to solve the above-mentioned problems, the inventors have conducted various studies on polymers that can be applied to color filters and the like. As a result, they have found that by having at least two specific monomer units in a specific range, an excellent heat-resistant colorability can be obtained Hardened object. In addition, the present inventors found that such a polymer and a curable resin composition containing the polymer are particularly suitable as a polymer and a resin composition for forming components such as color filter applications, and completed the present invention.

In the present invention, "heat-resistant colorability" means that the polymer is not easy to produce yellowing and other discoloration when heated. characteristic.

That is, the present invention is a polymer characterized by having 10-60% by mass of monomer units represented by the following general formula (I), and containing -COO*R ⁴ (R ⁴ is a monovalent organic group, The carbon atom bonded to O* is a tertiary carbon atom) group of vinyl monomer units 5 to 80% by mass.

(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 with a carbon number of 1-12; R ³ represents a divalent organic group ; X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group or a phosphoric acid group; m represents the average number of repeating units of the monomer unit represented by the general formula (I), and is a number greater than 1; n is 0 or 1)

The above-mentioned polymer is preferably a ring structure-containing polymer having a ring structure in the main chain.

The above-mentioned polymer is preferably a polymer further having a hydroxyl group-containing monomer unit.

The above-mentioned polymer is preferably a polymer further having an aromatic vinyl monomer unit.

The above-mentioned polymer preferably has a content of (meth)acrylic acid units of less than 5% by mass.

The above-mentioned polymer preferably has an acid value of 40 to 160 mgKOH/g.

In addition, the present invention is also a curable resin composition characterized by containing the above-mentioned polymer and polymerizable compound.

In addition, the present invention is also a laminated body characterized by having a cured product of the aforementioned polymer or a cured product of the aforementioned curable resin composition on a substrate.

In addition, the present invention is also a color filter characterized by having a cured product of the above-mentioned curable resin composition on a substrate.

Furthermore, the present invention is also a display device characterized by including the above-mentioned color filter.

Since the polymer of the present invention contains the above-mentioned structure, it can provide a cured product excellent in heat-resistant coloration. The polymer of the present invention and the curable resin composition containing the above-mentioned polymer can be applied to various applications such as various optical components, electrical and electronic equipment, etc., and can be particularly applied to filters used in liquid crystal display devices or solid-state imaging devices. Color device.

Hereinafter, the present invention will be described in detail.

Furthermore, a combination of two or more of the preferred aspects of the present invention described below is also a preferred aspect of the present invention.

In addition, in this specification, "(meth)acrylate" means "acrylate and/or methacrylate", and "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid".

1. Polymer

<Form(1)>

The polymer of the present invention is characterized by having: 10-60% by mass of monomer units represented by the following general formula (I), and containing -COO*R ⁴ (R ⁴ is a monovalent organic group, bonded to O *The carbon atoms are tertiary carbon atoms) 5~80% by mass of vinyl monomer units.

(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 with a carbon number of 1-12; R ³ represents a divalent organic group ; X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group or a phosphoric acid group; m represents the average number of repeating units of the monomer unit represented by the general formula (I), and is a number greater than 1; n is 0 or 1)

Since the polymer of the present invention is composed of the above-mentioned constitution, yellowing during heating can be suppressed, that is, a cured product having excellent heat-resistant colorability can be provided.

It is speculated that the reason why the above polymer can provide a cured product with excellent heat resistance and colorability is that when the above polymer is heated, a part of the monomer unit represented by the above general formula (I) is detached to form a hydroxyl group at the terminal. The hydroxyl group captures the free radicals existing in the reaction system, thereby reducing the influence of the free radicals; and when the polymer is heated, the above-mentioned containing -COO*R ⁴ (R ⁴ is a monovalent organic group, which is bonded to The carbon atom of O* is a tertiary carbon atom). The tertiary carbon atom of the vinyl monomer unit is separated to form an acid group, and the acid group is cross-linked with the above-mentioned hydroxyl group, thereby forming a strong film (hardened product) .

In addition, the polymer of the present invention is excellent in curability, hardness of the cured product, solvent resistance, heat resistance, transparency, and adhesion to the substrate. Furthermore, when the above-mentioned polymer is applied to a resin composition containing a colored material, the concentration of the colored material in the obtained cured product can be increased, so that further thinning can be achieved, and the above-mentioned resin composition can be applied In the case of color filter use, it can further achieve high color purity or high light shielding rate of the black matrix.

It is speculated that the reasons why the above-mentioned polymers can improve the hardenability or the characteristics of the hardened product are: As described above, when the polymer is heated, the monomer units constituting the polymer or the hydroxyl groups generated therefrom are cross-linked with acid groups; and the hydroxyl groups capture free radicals existing in the reaction system. Furthermore, it is inferred that the reason for increasing the concentration of the colored material in the cured product is that by forming a cross-linked structure as described above, the resin greatly shrinks or evaporates, and the amount of resin in the cured product is relatively reduced.

The monomer units constituting the polymer of the present invention will be described in detail. Furthermore, in the present invention, "monomer unit" means a structural unit derived from a monomer.

<Monomer unit (A) represented by general formula (I)>

The polymer of the present invention has a monomer unit represented by the above-mentioned general formula (I) (hereinafter also referred to as "monomer unit (A)").

In the above general formula (I), R ¹ represents a hydrogen atom or a methyl group. Furthermore, it is preferable that it is a methyl group in terms of heat resistance or water spot suppression effect is good.

Furthermore, in the present invention, "moisture" means that after the hardened product is brought into contact with a water-soluble solution such as a developer and the water-soluble solution is removed, the part that has been in contact with it will become cloudy and other discoloration, forming a shade on the hardened product Uneven.

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 above-mentioned divalent linear, branched or cyclic saturated or unsaturated hydrocarbon groups include alkylene, arylene, and divalent hydrocarbon groups having an alicyclic structure. Among them, preferred are Alkylene. Examples of the alicyclic structure include a cyclohexane skeleton, an adamantane skeleton, and a norbornene skeleton. In addition, these may have a substituent.

Examples of R ² preferably include alkylene groups such as methylene, ethylene, propylene, butylene, heptyl, octyl, and dodecylene; Arylene groups such as phenyl, phenylene, naphthylene, etc.; these groups are substituted by functional groups such as hydroxyl groups, etc.

Among them, as R ² , an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 1 to 5 carbon atoms is more preferred.

R ³ represents a divalent organic group. As the above-mentioned divalent organic group, a chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having a carbon number of 1 to 10 is preferably exemplified, and a divalent hydrocarbon group having a carbon number of 1 to 5 is more preferable. Chain or branched saturated hydrocarbon group or unsaturated hydrocarbon group. The above-mentioned organic group may have a substituent.

Examples of R ³ include alkylene groups such as methylene, ethylene, propylene, trimethylene, butylene, ethylethylene, hexylene, octylene, and dodecylene; Ethylene, propenylene, isopropenylene, butenylene, pentenylene, hexenylene and other alkenylene groups; cyclopropylene, cyclobutylene, cyclopentenyl, cyclohexylene, etc. Cycloalkylenes such as ,bornanyl and adamantyl; arylalkylenes such as phenylene, phenylene, naphthyl, and stilbene; alkyl ether groups such as diethyl ether and propyl ether; containing this Equal groups and -O-, -S-, -SO-, -SO ₂ -and other bond groups.

Among them, in terms of further excellent heat-resistant colorability, R ^{3 is} preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 5 carbon atoms base.

X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group, or a phosphoric acid group. Among them, in terms of further excellent heat-resistant colorability, X is preferably a carboxyl group.

m represents the average number of repeating units of the monomer unit represented by the general formula (I), and is a number of 1 or more.

n is 0 or 1, preferably 1.

As the monomer providing the above-mentioned monomer unit (A), preferably, β-carboxyethyl (meth)acrylate, mono(2-propenoxyethyl) succinate, mono(2-methyl succinate) Unsaturated monocarboxylic acids with chain extension between unsaturated groups and carboxyl groups such as oxypropenyloxyethyl) ester, etc., more preferably β-carboxyethyl (meth)acrylate, mono(2-propene succinate) Succinic acid mono(2-methacryloxyethyl) ester, succinic acid mono(2-methacryloxyethyl) ester, more preferably succinic acid mono(2-methacryloxyethyl) ester is mentioned. By polymerizing a monomer component containing such a compound, a polymer having the above-mentioned monomer unit (A) can be obtained.

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

The content of the monomer unit (A) in the polymer is 10-60% by mass relative to 100% by mass of all monomer units of the polymer. The content of the monomer unit (A) is more excellent in heat-resistant coloration, relative to 100% by mass of all monomer units of the polymer, preferably 15% by mass or more, more preferably 20% by mass or more Moreover, it is preferably 50% by mass or less.

Specifically, the content of the monomer unit (A) is preferably 20-60% by mass, more preferably 20-50% by mass relative to 100% by mass of all monomer units of the polymer.

Also, from the viewpoint of the water spot suppression effect, the content of the monomer unit (A) relative to 100% by mass of all monomer units of the polymer, preferably 15% by mass or more, more preferably 20% by mass or more .

<Containing -COO*R ⁴ -group vinyl monomer unit (B)>

The polymer of the present invention further has a ^{vinyl monomer unit containing -COO*R 4} (R ⁴ represents a monovalent organic group, and the carbon atom bonded to O* is a tertiary carbon atom) group (hereinafter also referred to as "Vinyl monomer unit (B)").

To the vinyl-based monomer unit (B) is, -COO * R ⁴ R ⁴ represents a group of the monovalent organic group bonded to the carbon atom O * three carbon atoms. The tertiary carbon atom means that the other carbon atoms bonded to the carbon atom are 3 carbon atoms.

As the above-mentioned monovalent organic group, preferably, a chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 91 carbon atoms is monovalent. The above-mentioned organic group may have a substituent.

The carbon number of R ⁴ is more preferably 1 to 50 carbons, further preferably 1 to 35 carbons, and particularly preferably 1 to 20 carbons.

R ^{4 is} preferably an organic group having the same valence as A in the following formula (a).

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

The polymer having the above-mentioned tertiary carbon-containing (meth)acrylate-based monomer unit can be obtained by polymerizing a monomer component containing a tertiary carbon-containing (meth)acrylate-based monomer.

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

The tertiary carbon-containing (meth)acrylate monomer is preferably a compound having one polymerizable carbon-carbon double bond in the molecule, that is, having one (meth)acrylic acid group (CH ₂ = The compound of C(R ⁵ )-C(=O)-), for example, is preferably a compound represented by the following general formula (a); CH ₂ =C(R ⁵ )-C(=O)-OA (a )

(In the formula, R ⁵ represents a hydrogen atom or a methyl group; A represents a monovalent organic group containing a structure having tertiary carbon atoms on the oxygen atom side).

In the above general formula (a), the monovalent organic group represented by A can be represented by -C(R ⁶ )(R ⁷ )(R ⁸ ), for example. In this case, R ⁶ , R ⁷ and R ^{8 are the} same or different, and are preferably a hydrocarbon group with 1 to 30 carbon atoms. The above-mentioned hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, may have a cyclic structure, or may have a substituent. In addition, R ⁶ , R ⁷ , and R ⁸ may be connected to each other at the terminal portion to form a ring structure.

Regarding the carbon number of the organic group represented by A, it is adjacent to _{the oxygen atom of the (meth)acryloyl group (CH 2} =C(R ⁵ )-C(=O)-) and the one in the adjacent A In terms of the easy volatilization of the new compound formed by cutting the OC bond between the tertiary carbon atoms, it is preferably 12 or less, and more preferably 9 or less. In addition, the organic group represented by A may have a branched structure.

Here, in the above-mentioned tertiary carbon-containing (meth)acrylate monomer, the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth)acrylic acid group is preferably one of the adjacent carbon atoms At least one is bonded to a hydrogen atom. For example, the (meth)acrylate monomer containing tertiary carbon is a compound represented by the general formula (a) and A is a group represented by -C(R ⁶ )(R ⁷ )(R ⁸ ) In the case, it is suitable ^{that at least one of R 6} , R ⁷ and R ⁸ contains a carbon atom with more than one hydrogen atom and the carbon atom is bonded to a tertiary carbon atom. In this form, by heating, the OC bond between the oxygen atom adjacent to the (meth)acrylic acid group and the tertiary carbon atom adjacent to it is cut to produce (meth)acrylic acid, and at the same time , The tertiary carbon atom and its adjacent carbon atom form a double bond (C=C), thereby generating new compounds more stably.

The new compound thus formed is preferably a volatile one. In this case, the new compound volatilizes from the cured product, thereby reducing the thickness of the cured product (cured film). For example, when using a curable resin composition containing the above-mentioned polymer and a colored material, the film thickness of the cured product (cured film) is reduced. The concentration of colored materials increases after heating. Therefore, it is possible to achieve further thinning and to achieve higher color purity or higher light-shielding rate of the black matrix. In consideration of this aspect, the above-mentioned R ⁶ , R ⁷ and R ^{8 are the} same or different, preferably a saturated hydrocarbon group with 1 to 15 carbons, more preferably a saturated hydrocarbon group with 1 to 10 carbons, and more preferably a carbon number Saturated hydrocarbon groups of 1 to 5, and saturated hydrocarbon groups of 1 to 3 carbons are particularly preferred.

The above-mentioned tertiary carbon-containing (meth)acrylate monomer is preferably tertiary butyl (meth)acrylate or tertiary amyl (meth)acrylate.

From the viewpoint of developability or water spot suppression effect, the tertiary carbon-containing (meth)acrylate monomer is preferably a tertiary carbon-containing methacrylate monomer, more preferably methacrylic acid Tertiary butyl ester or tertiary amyl methacrylate.

The said polymer may have only 1 type of the said thing as the 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 80% by mass relative to 100% by mass of all monomer units of the polymer. The content of the vinyl-based monomer unit (B) relative to 100% by mass of all monomer units of the polymer is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more In addition, it is preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less.

In terms of further excellent heat-resistant colorability, the content of the above-mentioned vinyl monomer unit (B) relative to 100% by mass of all monomer units, more preferably 10 to 70% by mass, and still more preferably 20 to 60 quality%.

