KR102366344B1 - Polymers, curable resin compositions, and uses thereof - Google Patents

Abstract

This invention can fully suppress yellowing at the time of heating, and provides the polymer which can be applied to high coloring, and curable resin composition containing the said polymer. 10 to 60 mass % of monomer units represented by the following general formula (I), and -COO ^{* R4} ( ^R4 is a monovalent organic group, and the carbon atom couple|bonded with O ^* is a tertiary carbon It is a polymer characterized by having 5-80 mass % of vinylic monomer units containing a group.

Description

Polymers, curable resin compositions, and uses thereof

The present invention relates to a novel polymer. In more detail, it is related with the polymer excellent in heat-resistant coloring property, the curable resin composition containing the said polymer, the color filter which has the hardened|cured material of the said curable resin composition, and a display device.

BACKGROUND ART Polymers that can be cured by heat or active energy rays are applied to various uses depending on the properties of the polymer. Examples of such uses include, for example, color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used for liquid crystal display devices and solid-state imaging devices, and various optical members and electrical/electronic devices. There is, and further examination is repeated about a copolymer suitable for these uses.

Among the above-mentioned uses, a color filter is a main member which comprises a liquid crystal display device, a solid-state image sensor, etc., and generally a board|substrate and pixels of at least three primary colors (red (R), green (G), and blue (B)) In addition to and resin black matrix (BM) which partitions them, it coat|covers and protects a pixel and a resin black matrix, and is comprised from the protective film etc. which are formed in order to planarize those unevenness|corrugation.

Usually, when performing pixel formation of a color filter using a curable resin composition, with respect to one pixel color, the resist formed by (1) the application|coating process of apply|coating curable resin composition to the whole surface of a board|substrate, (2) application|coating process After curing the exposed portion by pattern exposure of the film through a photomask, an exposure step of insolubilizing the cured portion, (3) removing the unexposed portion with a developer, and further curing the exposed portion by baking (bake) A method of performing a firing (bake) treatment step and repeating the same step as this for each color is adopted. In consideration of the application of such a color filter to a use, etc., various physical properties such as curability, solvent resistance after curing, adhesion to a substrate, heat resistance and transparency are required for the resin to be used or a curable resin composition containing the resin.

Up to now, various proposals have been made for resins having such various physical properties.

For example, in Patent Document 1, as a polymer excellent in heat resistance, a polymer obtained by copolymerizing an N-substituted maleimide and/or a specific ether dimer, vinyltoluene, and a monomer having an acid group as a monomer component is proposed.

However, in a resin composition containing a polymer derived from maleimide, since the maleimide-based polymer contains a nitrogen atom, the polymer is colored yellow to yellowish brown upon heating, and there is a problem that the transparency of the cured film becomes insufficient. On the other hand, the polymer which can form the coating film excellent also in transparency with heat resistance is proposed.

For example, in Patent Document 2, a specific monomer that is an ether dimer of 2-(hydroxyalkyl)acrylic acid ester, an unsaturated monomer containing a carboxyl group, and a hydroxyl group as a polymer capable of forming a coating film having excellent heat resistance and transparency A polymer formed by copolymerizing an unsaturated monomer containing as a monomer component has been proposed.

Further, in Patent Document 3, a monomer having a tertiary carbon-containing (meth)acrylate-based monomer unit and a hydroxyl group that can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to a substrate, heat resistance, and transparency. Curable resin composition containing the (meth)acrylate polymer which has a unit, a polymeric compound, and a photoinitiator is proposed.

Moreover, as a curable resin composition suitable for a color filter use, in patent document 4, for example, a carboxyl group is arrange|positioned in the side chain which separated the number of elements 7 or more from the main chain, and has a radically polymerizable double bond in a side chain, A photosensitive resin composition comprising a carboxyl group-containing radically polymerizable copolymer is disclosed.

Japanese Patent Laid-Open No. 2009-40999 Japanese Patent Laid-Open No. 2012-82317 Japanese Laid-Open Patent Publication No. 2015-42697 Japanese Laid-Open Patent Publication No. 2012-193219

In recent years, reduction in size, thickness reduction, and energy saving of an optical member, an electric/electronic device, etc. are progressing, and high-quality performance is requested|required by members, such as a color filter used with it. However, it is difficult to say that such requests are sufficiently met, and there is still room for improvement. In particular, in color filter applications, high luminance and high contrast of display panels are strongly demanded with quality improvement and application expansion of color liquid crystal display devices, etc., and yellowing of polymers during heating is further suppressed compared to the prior art, The development of polymers applicable to high-pigmentation is required.