In addition, in terms of excellent developability and water spot suppression effect, the content of the vinyl-based monomer unit (B) is preferably 5 to 70 mass% with respect to 100% by mass of all monomer units of the polymer. % Is more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 65% by mass or less, and still more preferably 60% by mass or less.

<Monomer unit with ring structure in the main chain (C)>

The polymer of the present invention is preferably a ring structure-containing polymer having a ring structure in the main chain. By further containing a ring structure in the main chain, the heat resistance of the polymer can be further improved.

As said ring structure, an imide ring, a tetrahydrofuran ring, a lactone ring, etc. are mentioned. In order to have these ring structures, the above-mentioned ring structure-containing polymer preferably contains a monomer unit having a ring structure in the main chain (hereinafter also referred to as "monomer unit (C)").

As the monomer providing the above monomer unit (C), for example, a monomer having a double bond-containing ring structure in the molecule or a monomer that undergoes cyclization polymerization to form a polymer having a ring structure in the main chain, and after polymerization, it forms a ring The structure of the monomer, etc. Among them, from the viewpoints of good heat resistance, hardness, and dispersibility of colored materials, it is preferably selected from the group consisting of N-substituted maleimide monomers, 2,2'-(oxydimethylene) At least one monomer from the group consisting of dialkyl diacrylate monomers and α-(unsaturated alkoxyalkyl) acrylate monomers, in terms of further excellent heat-resistant coloration properties , More preferably at least one selected from the group consisting of N-substituted maleimide-based monomers and 2,2'-(oxydimethylene) dialkyl diacrylate-based monomers monomer. Moreover, in terms of enhancing the effect of suppressing water spots, an N-substituted maleimide-based monomer is preferable.

Examples of the above-mentioned N-substituted maleimide-based monomers include N-cyclohexyl maleimide, N-phenyl maleimide, and N-methyl maleimide Diimide, N-ethyl maleimide, N-isopropyl maleimide, N-tertiary butyl maleimide, n-dodecyl maleimide Diamidimine, N-benzyl maleimide, N-naphthyl maleimide, etc., one kind or two or more kinds of these can be used. Among them, in terms of transparency, it is more N-phenylmaleimide, N-benzyl maleimide, N-cyclohexyl maleimide are preferred, and N-cyclohexyl maleimide is particularly preferred. Imine. In addition, in terms of improving the heat-resistant coloring resistance and the effect of suppressing water spots, N-phenylmaleimide and/or N-cyclohexylmaleimide are more preferred, and more preferred are N-phenylmaleimide and/or N-cyclohexylmaleimide. N-phenylmaleimide.

Examples of the N-benzyl maleimide include: benzyl maleimide; p-methylbenzyl maleimide, p-butylbenzyl maleimide Alkyl-substituted benzyl maleimide such as imines; phenolic hydroxy-substituted benzyl maleimide such as p-hydroxybenzyl maleimide; o-chlorobenzyl maleimide Halogen substituted benzyl maleimide, such as dichlorobenzyl maleimide, o-dichlorobenzyl maleimide, and p-dichlorobenzyl maleimide.

Examples of the above-mentioned 2,2'-(oxydimethylene) dialkyl diacrylate monomer include: 2,2'-[oxybis(methylene)]bis-2-acrylic acid diacrylate Methyl ester, 2,2'-[oxybis(methylene)]bis-2-acrylic acid diethyl ester, 2,2'-[oxybis(methylene)]bis-2-acrylic acid di(normal Propyl) ester, 2,2'-[oxybis(methylene)]bis-2-acrylate di(isopropyl) ester, 2,2'-[oxybis(methylene)]bis- 2-Di(n-butyl) acrylate, 2,2'-[oxybis(methylene)]bis-2-di(isobutyl) acrylate, 2,2'-[oxybis(methylene) (Methyl)]bis(tert-butyl)bis-2-acrylate, 2,2'-[oxybis(methylene)]bis(tert-pentyl)bis-2-acrylate, 2,2 '-[Oxybis(methylene)]bis-2-acrylate bis(stearyl)ester, 2,2'-[oxybis(methylene)]bis-2-acrylate bis(lauryl) Esters, 2,2'-[oxybis(methylene)]bis-2-acrylate bis(2-ethylhexyl) ester, etc. Among these, 2,2'-[oxybis(methylene)]bis-2-acrylate dimethyl is more preferable from the viewpoints of transparency, dispersibility, industrial availability, and the like.

As said α-(unsaturated alkoxyalkyl) acrylate-based monomers, for example, α-(allyloxymeth)acrylate-based monomers can be cited.

As specific examples of the above-mentioned α-(allyloxymeth)acrylate monomers, for example, α-allyloxymethacrylic acid; α-allyloxymethylmethacrylate, α-ene Propoxy methacrylic acid Ethyl, α-allyloxy n-propyl methacrylate, α-allyloxy isopropyl methacrylate, α-allyloxy n-butyl methacrylate, α-allyloxy methyl Second butyl acrylate, third butyl α-allyloxy methacrylate, α-allyloxy n-pentyl methacrylate, α-allyloxy second pentyl methacrylate, α-ene Third amyl propoxy methacrylate, α-allyloxy n-hexyl methacrylate, α-allyloxy second hexyl methacrylate, α-allyloxy n-heptyl methacrylate, α-allyloxy n-octyl methacrylate, α-allyloxy methacrylate second octyl, α-allyloxy methacrylate third octyl, α-allyloxy methacrylate 2-Ethylhexyl ester, α-allyloxy heptyl methacrylate, α-allyloxy nonyl methacrylate, α-allyloxy decyl methacrylate, α-allyloxy methyl Undecyl acrylate, α-allyloxy lauryl methacrylate, α-allyloxy tridecyl methacrylate, α-allyloxy myristyl methacrylate, α- Allyloxy pentadecyl methacrylate, α-allyloxy cetyl methacrylate, α-allyloxy heptadecyl methacrylate, α-allyloxy methacrylate Stearyl ester, nonadecyl α-allyloxy methacrylate, eicosyl α-allyloxy methacrylate, behenyl α-allyloxy methacrylate, α-ene (Α-allyloxy meth) alkyl acrylate monomers such as propoxy methacrylate and other alkyl esters; α-allyloxy methoxyethyl methacrylate, α-allyloxy methyl Methoxy ethoxy ethyl acrylate, α-allyloxy methoxy ethoxy ethoxy ethyl methacrylate, α-allyloxy 3-methoxy butyl methacrylate, α -Allyloxy ethoxy ethyl methacrylate, α-allyloxy ethoxy ethoxy ethyl methacrylate, α-allyloxy phenoxy ethyl methacrylate, α-ene (Α-allyloxymethyl) alkoxyalkyl acrylate monomers such as propoxy phenoxy ethoxy ethyl methacrylate; α-allyloxy hydroxyethyl methacrylate, α -Allyloxy hydroxypropyl methacrylate, α-allyloxy hydroxybutyl methacrylate, α-allyloxy fluoroethyl methacrylate, α-allyloxy difluoroethyl methacrylate Ester, α-allyloxy chloroethyl methacrylate, α-allyloxy dichloroethyl methacrylate, α-allyloxy bromoethyl methacrylate, α-allyloxymethyl Dibromoethyl acrylate, α-allyloxy vinyl methacrylate, α-allyloxy allyl methacrylate, α- Allyloxy methallyl methacrylate, α-allyloxy crotonyl methacrylate, α-allyloxy propylene methacrylate, α-allyloxy cyclopentyl methacrylate , Α-allyloxy cyclohexyl methacrylate, α-allyloxy methacrylate 4-methylcyclohexyl, α-allyloxy methacrylate 4-tert-butylcyclohexyl, α-allyloxy tricyclodecyl methacrylate, α-allyloxy isobornyl methacrylate, α-allyloxy adamantyl methacrylate, α-allyloxy methacrylate Dicyclopentadiene ester, α-allyloxy phenyl methacrylate, α-allyloxy methyl phenyl methacrylate, α-allyloxy dimethyl phenyl methacrylate, α- Allyloxy trimethylphenyl methacrylate, α-allyloxy methacrylate 4-tert-butylphenyl, α-allyloxy benzyl methacrylate, α-allyloxymethyl Diphenyl methyl acrylate, α-allyloxy diphenyl ethyl methacrylate, α-allyloxy triphenyl methyl methacrylate, α-allyloxy cinnamyl methacrylate, α-allyloxy naphthyl methacrylate, α-allyloxy anthracene methacrylate, etc. Among them, the alkyl (α-allyloxymeth)acrylate monomer is suitable. As the above-mentioned (α-allyloxy meth) acrylate alkyl ester monomer, α-allyloxy methacrylic acid is particularly preferred from the viewpoints of transparency, dispersibility, and industrial availability. Methyl ester (also known as methyl (α-allyloxymeth)acrylate).

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

As a monomer providing the above-mentioned monomer unit (C), an alkyl 2-(hydroxyalkyl)acrylate can be preferably mentioned. Alkyl 2-(hydroxyalkyl)acrylate can react with (meth)acrylic acid to form a lactone ring structure in the main chain. As said lactone ring structure, the ring structure represented by the following general formula (II) is mentioned, for example.

In the above general formula (II), R ⁹ represents an alkyl group having 1 to 20 carbon atoms, R ¹⁰ represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and R ¹¹ represents a hydrogen atom or a methyl group. n is 1 or 2.

R ⁹ and R ¹⁰ are respectively the same as ^{R 9} and R ¹⁰ in the following general formula (III).

As said 2-(hydroxyalkyl) acrylate alkyl ester, the compound represented by the following general formula (III) is mentioned.

(In the general formula (III), R ⁹ represents an alkyl group with 1 to 20 carbons, and R ¹⁰ represents a hydrogen atom or an organic residue with 1 to 20 carbons; n is 1 or 2)

In the above general formula (III), R ⁹ represents an alkyl group having 1 to 20 carbon atoms. The above-mentioned alkyl group may be linear or branched.

In terms of monomer solubility, ^{the carbon number of R 9} is preferably 1-10, more preferably 1-6.

Examples of R ⁹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, pentyl, hexyl, octyl, or 2-ethyl Hexyl etc. Preferably it is methyl.

In the above general formula (III), R ¹⁰ is a hydrogen atom or an organic residue with 1 to 20 carbon atoms.

Examples of the above-mentioned organic residues having 1 to 20 carbon atoms include: alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, and propyl groups; unsaturated aliphatic groups having 1 to 20 carbon atoms such as vinyl and propenyl groups. Hydrocarbyl group; Aromatic hydrocarbon groups with 1 to 20 carbon atoms such as phenyl and naphthyl groups; In the alkyl group, the unsaturated aliphatic hydrocarbon group, and the aromatic hydrocarbon group, one or more of the hydrogen atoms is substituted with a hydroxyl group, a carboxyl group, and an ether A group derived from at least one of a group and an ester group, etc. Among them, R ¹⁰ is preferably a hydrogen atom from the viewpoint of the hydrophilicity of the lactone ring.

Examples of the aforementioned 2-(hydroxyalkyl)alkyl acrylate include 2-(1-hydroxyalkyl)alkyl acrylate and 2-(2-hydroxyalkyl)alkyl acrylate. Specifically, for example, Enumeration 2 -(1-hydroxymethyl) methyl acrylate, 2-(1-hydroxymethyl) ethyl acrylate, 2-(1-hydroxymethyl) isopropyl acrylate, 2-(1-hydroxymethyl) acrylate Butyl ester, tert-butyl 2-(1-hydroxymethyl)acrylate, 2-ethylhexyl 2-(1-hydroxymethyl)acrylate, etc. Among them, methyl 2-(1-hydroxymeth)acrylate and ethyl 2-(1-hydroxymeth)acrylate are preferred. These may be used individually by 1 type, and may be used in combination of 2 or more types.

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

In terms of further improvement in heat-resistant coloration, the content of the monomer unit (C) in the polymer is 100% by mass relative to all monomer units of the polymer, preferably 2% by mass or more, more preferably It is 5% by mass or more, more preferably 10% by mass or more, particularly preferably 15% by mass or more, more preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less, It is particularly preferably 50% by mass or less, and particularly preferably 40% by mass or less.

Specifically, the content of the monomer unit (C) relative to 100% by mass of all monomer units of the polymer is preferably 2-60% by mass, more preferably 5-50% by mass, and still more preferably 5 ~40% by mass.

In terms of improving the developability or water spot suppression effect of the above-mentioned polymer, the content of the above-mentioned monomer unit (C) relative to 100% by mass of all monomer units of the above-mentioned polymer, preferably 10 to 70% by mass , More preferably 15-60% by mass.

<Hydroxy-containing monomer unit (D)>

The polymer of the present invention may further have a hydroxyl-containing monomer unit (hereinafter also referred to as "monomer unit (D)"). By further containing a hydroxyl group-containing monomer unit, the heat-resistant colorability can be further improved. It is presumed that the reason is that the hydroxyl group captures the free radicals present in the reaction system to reduce the influence of the free radicals; and reacts with the acid group formed by the detachment of the tertiary carbon atoms of the vinyl monomer unit (B). A cross-linked structure is formed to form a strong film (hardened product).

The above-mentioned hydroxyl-containing monomer is not particularly limited as long as it is a compound having a hydroxyl group and a polymerizable double bond in the molecule. For example, 2-hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferably mentioned. 2-hydroxypropyl ester, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 2,3-hydroxypropyl (meth)acrylate, more preferably 2-hydroxyethyl (meth)acrylate. By polymerizing such a monomer component containing a hydroxyl-containing monomer, a polymer having the above-mentioned monomer unit (D) can be obtained.

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

In terms of further improvement of the heat-resistant colorability, the content of the monomer unit (D) in the polymer relative to 100% by mass of all monomer units of the polymer, preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, particularly preferably 30% by mass or less, The best content is 20% by mass or less.

Specifically, the content of the monomer unit (D) is preferably 1 to 30% by mass, more preferably 5 to 20% by mass relative to 100% by mass of all monomer units of the polymer.

In terms of improving the developability or water spot suppression effect of the above-mentioned polymer, the content of the above-mentioned monomer unit (D) relative to 100% by mass of all monomer units of the above-mentioned polymer, preferably 1-60% by mass , More preferably 5 to 55% by mass, and still more preferably 10 to 50% by mass.

<Aromatic vinyl monomer unit (E)>

The polymer of the present invention may further have an aromatic vinyl monomer unit (hereinafter also referred to as "monomer unit (E)"). By further having an aromatic vinyl-based monomer unit, in addition to improving the heat-resistant colorability, the developability and the effect of suppressing water spots can be improved.

The above-mentioned aromatic vinyl monomer unit is a structural unit derived from an aromatic vinyl monomer, preferably a structural unit derived from a monomer having an aromatic group and a vinyl group.

As said aromatic group, the group containing a benzene ring, a naphthalene ring, etc. are mentioned, Especially, the group containing a benzene ring is preferable.

The above-mentioned 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 above-mentioned aromatic vinyl monomer include styrene, vinyl toluene, α-methylstyrene, xylene, methoxystyrene, and ethoxystyrene. Among them, In terms of improving thermal decomposition resistance, styrene and vinyl toluene are preferred, and in terms of high dissolution rate in organic solvents or alkaline solutions, vinyl toluene is more preferred. By polymerizing such an aromatic vinyl-based monomer-containing monomer component, a polymer having the above-mentioned monomer unit (E) can be obtained.

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

In terms of the further improvement of the heat-resistant colorability of the polymer, the content of the monomer unit (E) in the polymer relative to 100% by mass of all monomer units, preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, particularly preferably 10% by mass or more, most preferably 15% by mass or more, and more preferably 80% by mass or less, It is more preferably 70% by mass or less, still more preferably 60% by mass or less, particularly preferably 50% by mass or less, and most preferably 40% by mass or less.

Specifically, the content of the monomer unit (E) is preferably 1-60% by mass, more preferably 2-50% by mass, and still more preferably 3-40% by mass relative to 100% by mass of all monomer units. .

In terms of improving the developability or water spot suppression effect of the above-mentioned polymer, the content of the above-mentioned monomer unit (E) relative to 100% by mass of all monomer units, preferably 5 to 80% by mass, more preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

<Other monomer units (F)>

In addition to the aforementioned monomer units, the polymer of the present invention may optionally contain other polymerizable monomer units (hereinafter also referred to as "monomer units (F)"). Examples of the above-mentioned other polymerizable monomer units include (meth)acrylate-based monomers derived from acid group-containing monomers other than the monomers that provide the above-mentioned vinyl-based monomer unit (B), and other copolymerizable monomers. The monomer and other monomer units.

Examples of the acid group-containing monomer include compounds having an acid group and a polymerizable double bond in the molecule other than the monomer unit (A).

Examples of the acid group include: a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, a sulfonic acid group, etc., and a functional group that neutralizes with a base. It may have only one of these, or two. More than species. Among them, a carboxyl group or a carboxylic anhydride group is preferred, and a carboxyl group is more preferred.

As said polymerizable double bond, a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group etc. are mentioned, for example.

Specific examples of the acid group-containing monomer include: (meth)acrylic acid, crotonic acid, cinnamic acid, vinyl benzoic acid, and other unsaturated monocarboxylic acids; maleic acid, fumaric acid, etc. Unsaturated polycarboxylic acids such as acid, itaconic acid, citraconic acid, and meconic acid; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; Lightester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.), etc. containing phosphoric acid Unsaturated compounds and so on. Among these, from the viewpoints of versatility and availability, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) are suitably used. In terms of reactivity, suppression of water spots, heat-resistant coloration, etc., unsaturated monocarboxylic acids are more preferable, and (meth)acrylic acid (that is, acrylic acid and/or methacrylic acid) are more preferable.

Examples of (meth)acrylate monomers other than the monomer providing the above-mentioned vinyl monomer unit (B) include: methyl (meth)acrylate, ethyl (meth)acrylate, (former) Base) n-propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, n-pentyl (meth)acrylate, first (meth)acrylate Dipentyl ester, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, (meth)acrylate Base) octyl acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentane (meth)acrylate Ester, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylamine (meth)acrylate Ethyl ester, 1,4-dioxaspiro[4,5]dec-2- methacrylate, (meth)acryloyl mopholin, 4-(meth)acryloyloxymethyl- 2-Methyl-2-ethyl-1,3-dioxolane (dioxolane), 4-(meth)propenyloxymethyl-2-methyl-2-isobutyl-1, 3-Dioxolane, 4-(meth)propenyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)propene Acetyloxymethyl-2,2-dimethyl-1,3-dioxolane and the like.

Examples of the above-mentioned other copolymerizable monomers include one or two or more of the following compounds.

(Meth)acrylamides such as N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, etc.; polystyrene, poly(methyl)acrylate, Polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactone are equivalent to macromonomers with (meth)acrylic acid groups at the single end of the polymer molecular chain; 1, Conjugated dienes such as 3-butadiene, isoprene, and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; methyl vinyl ether, Ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxy Vinyl ethers such as ethyl vinyl ether, methoxy ethoxy ethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, etc.; N-vinyl N-vinyl compounds such as pyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorphine, N-vinylacetamide, etc.; (meth)acrylic isocyanate Unsaturated isocyanates such as ethyl ester and allyl isocyanate.

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

When the above-mentioned polymer has the above-mentioned monomer unit (F), the content of the above-mentioned monomer unit (F) is 100% by mass relative to all monomer units of the above-mentioned polymer, preferably 1% by mass or less Above, it is more preferably 2% by mass or more, still more preferably 3% by mass or more, particularly preferably 5% by mass or more, most preferably 10% by mass or more, more preferably 60% by mass or less, more preferably 55% by mass % Or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

In terms of further improving the heat-resistant coloring resistance of the polymer, the content of the monomer unit (F) relative to 100% by mass of all monomer units of the polymer, preferably 1-60% by mass, more preferably It is 2-50 mass %, More preferably, it is 3-40 mass %.

In terms of improving the developability or water spot suppression effect of the polymer, the content of the monomer unit (F) relative to 100% by mass of all monomer units of the polymer, preferably 1-60 mass %, more preferably 5 to 55% by mass, and still more preferably 10 to 50% by mass.

Regarding the above polymer, the content of the acid group-containing monomer unit (preferably (meth)acrylic acid unit) relative to 100% by mass of all monomer units of the above polymer, preferably less than 5% by mass, more preferably It is less than 3% by mass, and more preferably less than 1% by mass. If the content of the acid group-containing monomer unit is less than 5% by mass, a cured product with even more excellent heat-resistant colorability can be obtained.

The acid value of the polymer of the present invention is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 60 mgKOH/g or more, more preferably 180 mgKOH/g or less, more preferably 170 mgKOH/g or less It is more preferably 160 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less.

From the standpoint of heat-resistant coloration, the acid value of the polymer is preferably 40~180mgKOH/g, more preferably 40~160mgKOH/g, still more preferably 50~150mgKOH/g, and particularly preferably 60~140mgKOH/g g.

From the viewpoint of developability and water spot suppression, 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 above acid value is the value measured by neutralization titration using potassium hydroxide (KOH) solution.

The weight average molecular weight of the polymer of the present invention is not particularly limited, preferably 2000 Above, more preferably 3000 or more, still more preferably 4000 or more, still more preferably 5000 or more, particularly preferably 6000 or more, most preferably 7000 or more, more preferably 1000000 or less, more preferably 80,000 or less, and more It is preferably less than 50,000, particularly preferably less than 40,000, and most preferably less than 35,000.

From the viewpoint of heat-resistant coloration, the weight average molecular weight of the polymer is preferably 2,000 to 1,000,000, more preferably 3,000 to 80,000, and still more preferably 4,000 to 50,000.

From the viewpoint of developability and water spot suppression, the weight average molecular weight of the above-mentioned polymer is preferably 5,000 to 50,000, more preferably 6,000 to 40,000, and still more preferably 7,000 to 35,000.

The weight average molecular weight of the above polymer is a value measured by gel permeation chromatography (GPC) using the method described in the examples.

The polymer is preferably prepared by coating a resin composition containing the polymer on a glass substrate to form a laminated body with a coating film, and drying the laminated body at 100°C for 3 minutes, followed by heat treatment at 250°C for 3 hours In this case, the b* value of the coating film side surface of the above-mentioned laminate is 6 or less calculated in accordance with JIS Z 8729. The above-mentioned b* value is standardized by CIE. In Japan, it is based on the L*a*b* color system adopted by JIS Z 8729 to express the value of chromaticity.

The above-mentioned b* value is more preferably 5 or less, still more preferably 4 or less, still more preferably 1.5 or less, particularly preferably 1.0 or less, and most preferably 0.5 or less.

The measurement of the above-mentioned b* value is performed using a laminate in which a resin composition containing the above-mentioned polymer is coated on a glass substrate to form a coating film.

Specifically, the above-mentioned resin composition was coated on a glass substrate in a coating amount (in terms of solid content) in ^{the range of 0.4 to 1.2 mg/cm 2} , and dried at 100° C. for 3 minutes to obtain a formation on the glass substrate. A laminate having a coating film of the above-mentioned resin composition. Then, the obtained laminate was further heat-treated at 250°C for 3 hours, and then cooled to normal temperature, and the b* value of the coating film side surface was measured using a color difference meter. The above-mentioned resin composition is measured using at least two laminates, and an approximate straight line between the coating amount (x) and the b* value (y) is prepared as a calibration curve based on the results. Using the above calibration curve, the b* value when the coating amount is 0.6 mg/cm ² is obtained, and this is set as the above b* value in the present invention.

As the glass substrate, for example, soda lime glass AS-2K (manufactured by Toshin Riko Co., Ltd.) is preferably used.

The said resin composition is prepared by adding antioxidant Irganox 1010 (manufactured by BASF Corporation) to the polymer solution obtained by the manufacture of the said polymer so that it may become 0.5 mass% with respect to 100 mass% of resin solid content.

As the color difference meter, for example, ZE6000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) is preferably used.

<Form (2) and (3)>

Moreover, as another form of the preferable polymer which is excellent in heat-resistant colorability, the following forms (2) and (3) are mentioned. In particular, the aspect (3) can provide a cured product having excellent developability and suppressed water spots in addition to being excellent in heat-resistant colorability. In addition, the polymers of these forms (2) and (3) are also one of the present invention.

Form (2):

A cyclic structure-containing polymer whose main chain has a cyclic structure, and the above-mentioned cyclic structure-containing polymer has a monomer unit represented by the following general formula (I), and contains -COO*R ⁴ (R ⁴ represents a monovalent The organic groups, the carbon atoms bonded to O* are tertiary carbon atoms) vinyl monomer units and hydroxyl-containing monomer units.

(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 with a carbon number of 1-12; R ³ represents a divalent organic group ; X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group or a phosphoric acid group; m represents the average number of repeating units of the monomer unit represented by the general formula (I), and is a number greater than 1; n is 0 or 1)

Form (3):

A polymer having an aromatic vinyl monomer unit and a vinyl monomer unit (X) in which the side chain part has an acid group and the acid group is located at a position separated from the main chain by 5 atoms or more.

It is preferable that the "cyclic structure-containing polymer having a ring structure in the main chain" in the form (2) has the same monomer unit as the monomer unit (C) of the above form (1), which is represented by the general formula (I) "The monomer unit" is the same as the monomer unit (A) of the above form (1), "Contains -COO*R ⁴ (R ⁴ represents a monovalent organic group, and the carbon atom bonded to O* is tertiary The vinyl monomer unit of the carbon atom) group is the same as the vinyl monomer unit (B) of the above-mentioned form (1), and the “hydroxyl-containing monomer unit” is the same as the monomer unit of the above-mentioned form (1) (D) The same ones.

It is speculated that the reason why a cured product with excellent heat-resistant colorability can be provided in the form (2) is that when the ring-containing structure polymer is heated, a part of the monomer unit represented by the general formula (I) is detached to form a hydroxyl group. The hydroxyl group and the hydroxyl group of the above-mentioned hydroxyl-containing monomer unit capture the free radicals present in the reaction system to reduce the influence of the free radicals; and when the above-mentioned ring-containing polymer is heated, the above-mentioned -COO*R ⁴ (R ⁴ Represents a monovalent organic group, the carbon atom bonded to O* is a tertiary carbon atom) The tertiary carbon atom of the vinyl monomer unit is separated to form an acid group, and the acid group is cross-linked with the above-mentioned hydroxyl group, This forms a firm film (hardened product).

The polymer of the aspect (2) may further have arbitrary monomer units, and examples of the above-mentioned arbitrary monomer units include the monomer units described in the aspect (1). The content of each monomer unit is preferably the same as the aspect (1).

In addition, the acid value, weight average molecular weight, and b* value of the polymer of the form (2) are preferably the same as those of the polymer of the above-mentioned form (1).

The "aromatic vinyl monomer unit" in the form (3) is preferably the same as the above form The monomer units (E) of (1) are the same.

It is presumed that the reason why a cured product with suppressed water spots can be provided in the form (3) is that the above-mentioned polymer has an aromatic vinyl-based monomer unit, and the hydrophobicity of the obtained cured product is improved. Furthermore, it is presumed that the reason for the excellent developability is that the above-mentioned polymer has the above-mentioned vinyl-based monomer unit (X), so that the carboxyl group exhibiting alkali developability can be arranged farther from the main chain of the polymer with high hydrophobicity. Position to increase the probability of contact with the developer.

The "vinyl-based monomer unit (X) in which the side chain portion has an acid group and the acid group is located at a position separated by 5 atoms or more from the main chain" in the polymer of the form (3) will be described.

Examples of the above acid groups include functional groups such as carboxyl groups, phenolic hydroxyl groups, carboxylic acid anhydride groups, phosphoric acid groups, and sulfonic acid groups that undergo a neutralization reaction with alkaline water. It may have only one of these, or may have Two or more kinds. Among them, as the above-mentioned acid group, a carboxyl group or a carboxylic anhydride group is preferred, and a carboxyl group is more preferred.

The above-mentioned acid group is located 5 atoms or more away from the main chain. In the present invention, the so-called acid group located at a position more than 5 atoms apart from the main chain refers to the following state: the position of the carbon atom on the main chain of the polymer to which the side chain is bonded is set to 0 (zero), from which Starting from the position, there is an acid group at the position after the 5th atom in the side chain. The atoms on the side chain may also be atoms other than carbon or substituents. Specifically, it can be considered that, for example, in the case of the following formula (b), the acid group X in the formula is located 5 atoms away from the main chain, and in the case of the formula (c), the acid group X is located in the main chain. The chains are separated by 7 atoms.

In the above-mentioned vinyl monomer unit (X) in the polymer of the form (3), in terms of further excellent developability, the above-mentioned acid group is preferably located at a position separated by 5 atoms or more from the main chain . In terms of the solubility of the above-mentioned acid group in the developer, it is preferably located at a distance of less than 18 atoms, more preferably located at a distance of 16 atoms or less, and more preferably at a distance of 16 atoms or less. Positions below 14 atoms apart.

As said vinyl-based monomer unit (X), it is preferable to cite the same thing as the monomer unit (A) of the said aspect (1).

In the aspect (3), the content of the aforementioned monomer unit (A) relative to 100% by mass of all monomer units, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more, Furthermore, it is more preferably 65% by mass or less, and still more preferably 60% by mass or less.

The polymer of the form (3) preferably further contains an N-substituted maleimide-based monomer unit (Y). Since the above polymer has an N-substituted maleimide-based monomer unit, it is possible to provide a cured product with a more excellent water spot suppression effect, and also can provide a cured product with excellent heat-resistant colorability.

Regarding the effect of suppressing water spots further improved by the polymer of the form (3) further having the N-substituted maleimide-based monomer unit (Y), it is presumed that the reason is as follows. That is, when the above-mentioned polymer has an N-substituted maleimide-based monomer unit (Y), the above-mentioned polymerization The compound can be obtained by polymerizing a monomer that provides the monomer unit (E) and the vinyl monomer unit (X) together with an N-substituted maleimide monomer. During the polymerization, the aromatic vinyl monomer and the N-substituted maleimide monomer that provide the above monomer unit (E) have good alternating copolymerizability, so they are easy to be introduced adjacent to each other in the polymer . Therefore, it is inferred that in the polymer, the hydrophobic monomer unit (E) and the N-substituted maleimide monomer unit (Y) have a high ratio, and the hydrophilic vinyl system The portion where the ratio of the monomer unit (X) is large can further exert the effect of suppressing water spots and further improve the developability.

As the N-substituted maleimide-based monomer unit (Y) in the above-mentioned aspect (3), it is preferable to cite N derived from the monomer that provides the above-mentioned monomer unit (C) in the aspect (1). The monomer unit of the same monomer as the substituted maleimide monomer, more preferably selected from the group consisting of N-phenyl maleimide monomer unit and N-cyclohexyl maleimide monomer unit At least one of the group consisting of amine monomer units.

The polymer of form (3) may further have arbitrary monomer units. As the above-mentioned arbitrary monomer unit, the monomer unit described in the aspect (1) can be mentioned. The content of each monomer unit is preferably the same as that of the aspect (1), unless otherwise stated.

In the polymer of form (3), the content ratio (E)/(X) of the above-mentioned monomer unit (E) and the above-mentioned vinyl monomer unit (X) is preferably 10/60~60 in molar ratio /10. If the said content ratio is the said range, the suppression effect of water spot and developability will be more excellent. The content ratio (E)/(X) is more preferably 13/55 to 55/13, and still more preferably 15/50 to 50/15.

In the polymer of form (3), among the monomer units (E), the vinyl monomer units (X), and the N-substituted maleimide monomer units (Y) In the case, in terms of fully exerting the inhibitory effect of water spots regardless of other ingredients, the content ratio [(E)+(Y)]/(X) in the above-mentioned polymer is expressed in molar ratio It is preferably 15/60~70/10, more preferably 20/55~65/13, and still more preferably 25/50~60/15.

In the polymer of form (3), the monomer unit (E) and the above N When the maleimide-based monomer unit (Y), the above-mentioned vinyl-based monomer unit (X), and the above-mentioned monomer unit (B) are substituted, among the monomer units in the above-mentioned polymer The content ratio [(E)+(Y)]/[(X)+(B)] in molar ratio is preferably 20/80~70/30, more preferably 25/75~65/35, and more preferably It is 30/70~60/40.

In addition, in the polymer of the form (3), the total amount of the monomer unit (A) and the vinyl monomer unit (X) is preferably 100 mol% with respect to the total monomer components of the polymer. It is less than 80 mol%. If the above-mentioned total amount is in the above-mentioned range, the effect of suppressing water spots is even more excellent. The said total amount is more preferably 70 mol% or less with respect to 100 mol% of all monomer components. In addition, from the viewpoint of developability, the total amount is preferably 20 mol% or more with respect to 100 mol% of all monomer components, and more preferably 25 mol% or more.

The acid value, weight average molecular weight, and b* value of the polymer of the form (3) are preferably the same as those of the polymer of the above form (1).

<Manufacturing method of polymer>

As the method for producing the polymer of the present invention, for example, as long as it is a polymer of the form (1), a polymer having at least the above-mentioned monomer unit (A) and vinyl monomer unit (B) can be obtained , There is no particular limitation, and the following methods can be mentioned: making the monomers containing the monomers providing the above-mentioned monomer units (A) and (B), and optionally the monomers providing the above-mentioned monomer units (C) to (F) The monomer components are polymerized by a known method. In the form (2) and the form (3), it is similarly preferable to polymerize the monomer component containing at least the monomer providing the necessary monomer unit by a known method.

The method for polymerizing the above-mentioned monomer components is not particularly limited, and generally used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Among them, in terms of industrial advantage and easy realization of structural adjustments such as molecular weight, solution polymerization is preferred. In addition, the polymerization mechanism of the above-mentioned monomer components may use a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, etc. In terms of industrial advantage, it is preferably a polymerization based on a free radical polymerization mechanism. method.

The blending amount of the above-mentioned monomer components during polymerization is not particularly limited as long as it can obtain a polymer that provides a cured product with excellent heat-resistant colorability, and further, excellent developability, and water spot is suppressed. What is necessary is just to design suitably so that the content of a volume unit will become the said range.

For example, in the case of the polymer of the form (1), as the monomer component, it is preferable to provide the monomer (10-60% by mass) of the monomer unit (A) and the vinyl monomer unit ( B) The monomer (5~80% by mass), more preferably the monomer (20~60% by mass) that provides the above monomer unit (A), and the monomer that provides the above vinyl monomer unit (B) (5~80% by mass), and the monomer (2-60% by mass) that provides the above-mentioned monomer unit (C), and more preferably, the monomer (20-50% by mass) that provides the above-mentioned monomer unit (A) , Provide the monomer (10~70% by mass) of the above-mentioned vinyl-based monomer unit (B), provide the monomer (5-50% by mass) of the above-mentioned monomer unit (C), and (meth)acrylic acid (not included) Up to 5 mass%).

Also, for example, in the case of the polymer of the above-mentioned aspect (2), as the monomer component, it is preferable to include a monomer (10-60% by mass) that provides the above-mentioned monomer unit (A), and provides the above-mentioned vinyl-based monomer. The monomer (5~80% by mass) of the body unit (B), the monomer (1-30% by mass) that provides the above-mentioned monomer unit (D), and the monomer (2~) that provides the above-mentioned monomer unit (C) 60% by mass), more preferably including monomers (20-50% by mass) that provide the aforementioned monomer unit (A), monomers (10-70% by mass) that provide the aforementioned vinyl-based monomer unit (B), Provide the monomer (5-20% by mass) of the above-mentioned monomer unit (D), provide the monomer (5-50% by mass) of the above-mentioned monomer unit (C), and other polymerizable monomers (2-50% by mass) ), further preferably comprising a monomer (20-50% by mass) that provides the aforementioned monomer unit (A), a monomer (20-60% by mass) that provides the aforementioned vinyl-based monomer unit (B), and the aforementioned The monomer (5-20% by mass) of the monomer unit (D), the monomer (5-40% by mass) that provides the above-mentioned monomer unit (C), and (meth)acrylic acid (less than 5% by mass).

The polymerization initiation method of the above-mentioned polymerization reaction is as long as it can be self-heated, electromagnetic wave (for example, infrared, ultraviolet, X-ray, etc.), electron beam and other active energy sources can supply the monomer components to start the polymerization. The method of starting the required energy is sufficient, and if a polymerization initiator is used in combination, the energy required for starting the polymerization can be greatly reduced, and the reaction can be easily controlled, so it is preferred. The molecular weight of the polymer obtained by polymerizing the above-mentioned monomer components can be controlled by adjusting the amount or kind of polymerization initiator, polymerization temperature, kind or amount of chain transfer agent, and the like.

When the above-mentioned monomer components are polymerized by the solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inactive to the polymerization reaction. It depends on the polymerization mechanism and the type of monomer used. The polymerization conditions such as the amount, polymerization temperature, and polymerization concentration may be appropriately set. In the case where a solvent is used as a diluent when preparing a curable resin composition later, it is preferable to use a solvent containing the solvent for solution polymerization of monomer components in terms of efficiency.

As the above-mentioned solvent, the same solvents as those described in JP 2015-157909 A can be cited, and one or two or more of them can be used. Among these solvents, it is more preferable to use propylene glycol monomethyl in terms of the solubility of the obtained polymer, the smoothness of the surface when forming the coating film, the small impact on the human body and the environment, and the ease of industrial availability. Ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethyl lactate.

As the usage-amount of the said solvent, with respect to 100 mass parts of said monomer components, it is preferable that it is 50-1000 mass parts, and it is more preferable that it is 100-500 mass parts.

In the case where the above-mentioned monomer components are polymerized by a free radical polymerization mechanism, it is industrially advantageous to use a polymerization initiator that generates free radicals by heat, so it is preferred. As such a polymerization initiator, it is not particularly limited as long as it generates radicals by supplying thermal energy, as long as it is appropriately selected according to polymerization conditions such as the polymerization temperature, solvent, and the type of monomer to be polymerized. In addition, a polymerization initiator and reducing agents such as transition metal salts or amines may be used in combination.

As the polymerization initiator, for example, cumene hydroperoxide, dicumyl benzene hydroperoxide, di-tert-butyl peroxide, laurel peroxide, peroxide Benzoyl, tert-butyl peroxide isopropyl carbonate, tert-butyl peroxide 2-ethylhexanoate, Azobisisobutyronitrile, 1,1'-azobis(cyclohexanonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( 2-Methylpropionate) dimethyl, hydrogen peroxide, persulfate, etc. are usually peroxides or azo compounds used as polymerization initiators. These can be used individually or in combination of 2 or more types.

The amount of the polymerization initiator used is not particularly limited, as long as it is appropriately set according to the type or amount of the monomers used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, and the molecular weight of the target polymer. 100 parts by mass of the aforementioned monomer components are preferably 0.1-20 parts by mass, more preferably 0.5-15 parts by mass.

In addition, in the above polymerization, a chain transfer agent may be used as necessary. It is preferable to use a polymerization initiator and a chain transfer agent in combination. If a chain transfer agent is used during polymerization, it tends to suppress the increase in molecular weight distribution or gelation.

As said chain transfer agent, the solvent similar to the solvent described in Unexamined-Japanese-Patent No. 2015-157909 can be mentioned, 1 type, or 2 or more types of these can be used. Among them, in terms of availability, anti-crosslinking ability, and low degree of reduction in polymerization rate, it is preferable to cite mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans, mercapto alcohols, and aromatics. Mercaptans, mercapto isocyanurates and other compounds having mercapto groups, more preferably alkyl mercaptans, mercapto carboxylic acids, mercapto carboxylic acid esters, and more preferably n-dodecyl sulfide Alcohol, mercaptopropionic acid.

The amount of the chain transfer agent used is not particularly limited, as long as it is appropriately set according to the type or 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. For example, in order to obtain a polymer having a weight average molecular weight of several thousands to tens of thousands, it is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15 parts by mass relative to 100 parts by mass of the aforementioned monomer components.

Regarding the above-mentioned polymerization conditions, the polymerization temperature may be appropriately set according to the type or amount of the monomer used, the type or amount of the polymerization initiator, etc., for example, it is preferably 50 to 150°C, more preferably 70 to 120°C. In addition, the polymerization time can also be appropriately set in the same manner. For example, it is preferably 1 to 5 hours, and more preferably 2 to 4 hours.

2. Curable resin composition

The above-mentioned polymer can be combined with a polymerizable compound to form a curable resin composition. Since the said curable resin composition contains the said polymer, it can provide the hardened|cured material excellent in heat-resistant coloring property. In addition, it is possible to provide a cured product with excellent water spot suppression effect and developability, curability or adhesion to the substrate, surface hardness, heat resistance, solvent resistance, etc.

In this way, the above-mentioned polymer and a curable resin composition containing a polymerizable compound are also one of the present invention.

In the curable resin composition of the present invention, the content of the above-mentioned polymer is not particularly limited, as long as it is appropriately designed according to the application or the blending of other components, for example, relative to the total solid content of the curable resin composition 100 Mass%, preferably 5 mass% or more, more preferably 7 mass% or more, still more preferably 10 mass% or more, particularly preferably 15 mass% or more, most preferably 20 mass% or more, and more preferably 80 % By mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, particularly preferably 55% by mass or less, and most preferably 50% by mass or less.

When the polymer of the above-mentioned form (1) or (2) is included, the content of the polymer is 100% by mass relative to the total solid content of the curable resin composition, preferably 5 to 80% by mass, and more preferably It is 7 to 70% by mass, and more preferably 10 to 60% by mass. When the polymer of the above-mentioned form (3) is included, the content of the polymer is 100% by mass relative to the total solid content of the curable resin composition, preferably 10-60% by mass, more preferably 15-55 % By mass, more preferably 20-50% by mass.

Furthermore, the so-called "total solid content" refers to the total amount of the components that form the hardened substance (except for the solvent that volatilizes when the hardened substance is formed).

<Polymerizable compound>

The above-mentioned polymerizable compounds can be polymerized by irradiation of active energy rays such as free radicals, electromagnetic waves (e.g., infrared, ultraviolet, X-rays, etc.), electron beams, etc., which have polymerizable unsaturated bonds (also known as polymerizable unsaturated groups). ) Of low-molecular-weight compounds. For example, there is one polymerizable molecule in the molecule. Monofunctional compounds with saturated groups and polyfunctional compounds with two or more.

Examples of the monofunctional compound include: N-substituted maleimide monomers; (meth)acrylates; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids Acids; unsaturated monocarboxylic acids with chain extension between unsaturated groups and carboxyl groups; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds ; Unsaturated isocyanates, etc. In addition, monomers having active methylene groups or active methine groups can also be used.

As said polyfunctional compound, the following compounds etc. are mentioned, for example.

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 Base) acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide two (meth)acrylate, bisphenol F alkylene oxide two (Meth)acrylate and other difunctional (meth)acrylate compounds; trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, glycerol tri(methyl) ) Acrylate, neopentylerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dineopentylerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate )Acrylate, trineopentaerythritol hepta(meth)acrylate, trineopentaerythritol octa(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, ring Ethylene oxide addition di-trimethylolpropane tetra (meth) acrylate, ethylene oxide addition neopentyl erythritol tetra (meth) acrylate, ethylene oxide addition dineopentaerythritol hexa (Meth)acrylate, propylene oxide addition, trimethylolpropane tri(meth)acrylate, propylene oxide addition, di-trimethylolpropane tetra(meth)acrylate, propylene oxide addition Neopentyl erythritol tetra (meth) acrylate, propylene oxide addition dineopentaerythritol hexa (meth) acrylate, ε-caprolactone addition trimethylolpropane tri (meth) acrylate, ε-caprolactone addition di-trimethylolpropane tetra(meth)acrylate, ε-caprolactone addition neopentylerythritol tetra(meth)acrylate, ε-caprolactone addition two new Pentyleneerythritol hexa(meth)acrylate, dineopentaerythritol pentaacrylate succinic acid modified product, neopentylerythritol triacrylate succinic acid modified product, dineopentaerythritol pentaacrylate phthalic acid modified product , Neopentylerythritol triacrylate phthalic acid modifier, the following formula:

Multifunctional (meth)acrylate compounds with three or more functions, such as modified products of dineopentaerythritol hexaacrylate, etc.; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol diethylene 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, Di-trimethylolpropane tetravinyl ether, glycerol trivinyl ether, neopentyl erythritol tetravinyl ether, dineopentyl erythritol pentavinyl ether, dineopentyl erythritol hexavinyl ether, ethylene oxide added trihydroxy Methyl propane trivinyl ether, ethylene oxide addition di-trimethylolpropane tetravinyl ether, ethylene oxide addition neopentyl erythritol tetravinyl ether, ethylene oxide addition dineopentaerythritol six Multifunctional vinyl ethers such as vinyl ether; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxy (meth)acrylate Ethyl, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-(meth)acrylate Vinyloxypentyl ester, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate Ester, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate Ester and other vinyl ether group-containing (meth)acrylates; 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, di-trimethylol Alkyl propane tetraallyl ether, glycerol triallyl ether, neopentylerythritol tetraallyl ether, dineopentylene pentaerythritol pentaallyl ether, dineopentyl erythritol hexaallyl ether, ethylene oxide addition trihydroxy Methylpropane triallyl ether, ethylene oxide addition di-trimethylolpropane tetraallyl ether, ethylene oxide addition neopentylerythritol tetraallyl ether, ethylene oxide addition dineopentyl ether Polyfunctional allyl ethers such as tetraol hexaallyl ether; allyl-containing (meth)acrylates such as allyl (meth)acrylate; trimeric isocyanate (acryloxyethyl) Esters, tris(methacryloxyethyl) isocyanate, alkylene oxide addition tris(acryloxyethyl) isocyanate, alkylene oxide addition melisocyanurate Tris(methacryloxyethyl) ester and other multifunctional (meth)acrylic acid group-containing trimer isocyanates; Triallyl isocyanate and other multifunctional allyl-containing trimer isocyanates Class; by tolylene diisocyanate (tolylene diisocyanate), isophorone diisocyanate, stubble group diisocyanate and other multifunctional isocyanate and (meth) hydroxyethyl acrylate, (meth) acrylate 2- Polyfunctional urethane (meth)acrylates (urethane (meth)acrylates) obtained by the reaction of hydroxyl-containing (meth)acrylates such as hydroxypropyl esters; polyfunctional aromatic vinyls such as divinylbenzene, etc. . These polymerizable compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

Among the above-mentioned 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 number of functions of the polyfunctional polymerizable compound is preferably 3 or more, and more preferably 4 or more. In addition, the number of functions is preferably 10 or less, more preferably 8 or less.

In addition, the molecular weight of the polymerizable compound is not particularly limited, but from the viewpoint of handling, it is preferably 2000 or less, for example.

As the above-mentioned polyfunctional polymerizable compound, among them, from the viewpoints of reactivity, economy, availability, etc., a polyfunctional (meth)acrylate compound, a polyfunctional amine ester (meth)acrylate compound, and a polyfunctional amine ester (meth)acrylate compound are preferred. A compound having a (meth)acryloyl group, such as a trimeric isocyanate compound of a (meth)acryloyl group, is more preferably a polyfunctional (meth)acrylate compound. By containing the compound having a (meth)acryloyl group, the resin composition becomes more excellent in photosensitivity and curability, and a cured product with higher hardness and high transparency can be obtained. As the above-mentioned polyfunctional polymerizable compound, it is more preferable to use a trifunctional or higher polyfunctional (meth)acrylate compound.

The above-mentioned polymerizable compounds may be used singly or in combination of two or more kinds.

In the curable resin composition of the present invention, the content of the above-mentioned polymerizable compound is within the range that exerts the effects of the present invention, and it is not particularly limited and can be set appropriately, so that the curable resin composition can have an appropriate viscosity. On the other hand, with respect to 100% by mass of the total solid content of the curable resin composition of the present invention, it is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, and , Preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, particularly preferably 55% by mass or less, and most preferably 50% by mass or less. From the viewpoint of heat-resistant coloration, the content of the polymerizable compound is preferably 2 to 80% by mass, more preferably 5 to 70% by mass relative to 100% by mass of the total solid content of the curable resin composition. More preferably, it is 10-60 mass %.

Also, from the viewpoint of developability and water spot suppression effect, the content of the polymerizable compound is 100% by mass relative to the total solid content of the curable resin composition, preferably 2-60% by mass, and more preferably 5 to 55% by mass, more preferably 10 to 50% by mass.

<Photopolymerization initiator>

The curable resin composition preferably further contains a photopolymerization initiator. By containing the photopolymerization initiator, the curability of the curable resin composition can be improved, and the performance of the obtained cured product can be improved.

As the above-mentioned photopolymerization initiator, a radical polymerizable photopolymerization initiator is preferably mentioned. free The base polymerizable photopolymerization initiator is one that generates polymerization initiation radicals by irradiation of active energy rays such as electromagnetic waves or electron rays.

啉基丙烷-1-酮(「IRGACURE 907」，BASF公司製造)、2-苄基-2-二甲胺基-1-(4-N-

啉基苯基)-丁酮-1(「IRGACURE 369」，BASF公司製造)、2-二甲胺基-2-(4-甲基-苄基)-1-(4-嗎福林-4-基-苯基)-丁烷-1-酮(「IRGACURE 379」，BASF公司製造)等烷基苯酮(alkylphenone)系化合物；2,2-二甲氧基-1,2-二苯基乙烷-1-酮(「IRGACURE 651」，BASF公司製造)、苯基乙醛酸甲酯(「DAROCUR MBF」，BASF公司製造)等二苯乙二酮縮酮(benzil ketal)系化合物；1-羥基環己基苯基酮(「IRGACURE 184」，BASF公司製造)、2-羥基-2-甲基-1-苯基-丙烷-1-酮(「DAROCUR 1173」，BASF公司製造)、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮(「IRGACURE 2959」，BASF公司製造)、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)苄基]-苯基}-2-甲基-丙烷-1-酮(「IRGACURE 127」，BASF公司製造)、[1-羥基環己基苯基酮+二苯甲酮](「IRGACURE 500」，BASF公司製造)等羥基酮系化合物等；此外可列舉：日本專利特開2013-227485號公報段落[0084]~[0086]中例示之烷基苯酮系化合物；1,2-辛二酮，1-[4-(苯硫基)苯基]-,2-(O-苯甲醯基肟)](「OXE01」，BASF公司製造)、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(「OXE02」，BASF公司製造)、1,2-辛二酮，1-[4-(苯硫基)-,2-,(O-苯甲醯基肟)]，乙酮(「OXE03」，BASF公司製造)、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(「OXE04」，BASF公司製造))等肟酯系化合物；二苯甲酮系化合物；安 息香系化合物；9-氧硫

系化合物；鹵甲基化三

系化合物；鹵甲基化

二唑系化合物；聯咪唑系化合物；二茂鈦系化合物；苯甲酸酯系化合物；吖啶系化合物等；氧化膦系化合物等。其中，較佳為烷基苯酮系化合物。 As said photopolymerization initiator, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-N-

Linylpropan-1-one ("IRGACURE 907", manufactured by BASF Corporation), 2-benzyl-2-dimethylamino-1-(4-N-

Alkylphenyl)-butanone-1 ("IRGACURE 369", manufactured by BASF Corporation), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4 -Yl-phenyl)-butan-1-one ("IRGACURE 379", manufactured by BASF Corporation) and other alkylphenone compounds; 2,2-dimethoxy-1,2-diphenyl Benzil ketal compounds such as ethane-1-one ("IRGACURE 651", manufactured by BASF) and methyl phenylglyoxylate ("DAROCUR MBF", manufactured by BASF); 1 -Hydroxycyclohexyl phenyl ketone ("IRGACURE 184", manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenyl-propane-1-one ("DAROCUR 1173", manufactured by BASF Corporation), 1- [4-(2-Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one ("IRGACURE 2959", manufactured by BASF Corporation), 2-hydroxy-1-{4 -[4-(2-Hydroxy-2-methyl-propanyl)benzyl]-phenyl}-2-methyl-propane-1-one ("IRGACURE 127", manufactured by BASF Corporation), [1- Hydroxy ketone compounds such as hydroxycyclohexyl phenyl ketone + benzophenone] ("IRGACURE 500", manufactured by BASF Corporation), etc.; in addition, examples include paragraphs of Japanese Patent Laid-Open No. 2013-227485 [0084]~[0086] Alkyl phenone compounds exemplified in; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzyl oxime)] ("OXE01", BASF Corporation), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ("OXE02", manufactured by BASF Corporation), 1,2-octanedione, 1-[4-(phenylthio)-,2-,(O-benzyloxime)], ethyl ketone ("OXE03" , Made by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ("OXE04", manufactured by BASF Corporation)) and other oxime ester-based compounds; benzophenone-based compounds; benzoin-based compounds; 9-oxysulfur

Series compounds; halomethylation three

Series compounds; halomethylation

Diazole-based compounds; biimidazole-based compounds; titanocene-based compounds; benzoate-based compounds; acridine-based compounds, etc.; phosphine oxide-based compounds, etc. Among them, alkylphenone compounds are preferred.

The said photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the above-mentioned photopolymerization initiator is not particularly limited as long as the effect of the present invention is exerted, and may be appropriately designed, for example, 100% by mass relative to the total solid content of the curable resin composition of the present invention. Preferably it is 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1 mass% or more, still more preferably 2 mass% or more, particularly preferably 3 mass% or more, most preferably 5 mass% or more, Furthermore, it is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

From the viewpoint of better heat-resistant colorability, the content of the photopolymerization initiator is preferably 0.1-30% by mass, and more preferably 0.5 to 100% by mass relative to the total solid content of the curable resin composition. 25% by mass, more preferably 1-20% by mass.

From the viewpoint of developability and water spot suppression effect, the content of the photopolymerization initiator is preferably 2 to 35% by mass relative to 100% by mass of the total solid content of the curable resin composition, and more preferably 3 ~30% by mass, more preferably 5-25% by mass.

Furthermore, if necessary, a photosensitizer, a photoradical polymerization accelerator, etc. may be used in combination of one type or two or more types. By using a photopolymerization initiator together with a photosensitizer and/or a photoradical polymerization accelerator, the sensitivity or curability is further improved. The photosensitizer and the photoradical polymerization accelerator are not particularly limited, and they may be appropriately selected from known ones generally used in the self-curing resin composition.

色素、香豆素色素、3-酮基香豆素系化合物、吡咯亞甲基(pyrromethene)色素等色素系化合物；4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸2-乙基己酯等二烷基胺基苯系化合物；2-巰基苯并噻唑、2 -巰基苯并

唑、2-巰基苯并咪唑等硫醇系供氫體等。 Examples of photosensitizers or photoradical polymerization accelerators that can be used in combination with the above-mentioned photopolymerization initiator include:

Pigments, coumarin pigments, 3-ketocoumarin compounds, pyrromethene pigments and other pigment compounds; ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2 -Dialkylaminobenzene compounds such as ethylhexyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzo

Thiol-based hydrogen donors such as azole and 2-mercaptobenzimidazole.

In the case of using the above photosensitizer and photoradical polymerization accelerator, its content is relative to the solid of the curable resin composition in terms of the curability, the influence caused by the decomposition product, and the balance of economy. The total amount of components is 100% by mass, preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, and still more preferably 0.05 to 10% by mass.

<Other ingredients>

In addition to the aforementioned polymer, polymerizable compound, and photopolymerization initiator, the curable resin composition of the present invention may also contain other components as necessary. Examples of other components include: solvents; colored materials (also called colorants); dispersants; heat-resistant enhancers; leveling agents; development aids; inorganic particles such as silica particles; silane-based, aluminum-based, and titanium Series and other coupling agents; fillers, epoxy resins, phenol resins, polyvinyl phenol and other thermosetting resins; multifunctional thiol compounds and other hardening aids; plasticizers; polymerization inhibitors; ultraviolet absorbers; antioxidants; extinction Antifoaming agent; Antistatic agent; Smoothing agent; Surface modifier; Thixotropic agent; Thixotropic auxiliary; Quinonediazide compound; Polyphenol compound; Cationic polymerizable compound; Acid generator, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types. These other ingredients should be appropriately selected and used, and the amount of use can also be appropriately designed.

For example, when the curable resin composition is used for color filter applications, the curable resin composition preferably contains a colored material.

(Solvent)

As the above-mentioned solvent, ordinary users in curable resin compositions can be used, as long as they are appropriately selected according to the purpose and use, and are not particularly limited. For example, the same solvents as those described in Japanese Patent Laid-Open No. 2015-157909 can be used. By. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The amount of the solvent used is not particularly limited as long as it is appropriately set according to the purpose and use. It is preferably contained 10 to 00 in 100% by mass of the total amount of the curable resin composition. quality%. More preferably, it is 20 to 80% by mass.

(Non-ferrous materials)

Examples of the above-mentioned colored materials include pigments and dyes. As the above-mentioned colored material, one of a pigment or a dye may be used, or a combination of a pigment and a dye may be used. For example, in the case of forming the red, blue, and green pixels of the color filter, it is advisable to use a known method of appropriately combining colored materials such as blue and purple, green and yellow to exert the required color characteristics. In addition, in the case of forming a black matrix, it is advisable to use black colored materials.

Among colored materials, pigments are preferred in terms of durability, and dyes are preferred in terms of brightness improvement such as panels. These can be appropriately selected according to the required characteristics. In the curable resin composition of the present invention, in terms of further improving the solvent resistance and heat-resistant colorability of the cured product, a pigment is preferred. As the pigment, the same pigment as that described in JP 2015-157909 A can be used.

As the above-mentioned dyes, for example, organic materials described in Japanese Patent Laid-Open No. 2010-9033, Japanese Patent Laid-Open No. 2010-211198, Japanese Patent Laid-Open No. 2009-51896, and Japanese Patent Laid-Open No. 2008-50599 can be used. dye. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, etc. are preferred.

These colored materials can be used individually by 1 type, and can also be used in combination of 2 or more types.

The content of the colored material is not particularly limited, and can be appropriately set according to the purpose and application. It may be 100% by mass relative to the total solid content of the curable resin composition, preferably 0.1% by mass or more, more preferably 1% by mass % Or more, more preferably 2 mass% or more, more preferably 5 mass% or more, most preferably 10 mass% or more, more preferably 80 mass% or less, more preferably 70 mass% or less, and still more preferably 60% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 12% by mass or less.

From the viewpoint of better heat-resistant colorability, the content of the colored material is 2 to 80% by mass relative to 100% by mass of the total solid content of the curable resin composition, more preferably 5 to 70% by mass, and more Preferably, it is 10-60% by mass.

From the viewpoint of developability and water spot suppression effect, the content of the colored material is 100% by mass relative to the total solid content of the curable resin composition, preferably 0.1-20% by mass, more preferably 1-15% by mass %, more preferably 2 to 12% by mass.

(Dispersant)

When the curable resin composition of the present invention contains the above-mentioned colored material, it is preferable to further contain a dispersant. By containing a dispersant, the dispersion of the colored material in the dispersion medium can be stabilized. There are no particular limitations on the above-mentioned dispersant, and known ones can be mentioned, for example, resin-type dispersants, surfactants, pigment derivatives and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of the above-mentioned resin-type dispersants include: polycarboxylates such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acids. Alkylamine salts, polysiloxanes, long-chain polyamino amide phosphates, hydrogen-containing polycarboxylates, produced by the reaction of poly(lower alkyleneimines) with polyesters with free carboxyl groups The formed amide or its salt, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, poly Vinylpyrrolidone, polyester series, modified polyacrylate, ethylene oxide/polypropylene oxide adduct, etc. As a commercial item of the said resin-type dispersing agent, the thing similar to the resin-type dispersing agent described in Unexamined-Japanese-Patent No. 2015-157909 can be mentioned.

Examples of the aforementioned surfactant include: polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, and monoethanolamine lauryl sulfate , Triethanolamine lauryl sulfate, ammonium lauryl sulfate, sodium stearate, sodium lauryl sulfate and other anionic surfactants; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene B Nonionic surfactants such as sorbitan monostearate and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; Alkyl betaines such as alkyl dimethyl amino acetic acid betaine, amphoteric surfactants such as alkyl imidazoline, etc.

系、陰丹士林系、苝系、二酮基吡咯并吡咯系等。 The above-mentioned pigment derivative is a compound with a structure having a functional group introduced into the pigment. Examples of the functional group include: sulfonic acid group, sulfonamide group and its quaternary salt, dialkylamino group, hydroxyl group, carboxyl group, and sulfonate Amine group, phthalimide group, etc. Examples of the structure of the pigment that becomes the matrix include: azo series, anthraquinone series, quinophthalone series, phthalocyanine series, quinacridone series, benzimidazolone series, isoindoline series, two

System, indanthrene system, perylene system, diketopyrrolopyrrole system, etc.

The content of the above-mentioned dispersant may be appropriately set according to the purpose or application. From the viewpoint of the balance of dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.), and transparency, for example, relative to curable resin The total solid content of the composition is 100% by mass, preferably 0.01-60% by mass. More preferably, it is 0.1-50 mass %, More preferably, it is 0.3-40 mass %.

(Antioxidants)

By containing an antioxidant, the curable resin composition of the present invention can further improve the heat-resistant coloration resistance of the cured product.

The antioxidant that can be used in the present invention is not particularly limited, as long as a known antioxidant is appropriately selected and used. Among them, hindered phenol-based antioxidants and phosphite-based antioxidants are preferred. These may be used individually by 1 type, and may be used in combination of 2 or more types.

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

<Preparation of curable resin composition>

The method for preparing the above-mentioned curable resin composition is not particularly limited, and a known method may be used. For example, a method of mixing and dispersing the above-mentioned components using various mixers or dispersers can be mentioned. method. The mixing and dispersing steps are not particularly limited, as long as they are carried out by known methods. In addition, it may further include other steps normally performed. Furthermore, when the curable resin composition contains a colored material, it is preferably prepared through a step of dispersing the colored material.

As the step of dispersing the colored material, for example, the following method can be cited: firstly, each specific amount of colored material (preferably organic pigment), dispersant and solvent are weighed, and the colored material is dispersed in fine particles using a dispersing machine to obtain a liquid Colored material dispersion liquid (also known as grinding slurry). Examples of the above-mentioned dispersing machine include paint conditioners, bead mills, roll mills, ball mills, jet mills, homogenizers, kneaders, mixers, and the like. As the above-mentioned dispersion treatment step, it is preferable to enumerate the following method: after kneading and dispersing by a roll mill, kneader, mixer, etc., then a media grinder such as a bead mill filled with beads of 0.01 to 1 mm is used. Micro-dispersion treatment. To the obtained slurry, a composition (preferably a transparent liquid) containing the above-mentioned polymer, polymerizable compound, and photopolymerization initiator, as well as a solvent or leveling agent, etc., is additionally stirred and mixed in advance, and The mixture is mixed to form a uniform dispersion solution to obtain a curable resin composition.

Furthermore, the obtained curable resin composition is preferably filtered by a filter or the like to remove fine dirt.

3. Laminated body

As described above, the polymer and curable resin composition of the present invention provide a cured product having excellent heat-resistant colorability or a cured product having excellent developability and suppressed water spots. In addition, the surface hardness of the above-mentioned cured product, adhesion to the substrate, heat resistance, and transparency are all excellent. In addition, a laminate having such a cured product of the aforementioned polymer or a cured product of the aforementioned curable resin composition on a base material (substrate) is also one of the present invention.

When the above-mentioned cured product is a cured film, the film thickness is preferably 0.1 to 20 μm. If the film thickness is in the above range, excellent heat-resistant coloring properties can be exhibited. In addition, various properties such as surface hardness, adhesion to the substrate, heat resistance, and transparency can also be fully exhibited. The above film thickness is more preferably 0.5 to 10 μm, more preferably 0.5 to 8 μm.

In addition, from the viewpoint of good developability or water spot suppression effect, the above-mentioned film thickness is more preferably 1 to 15 μm, and 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 following method may be mentioned: the above-mentioned polymer or the above-mentioned curable resin composition is applied to the substrate, and the applied product is dried and heated Or irradiate energy rays such as ultraviolet rays to harden it to obtain a hardened product.

The above-mentioned base material is not particularly limited, as long as it is appropriately selected according to the purpose or use, and examples thereof include base materials made of various materials such as glass plates and plastic plates.

The above-mentioned laminated body is preferably used for, for example, color filters, black matrixes, photosensitive spacers, black color filters used in liquid crystal, organic EL, quantum dot/micro LED liquid crystal display devices or solid-state imaging devices, touch panel display devices, etc. Various optical components such as spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, and electrical and electronic equipment. Among them, it is preferably used for color filters.

In this way, a color filter having a cured product of the above-mentioned curable resin composition is also one of the present invention. Hereinafter, the color filter will be described.

3-1. Color filter

The color filter of the present invention is constituted by a form having a cured product of the above-mentioned curable resin composition on a substrate.

Among the above-mentioned color filters, the cured product formed of the above-mentioned curable resin composition is particularly suitable as a black matrix or as a segment that needs to be colored like each pixel such as red, green, blue, and yellow, and is also suitable as The photosensitive spacer, the protective layer, the ribs for alignment control, etc. do not necessarily need colored knots.

As the substrate used in the above-mentioned color filter, for example, glass substrates such as white plate glass, blue plate glass, alkali-strengthened glass, blue plate glass coated with silica; made of polyester, polycarbonate, etc. Sheets, films or substrates composed of thermoplastic resins such as esters, polyolefins, polyolefins, ring-opening polymers of cyclic olefins or their hydrogenated products; composed of thermosetting resins such as epoxy resins and unsaturated polyester resins Sheets, films, or substrates; metal substrates such as aluminum, copper, nickel, and stainless steel; ceramic substrates; semiconductor substrates with photoelectric conversion elements; glass substrates with colored material layers on the surface (such as color filters for LCD), etc. The constituent components, etc. Among them, in terms of heat resistance, a glass substrate or a sheet, film, or substrate made of a heat-resistant resin is preferable. In addition, the above-mentioned substrate is preferably a transparent substrate.

Furthermore, if necessary, corona discharge treatment, ozone treatment, chemical treatment with silane coupling agent, etc. may be performed on the above-mentioned substrate.

<Method of manufacturing color filter>

In order to obtain the above-mentioned color filter, for example, it is suitable to adopt the following manufacturing method, that is, adopt a method including the following steps for each color of a pixel (that is, a pixel of each color), and repeat the same method for each color: The step of disposing the above-mentioned curable resin composition on the substrate (also referred to as the disposing step), the step of irradiating the curable resin composition disposed on the substrate with light (also referred to as the light irradiation step), and the process is performed by a developer The step of developing treatment (also referred to as the developing step) and the step of performing heating treatment (also referred to as the heating step). Furthermore, the order in which pixels of various colors are formed is not particularly limited.

(Configuration step (preferably coating step))

The above configuration step is suitably performed by coating. As a method of coating the said curable resin composition on a board|substrate, spin coating, slit coating, roll coating, cast coating, etc. are mentioned, for example, Any method can be used suitably.

In addition, in the above-mentioned arranging step, it is suitable to dry the coating film after coating the above-mentioned curable resin composition on a substrate. The drying of the coating film can be performed using a hot plate, IR oven, convection oven, etc., for example. Drying conditions can be appropriately selected according to the boiling point of the contained solvent components, the type of hardening components, the film thickness, the performance of the dryer, etc. It is usually suitable for 10 seconds to 300 seconds at a temperature of 50 to 160°C.

(Light irradiation step)

In the above light irradiation step, as the light source of the active light used, for example, xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, Light sources such as fluorescent lamps; laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers, etc. In addition, as the method of the exposure machine, a proximity type, a mirror projection type, and a step type can be cited, and the proximity type can be preferably used.

Furthermore, in the step of irradiating the active energy light, the active energy light can also be irradiated through a specific mask pattern according to the application. In this case, the exposed part is hardened, but the hardened part is insoluble or hardly soluble in the developer.

(Development step)

The development step is a step of performing a development process with a developer after the light irradiation step to remove the unexposed portion to form a pattern. Thereby, a patterned cured film can be obtained. The developing process can usually be carried out at a developing temperature of 10~50℃ by immersion development, spray development, brush development, ultrasonic development and other methods.

The developer used in the above-mentioned development step is not particularly limited as long as it dissolves the curable resin composition of the present invention. Generally, an organic solvent or an alkaline aqueous solution can be used, and a mixture of these can also be used. Furthermore, when an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development.

Examples of suitable organic solvents for the above-mentioned developer include ether-based solvents and alcohol-based solvents. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers Types, alkyl phenyl ethers, aralkyl phenyl ethers, diaromatic ethers, isopropanol, benzyl alcohol, etc.

In addition to the alkaline agent, the above-mentioned alkaline solution aqueous solution may also contain surfactants, organic solvents, buffers, dyes, pigments, etc. as needed. As an organic solvent in this case, it can be The above-mentioned suitable organic solvents as the developer are listed.

Examples of the alkali agent include inorganic alkalis such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, disodium hydrogen phosphate, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. Agents; amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. It can be used individually or in combination of 2 or more types.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinates; alkyl betaines, amino Amphoteric surfactants such as acids and the like can be used alone or in combination of two or more kinds.

(Heating step)

The heating step is a step of further hardening the exposed portion (hardened portion) by firing after the developing step (also referred to as a post-hardening step). For example, it can include: using a light source such as a high-pressure mercury lamp, such as ^{a post-exposure step with a light amount of 0.5~5J/cm 2} ; or, for example, a step of performing subsequent heating at a temperature of 60-260°C for 10 seconds to 120 minutes, etc. By performing this post-curing step, the hardness and adhesion of the patterned cured film can be made stronger. In addition, by this heating step, in the polymer of the present invention, a part of the monomer unit (A) is separated to form a hydroxyl group at the terminal, and the hydroxyl group is not separated from the acid group of the monomer unit (A) or other The acid groups of arbitrary monomer units react to form a cross-linked structure, and the curability of the curable resin composition of the present invention or the solvent resistance, heat-resistant coloration, etc. of the obtained cured product become more excellent. In addition, in the vinyl monomer unit (B) of the polymer, the tertiary carbon-containing part is separated to form a carboxyl group, and the carboxyl group reacts with the hydroxyl group to form a cross-linked structure, which improves the solvent resistance of the cured product. The curability becomes more excellent.

The cured film obtained by the above-mentioned heating step (that is, the above-mentioned curable resin group The thickness of the cured film obtained by thermal curing of the product is preferably 0.1-20 μm. By using the curable resin composition of the present invention, a cured film with a sufficiently reduced film thickness can be provided. In addition, since the film thickness is reduced, the concentration of the colored material per unit volume of the cured film increases, and the brightness of the color filter can be improved. The above-mentioned film thickness is more preferably 0.5 to 10 μm, and still more preferably 0.5 to 8 μm.

Furthermore, regarding the film thickness of the coating film (ie, cured film) obtained by the above heating step, if the film thickness of the coating film before heating is set to 100%, it is suitably 90% or less. It is more preferably 80% or less, and still more preferably 70% or less.

In the above heating step, the heating temperature is suitably 150°C or higher. Thereby, the part derived from a part of the above-mentioned vinyl-based monomer unit (B) is more effectively decomposed, and the curability and solvent resistance 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. Furthermore, it is preferably 270°C or lower, more preferably 260°C or lower, and still more preferably 250°C or lower.

The heating time in the above heating step is not particularly limited, and for example, it is suitably set to 5 to 60 minutes. In addition, the heating method is not particularly limited. For example, it can be performed using heating equipment such as a hot plate, a convection oven, and a high-frequency heating machine.

4. Display device

Furthermore, the present invention is also a display device characterized by including the above-mentioned color filter.

Furthermore, a display device member and a display device having a cured product formed of the above-mentioned curable resin composition are also included in a preferred embodiment of the present invention. The cured product (cured film) formed of the above-mentioned curable resin composition is stable, has excellent adhesion to substrates, etc., has high hardness, exhibits high smoothness, and has high transmittance, so it is particularly suitable as a transparent member , Also, it can also be used as a protective film or insulating film in various display devices

As the above-mentioned display device, for example, a liquid crystal display device, a solid-state imaging element, a touch panel display device, etc. are suitable.

Furthermore, when the above-mentioned cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multi-layer member composed of the above-mentioned cured film, or may be in the single layer or The multi-layered member is further combined with other layered members, and may also be a member including the above-mentioned cured film in the configuration.

As described above, the polymer of the present invention and the curable resin composition containing the polymer can provide a cured product excellent in heat-resistant coloration. In addition, the cured product obtained by using the polymer and curable resin composition of the present invention has excellent adhesion to the substrate, transparency, heat resistance, and the like. The polymer and curable resin composition of the present invention is used in color filters, black matrices, and photosensitive materials used in liquid crystals, organic EL, quantum dots, micro LED liquid crystal display devices or solid-state imaging devices, touch panel display devices, etc. It is very useful for various applications in the optical field, electrical and electronic fields, such as sexual spacers, black spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, etc.

Example

Examples are disclosed below to illustrate the present invention in more detail, but the present invention is not limited to these examples. Furthermore, as long as there are no special regulations, "parts" means "parts by mass", and "%" means "% by mass".

In this example, the measurement conditions of various physical properties and the like are as follows.

<Weight average molecular weight>

Using HLC-8220GPC (manufactured by Tosoh Corporation), using tetrahydrofuran as the eluent, and using TSK-gel Super HZM-M (manufactured by Tosoh Corporation) as the column, the gel permeation chromatography was used to measure the standard polystyrene Calculated by ethylene conversion.

<Solid content>

Accurately weigh about 1g of the copolymer solution in an aluminum cup, add about 2g of acetone to dissolve it, and let it stand at room temperature for about 2 hours for natural drying. After that, use a vacuum dryer (manufactured by EYELA) to dry in a vacuum at 140°C for 1.5 hours, then place to cool in a desiccator, and measure the quality of the aluminum cup the amount. Calculate the solid content (mass%) of the copolymer solution based on its mass reduction.

<acid value>

Accurately weigh 1.5~3g of the copolymer solution and dissolve it in a mixed solvent of 90g of acetone and 10g of water. Use an aqueous solution of potassium hydroxide with a concentration of 0.1 equivalent as the titrant, using an automatic titration device (manufactured by Hiranuma Sangyo Co., Ltd., product: COM-1700) Measure the acid value of the copolymer solution, and calculate the acid value per 1g of the polymer based on the acid value and solid content of the solution.

<Heat-resistant coloration (Method A)>

The antioxidant Irganox 1010 (manufactured by BASF Corporation) was added to the copolymer solution so that the concentration became 0.5% by mass to prepare a resin composition solution. Using a spin coater (manufactured by Mikasa Co., Ltd., 1H-D7), the resin composition solution was uniformly coated on a 5 cm square ^{so that the coating amount was 0.4 to 1.2 mg/cm 2 in terms of solid content.} On a glass substrate (Soda-lime glass AS-2K, manufactured by Toshin Rixing Co., Ltd.). At this time, for each resin composition, the number of revolutions of the spin coater was changed to change the coating amount (in terms of solid content), and two coated plates with different coating amounts were produced. The coating amount of one of the two sheets must be greater than 0.6 mg/cm ² , and the coating amount of the other sheet must be less than 0.6 mg/cm ² .

By drying these coated plates at 100°C for 3 minutes, a laminate in which a coating film was formed on a glass substrate was obtained. After removing the resin attached to the end of the glass substrate, using a Perfect Oven thermostat (manufactured by Espec), the obtained laminate was heated at 250°C for 3 hours and cooled to room temperature. After cooling, a colorimeter ZE6000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used to measure the coating film surface of the laminate to obtain the b* value after the heating test. For each coating film, an approximate straight line (calibration curve) between the coating amount (x) and b* value (y) was calculated based on the measured values of the two coating films prepared in the above manner, and the coating amount was 0.6 mg/ The b* value in the case of cm ² is the result of the heat-resistant coloration resistance of each coating film.

<Heat-resistant coloration (Method B)>

To the copolymer solution, a solvent (propylene glycol monomethyl ether acetate) was added so as to be blended as shown in Table 4 to prepare a resin composition solution (solid content 35% by mass). A spin coater (manufactured by Mikasa Co., Ltd., 1H-D7) was used to uniformly coat the resin composition solution on a 5 cm square glass ^{so that the coating amount was 1.0 to 3.0 mg/cm 2 in terms of solid content.} On the substrate (Soda-lime glass AS-2K, manufactured by Toshin Rixing Co., Ltd.). At this time, for each resin composition solution, the number of revolutions of the spin coater was changed to change the coating amount (in terms of solid content), and two coated plates with different coating amounts were produced. The coating amount of one of the two sheets must be greater than 1.6 mg/cm ² , and the coating amount of the other sheet must be less than 1.6 mg/cm ² .

After drying these coated sheets at 140°C for 1 hour, they were further dried at 180°C for 1 hour to obtain a laminate with a coating film formed on a glass substrate. After removing the resin adhering to the end of the glass substrate, using a Perfect Oven thermostat (manufactured by Espec), the obtained laminate was heated at 250°C for 2 hours, and then cooled to room temperature. After cooling, a colorimeter ZE6000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used to measure the coating film surface of the laminate to obtain the b* value after the heating test. For each coating film, an approximate straight line (calibration curve) between the coating amount (x) and b* value (y) was calculated based on the measured values of the two coating films prepared in the above manner, and the coating amount was adopted as 1.6 mg/ The b* value in the case of cm ² is the result of the heat-resistant coloration resistance of each coating film.

<Evaluation of Water Spots>

Using a spin coater, the obtained curable resin composition was coated on an alkali-free glass plate (10cm×10cm, manufactured by Geomatec) in such a way that the coating film thickness after drying became 3μm, and the heating plate was used at 100°C. After drying for 3 minutes, an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays ^{so that the irradiation amount became 100 mJ/cm 2.} After the exposure, a 0.04% by mass potassium hydroxide aqueous solution was sprayed on the coating film for 60 seconds using a rotary developing machine to perform spray development. Then, the exposed part was rinsed with pure water for 10 seconds, and then the moisture on the surface of the glass plate was removed by blowing air. The water spots (unevenness) of the coating film were observed using an optical microscope (magnification 100 times), and evaluation was performed based on the following criteria. In the following standards, ○, ○△, and △ are set to be practically problem-free levels.

○: Water spots cannot be confirmed by an optical microscope.

○△: Water spots can be confirmed with an optical microscope.

△: Water spots can be confirmed with the naked eye.

×: A part of the coating film peeled off during development.

××: The coating film was completely peeled off during development.

<Developability (development time)>

The curable resin composition obtained is applied to a glass substrate by spin coating, and after heat treatment (100°C, 3 minutes), the distance from the coating film is 100μm, and the width of the line is 6-100μm. ^{The mask of the opening of the line and the gap is 60mJ/cm 2} (365nm illuminance) with a UV alignment exposure machine (manufactured by Topcon Corporation, trade name "TME-150RNS") equipped with a 2.0kW ultra-high pressure mercury lamp. Convert) exposure amount for exposure. After exposure, use a rotary developing machine to spray (spray pressure 0.15MPa) 0.05% potassium hydroxide aqueous solution to dissolve and remove the unexposed part, and wash the exposed part with pure water for 10 seconds, and then remove the surface of the glass plate by blowing air On the water. By adjusting the spraying time of the potassium hydroxide aqueous solution, the shortest time (Break Time) (seconds) until the end of development was evaluated.

(Synthesis example 1)

Preparation of copolymer solution 1

As the reaction tank, prepare a separable flask equipped with a thermometer, a stirrer, a gas introduction tube, a condenser, and a dripping tank inlet. On the other hand, as a monomer dripping tank, prepare 2,2'-[oxybis( Methylene)) Dimethyl bis-2-acrylate (hereinafter referred to as "MD") 10.0 parts, tert-butyl methacrylate (hereinafter referred to as "t-BMA") 29.5 parts, 2-hydroxy methacrylate 15.0 parts of ethyl ester (hereinafter referred to as "HEMA"), 1.0 part of methyl methacrylate (hereinafter referred to as "MMA"), mono(2-propenoxyethyl) succinate (hereinafter referred to as "HOA- MS'') 44.5 parts, 2-ethyl peroxide 2 parts of tert-butyl caproate (“Perbutyl (registered trademark) O” manufactured by NOF Corporation; hereafter called “PBO”), 33 parts of propylene glycol monomethyl ether acetate (hereafter called “PGMEA”) The stirring and mixing person, as a chain transfer agent dropping tank, prepares a person who has thoroughly stirred and mixed 1.6 parts of n-dodecyl mercaptan (n-DM) and 7.7 parts of PGMEA.

141 parts of PGMEA was added to the reaction tank, and after nitrogen replacement, the temperature of the reaction tank was raised to 90° C. while stirring and heating with an oil bath. After the temperature of the reaction tank has stabilized to 90°C, start dripping from the monomer dripping tank and the chain transfer agent dripping tank. The dripping system was performed each 2.5 hours while maintaining the temperature at 90°C. After 60 minutes had passed after the completion of the dripping, the temperature was increased to make the reaction tank 110°C. After maintaining at 110°C for 3 hours, it was cooled to room temperature, whereby a copolymer solution 1 was obtained. Various physical properties are shown in Table 1.

(Synthesis example 2)

Preparation of copolymer solution 2

The amount of monomer added was 10.0 parts of MD, 32.5 parts of t-BMA, 15.0 parts of HEMA, 24.3 parts of MMA, and 18.2 parts of HOA-MS, except that the monomer dropping tank and chain were prepared in the same manner as in Synthesis Example 1. The transfer agent was dropped into the tank, and the same operation was performed to obtain a copolymer solution 2. Various physical properties are shown in Table 1.

(Synthesis example 3)

Preparation of copolymer solution 3

The amount of monomer added is set to MD 10.0 parts, t-BMA 26.5 parts, HEMA 15.0 parts, MMA 1.0 parts, and succinic acid mono(2-methacryloxyethyl) ester (hereinafter referred to as "HO-MS ") Except for 47.5 parts, in the same manner as in Synthesis Example 1, a monomer dropping tank and a chain transfer agent dropping tank were prepared, and the same operations were performed to obtain a copolymer solution 3. Various physical properties are shown in Table 1.

(Synthesis example 4)

Preparation of copolymer solution 4

In a separable type equipped with a thermometer, agitator, gas inlet tube, condenser tube and drip tank inlet 164 parts of PGMEA was added to the flask, and after nitrogen substitution, it heated and raised the temperature to 90 degreeC. On the other hand, as a monomer dropping tank, 10.0 parts of N-benzyl maleimide (hereinafter referred to as "BzMI"), 28.0 parts of t-BMA, 15.0 parts of HEMA, 1.0 parts of MMA, and HOA were prepared. -If 46.0 parts of MS and 2.2 parts of PBO have been thoroughly stirred and mixed, as a chain transfer agent dropping tank, 2.6 parts of n-DM and 17.4 parts of PGMEA are prepared to be thoroughly stirred and mixed. After the temperature of the reaction tank has stabilized to 90°C, start dripping from the monomer dripping tank and the chain transfer agent dripping tank. The dropping system was carried out for 3 hours while maintaining the temperature at 90°C. After completion of the dropping, the temperature was maintained at 90°C for 30 minutes, and thereafter the temperature was raised to 115°C, and aging was performed for 90 minutes to obtain a copolymer solution 4. Various physical properties are shown in Table 1.

(Synthesis example 5)

Preparation of copolymer solution 5

Using N-cyclohexyl maleimide (hereinafter referred to as "CHMI") instead of BzMI, except that the same monomer addition amount as in Synthesis Example 4 was used to prepare a monomer dropping tank and chain transfer agent dropping Tank, perform the same operation to obtain copolymer solution 5. Various physical properties are shown in Table 1.

(Synthesis Example 6)

Preparation of copolymer solution 6

As a reaction tank, prepare a separable flask equipped with a thermometer, a stirrer, a gas introduction tube, a condenser, and a dripping tank inlet. On the other hand, as a monomer dripping tank, prepare 10.0 parts for MD and 38.8 parts for t-BMA , MMA 2.0 parts, HO-MS 49.2 parts, PBO 2.0 parts, PGMEA 33.0 parts are thoroughly stirred and mixed, as a chain transfer agent dripping tank, prepare 1.4 parts of n-dodecyl mercaptan (n-DM), PGMEA 7.9 parts have been thoroughly stirred and mixed.

141 parts of PGMEA was added to the reaction tank, and after nitrogen replacement, the temperature of the reaction tank was raised to 90° C. while stirring and heating with an oil bath. After the temperature of the reaction tank has stabilized to 90°C, start dripping from the monomer dripping tank and the chain transfer agent dripping tank. The dripping system was performed each 2.5 hours while maintaining the temperature at 90°C. After the end of the dripping, the temperature began to rise after 60 minutes, so that the reaction tank became It is 110°C. After maintaining at 110° C. for 3 hours, it was cooled to room temperature, whereby a copolymer solution 6 was obtained. Various physical properties are shown in Table 2.

(Synthesis Example 7)

Preparation of copolymer solution 7

The addition amount of the monomer was set to 10.0 parts of MD, 41.8 parts of t-BMA, 2.0 parts of MMA, and 46.2 parts of HOA-MS, except that the monomer dropping tank and chain transfer agent dropping were prepared in the same manner as in Synthesis Example 6. Tank, perform the same operation to obtain copolymer solution 7. Various physical properties are shown in Table 2.

(Synthesis example 8)

Preparation of copolymer solution 8

The monomer addition amount was set to 10.0 parts of MD, 41.8 parts of t-BMA, 32.2 parts of MMA, and 16.0 parts of HOA-MS, except that the monomer dropping tank and chain transfer agent dropping were prepared in the same manner as in Synthesis Example 6. Tank, perform the same operation to obtain copolymer solution 8. Various physical properties are shown in Table 2.

(Synthesis Example 9)

Preparation of copolymer solution 9

164 parts of PGMEA was added to a separable flask equipped with a thermometer, a stirrer, a gas introduction tube, a condenser tube, and a drip tank introduction port, and after nitrogen substitution, it was heated to increase the temperature to 90°C. On the other hand, as a monomer dripping tank, prepare to fully stir and mix 10.0 parts of BzMI, 41.8 parts of t-BMA, 2.0 parts of MMA, 46.2 parts of HOA-MS, and 2.2 parts of PBO as a chain transfer agent dripping tank. , Prepare to fully stir and mix 2.2 parts of n-DM and 17.8 parts of PGMEA. After the temperature of the reaction tank has stabilized to 90°C, start dripping from the monomer dripping tank and the chain transfer agent dripping tank. The dropping system was carried out for 3 hours while maintaining the temperature at 90°C. After the dropwise addition was completed, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes to obtain a copolymer solution 9. Various physical properties are shown in Table 2.

(Synthesis example 10)

Preparation of copolymer solution 10

Except for using CHMI instead of BzMI, a monomer dropping tank and a chain transfer agent dropping tank were prepared with the same monomer addition amount as in Synthesis Example 9, and the same operation was performed to obtain a copolymer solution 10. Various physical properties are shown in Table 2.

(Synthesis Example 11)

Preparation of copolymer solution 11

Using N-phenylmaleimide (hereinafter referred to as "PhMI") instead of BzMI, except that the same monomer addition amount as in Synthesis Example 9 was used to prepare a monomer dropping tank and chain transfer agent dropping In the tank, the same operation was performed to obtain a copolymer solution 11. Various physical properties are shown in Table 2.

(Synthesis example 12)

Preparation of copolymer solution 12

Except that the amount of monomer added was 10.0 parts of MD, 41.8 parts of t-BMA, 32.8 parts of MMA, and 15.4 parts of AA, the monomer dropping tank and the chain transfer agent dropping tank were prepared in the same manner as in Synthesis Example 6. The same operation was performed to obtain a copolymer solution 12. Various physical properties are shown in Table 2.

(Examples 1-11, Comparative Example 1)

Using the obtained copolymer solutions 1 to 12, the heat-resistant coloring resistance was evaluated by the above-mentioned method A. The results are shown in Table 1 and Table 2.

In addition, the description in Table 1 and Table 2 shows the following.

MD: 2,2'-[oxybis(methylene)]bis-2-dimethyl acrylate

BzMI: N-benzyl maleimide

CHMI: Cyclohexyl maleimide

PhMI: Phenyl maleimide

t-BMA: tertiary butyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

MMA: methyl methacrylate

HOA-MS: Mono(2-propenoxyethyl) succinate

HO-MS: Mono(2-methacryloxyethyl) succinate

AA: Acrylic

MAA: Methacrylic acid

According to Table 1 and Table 2, it is confirmed that there are HOA-MS or HO-MS monomer units, and Compared with the polymer without HOA-MS or HO-MS monomer unit (Comparative Example 1), the t-BMA monomer unit polymer (Examples 1 to 11) has a very small b* value, and heat resistance Excellent colorability.

(Synthesis Example 13)

Preparation of copolymer solution 13

70 parts of propylene glycol monomethyl ether acetate was added to a reaction tank equipped with a thermometer, a stirrer, a gas introduction tube, a condenser tube, and a dripping tank introduction port, and after nitrogen replacement, it was heated to raise the temperature to 90°C. On the other hand, as the dripping tank (A), prepared by stirring and mixing 20 parts of BzMI, 80 parts of PGMEA, and 2 parts of PBO in a beaker. As the dripping tank (B), prepare vinyltoluene (hereinafter referred to as "VT") 20 parts, 20 parts t-BMA, 40 parts HO-MS, and 4 parts n-dodecyl mercaptan are stirred and mixed. After the temperature of the reaction tank reached 90°C, while maintaining the temperature, the dropwise addition took 3 hours from the start of the dropping tank to perform polymerization. After the dripping was completed, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C, and aging was performed for 90 minutes to obtain a copolymer solution 13. Table 3 shows various physical properties. In addition, the monomer composition of the obtained copolymer was BzMI/VT/t-BMA/HO-MS (mole ratio)=18/29/24/29.

(Synthesis example 14)

Preparation of copolymer solution 14

The addition amount of the monomer was set to 20 parts of CHMI, 20 parts of VT, 20 parts of t-BMA, and 40 parts of HO-MS, except that the same operation as in Synthesis Example 13 was performed to obtain a copolymer solution 14. Table 3 shows various physical properties. In addition, the monomer composition of the obtained copolymer was CHMI/VT/t-BMA/HO-MS (mole ratio)=19/28/24/29.

(Synthesis example 15)

Preparation of copolymer solution 15

The addition amount of the monomer was set to 20 parts of PhMI, 20 parts of VT, 20 parts of t-BMA, and 40 parts of HO-MS, except that the same operation as in Synthesis Example 13 was performed to obtain a copolymer solution 15. Various physical properties Shown in Table 3. In addition, the monomer composition of the obtained copolymer was PhMI/VT/t-BMA/HO-MS (mole ratio)=19/29/23/29.

(Synthesis Example 16)

Preparation of copolymer solution 16

The addition amount of the monomer was 10 parts of PhMI, 10 parts of VT, 40 parts of t-BMA, and 40 parts of HO-MS, except that the same operation as in Synthesis Example 13 was performed to obtain a copolymer solution 16. Table 3 shows various physical properties. In addition, the monomer composition of the obtained copolymer is PhMI/VT/t-BMA/HO-MS (mole ratio)=10/14/47/29.

(Synthesis Example 17)

Preparation of copolymer solution 17

The addition amount of the monomer was set to 20 parts of PhMI, 20 parts of VT, 30 parts of t-BMA, and 30 parts of HO-MS, except that the same operation as in Synthesis Example 13 was performed to obtain a copolymer solution 17. Table 3 shows various physical properties. In addition, the monomer composition of the obtained copolymer is PhMI/VT/t-BMA/HO-MS (mole ratio)=18/27/34/21.

(Synthesis Example 18)

Preparation of copolymer solution 18

The addition amount of the monomer was 10 parts of BzMI, 35 parts of t-BMA, 19.5 parts of MMA, 20 parts of HEMA, and 15.5 parts of AA. The same operation as in Synthesis Example 13 was performed except that the copolymer solution 18 was obtained. Table 3 shows various physical properties. In addition, the monomer composition of the obtained polymer is BzMI/t-BMA/MMA/HEMA/AA (mole ratio)=6/29/23/18/24.

(Synthesis Example 19)

Preparation of copolymer solution 19

The amount of monomer added is 10 parts of CHMI, 35 parts of t-BMA, 19.5 parts of dicyclopentane methacrylate (hereinafter referred to as "DCPMA"), 20 parts of HEMA, and 15.5 parts of AA. In addition, Advance The same operation as in Synthesis Example 13 was performed, and a copolymer solution 19 was obtained. Table 3 shows various physical properties. In addition, the monomer composition of the obtained polymer is CHMI/t-BMA/DCPMA/HEMA/AA (mole ratio)=7/32/12/20/29.

(Examples 12-16, Comparative Example 2)

Using the obtained copolymer solutions 13 to 18, method B was used to evaluate the heat-resistant coloring resistance. The results are shown in Table 4.

(Example 17)

In terms of solid content, 20 parts of copolymer solution 13, 50 parts of colored material composition (Blue), 20 parts of dineopentaerythritol hexaacrylate as a polymerizable compound, and Irgacure 907 as a photopolymerization initiator (Manufactured by BASF Corporation) 10 parts were mixed, and then propylene glycol monomethyl ether acetate (PGMEA) was added as a diluent solvent so that the solid content concentration became 20% by mass and stirred 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 5.

Furthermore, the above-mentioned colored material composition (Blue) was prepared by the following method.

*Preparation of colored material composition (Blue)

Resin solution for weighing and dispersion (Resin monomer composition: BzMI/cyclohexyl methacrylate/methyl methacrylate/methacrylic acid=30/30/30/10 (mass ratio), Mw: 10000, acid value : 65mgKOH/g, solid content in resin solution: 42%) 8.3 parts by mass, dispersant (manufactured by BYK-Chemie Japan, brand name "DISPERBYK-2001", non-volatile content 1.3g) 2.9 parts by mass, pigment (CI Pigment Blue 15: 6) 8.0 parts by mass are placed in a 225 ml container, and diluted with PGMEA so that the non-volatile content (solid content concentration) becomes 20% by mass. 64 g of zirconia beads with a diameter of 1.0 mm were added thereto, and after being shaken by a paint shaker for 3 hours for dispersion treatment, the zirconia beads were removed by decantation to obtain a colored material composition (Blue).

(Examples 18-21, Comparative Examples 3-4)

The copolymer solutions 14 to 19 were used so as to be blended as shown in Table 5, and curable resin compositions (2-1) to (7-1) were obtained by the same operation as in Example 17. The developability of the obtained curable resin composition was evaluated. The results are shown in Table 5.

(Example 22)

In terms of solid content, 45 parts of copolymer solution 13, 20 parts of the above colored material composition (Blue), 25 parts of dineopentaerythritol hexaacrylate as a polymerizable compound, and Irgacure as a photopolymerization initiator 10 parts of 907 (manufactured by BASF Corporation) were mixed, and a dilution solvent (PGMEA) was added and stirred so that the solid content concentration became 20% by mass, thereby obtaining a curable resin composition (1-2). The water spots of the curable resin composition (1-2) obtained were evaluated. The results are shown in Table 6.

(Examples 23 to 26, Comparative Examples 5 to 6)

The polymer solutions 14 to 19 were used so as to be blended as shown in Table 6, and curable resin compositions (2-2) to (7-2) were obtained by the same operation as in Example 22. The water spots of the curable resin composition obtained were evaluated. The results are shown in Table 6.

In addition, the description in Table 3 indicates the following.

BzMI: N-benzyl maleimide

CHMI: Cyclohexyl maleimide

PhMI: Phenyl maleimide

VT: Vinyl toluene

CHMA: Cyclohexyl methacrylate

t-BMA: tertiary butyl methacrylate

MMA: methyl methacrylate

DCPMA: Dicyclopentane methacrylate

HEMA: 2-hydroxyethyl methacrylate

AA: Acrylic

HO-MS: Mono(2-methacryloxyethyl) succinate

According to Table 4, it was confirmed that the polymer with HO-MS monomer unit and t-BMA monomer unit (Examples 12 to 16) was compared with the polymer without HO-MS monomer unit (Comparative Example 2) , The b* value becomes a small value, and the heat-resistant coloring resistance is excellent.

According to Tables 5 and 6, it was confirmed that the polymer having HO-MS monomer unit and t-BMA monomer unit (Examples 17~26) and the polymer not having HO-MS monomer unit (Comparative Example 3~ 6) In comparison, both the developability and the water spot suppression effect are excellent.

Claims (9)

A polymer having: 10-60% by mass of monomer units represented by the following general formula (I), and containing -COO*R ⁴ (R ⁴ is a monovalent organic group bonded to the carbon atom of O* 5~80% by mass of vinyl monomer units of tertiary carbon atoms) group; the polymer is a cyclic structure-containing polymer with a cyclic structure in the main chain,

(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 with a carbon number of 1-12; R ³ represents a divalent organic group ; X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group or a phosphoric acid group; m represents the average number of repeating units of the monomer unit represented by the general formula (I), and is a number greater than 1; n is 0 or 1). The polymer according to claim 1, wherein the polymer is a polymer further having a hydroxyl group-containing monomer unit. The polymer according to claim 1 or 2, wherein the polymer is a polymer further having an aromatic vinyl monomer unit. The polymer according to claim 1 or 2, wherein the content of (meth)acrylic acid units is less than 5% by mass. The polymer described in claim 1 or 2 has an acid value of 40 to 160 mgKOH/g. A curable resin composition containing the polymer according to any one of claims 1 to 5 and a polymerizable compound. A laminate having the polymer according to any one of claims 1 to 5 on a substrate The cured product or the cured product of the curable resin composition described in claim 6. A color filter having a cured product of the curable resin composition described in claim 6 on a substrate. A display device including the color filter described in claim 8.