This invention was made|formed in view of the said current situation, and it aims at providing the polymer which can fully suppress the yellowing at the time of heating, and can be applied to high coloring, and curable resin composition containing the said polymer.

In order to solve the above problems, the present inventors have studied various polymers applicable to color filters and the like, and by having at least two specific monomer units in a specific range amount, it has been found that a cured product excellent in heat color resistance is obtained. . Moreover, this inventor discovered that such a polymer and curable resin composition containing this polymer are especially preferable as a polymer and resin composition for forming members, such as a color filter use, came to complete this invention.

In the present invention, "heat-resistant colorability" means a characteristic in which discoloration such as yellowing is unlikely to occur upon heating of the polymer.

That is, according to the present invention, 10 to 60 mass% of a monomer unit represented by the following general formula (I), and -COO ^* R ⁴ (R ⁴ is a monovalent organic group, and the carbon atom bonded to O ^* is a third It is a primary carbon atom.) It has 5-80 mass % of vinylic monomer units containing a group, It is a polymer characterized by the above-mentioned.

[Formula 1]

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms. R ³ is 2 represents an organic group of valence.X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid 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 1 or more It is a number, where n is 0 or 1.)

It is preferable that the said polymer is a ring structure containing polymer which has a ring structure in a principal chain.

It is preferable that the said polymer is a polymer which has a hydroxyl-containing monomeric unit further.

It is preferable that the said polymer is a polymer which has an aromatic vinylic monomer unit further.

It is preferable that content of the said polymer is less than 5 mass % of a (meth)acrylic acid unit.

It is preferable that the said polymer is an acid value of 40-160 mgKOH/g.

This invention is also curable resin composition characterized by containing the polymer mentioned above and a polymeric compound further.

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

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

This invention is also provided with the color filter mentioned above, It is also a display apparatus characterized by the above-mentioned.

Since the polymer of this invention consists of the structure mentioned above, the hardened|cured material excellent in heat-resistant coloring property can be provided. The polymer of this invention and the curable resin composition containing the said polymer can be used suitably for various uses, such as various optical members and an electric/electronic device, Especially the color filter used for a liquid crystal display device, a solid-state image sensor, etc. can be preferably used for

Hereinafter, the present invention will be described in detail.

Moreover, what combined two or more of each preferable aspect of this invention described below is also a preferable aspect of this 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 contains 10 to 60 mass% of a monomer unit represented by the following general formula (I), and -COO ^* R ⁴ (R ⁴ is a monovalent organic group, and the carbon atom bonded to O ^* is a third It is a primary carbon atom.) It is characterized in that it has 5-80 mass % of vinylic monomer units containing a group.

[Formula 2]

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms. R ³ is 2 represents an organic group of valence.X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid 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 1 or more It is a number, where n is 0 or 1.)

Since the polymer of this invention consists of the structure mentioned above, yellowing at the time of heating can be suppressed, ie, the hardened|cured material excellent in heat-resistant coloring property can be provided.

The reason that the polymer can provide a cured product excellent in heat color resistance is that, when the polymer is heated, a part of the monomer unit represented by the general formula (I) is detached to form a hydroxyl group at the terminal, and the hydroxyl group is a reactive system ^The effect of ^radicals is ^reduced by capturing radicals ⁱⁿ It is a carbon atom.) The tertiary carbon atom of the vinyl monomer unit containing the group is detached to form an acid group, and it is assumed that a strong film (cured product) is formed by crosslinking the acid group and the above-mentioned hydroxyl group. do.

Moreover, the polymer of this invention is excellent also in sclerosis|hardenability, the hardness of hardened|cured material, solvent resistance, heat resistance, transparency, and adhesiveness to a base material. In addition, when the polymer is applied to a resin composition containing a color material, the color material concentration in the obtained cured product can be increased, so that further thinning can be realized, and the resin composition is applied to a color filter application. In this case, higher color purity and higher light-shielding ratio of the black matrix can be further achieved.

The reason that the polymer can improve the curability and properties of the cured product is that, as described above, when the polymer is heated, the monomer units constituting the polymer and the hydroxyl groups and acid groups generated from them are crosslinked. , it is estimated that the hydroxyl group captures radicals in the reaction system. In addition, the reason that the color material concentration in the cured product can be increased is that the resin highly shrinks by forming the cross-linked structure as described above, or the desorbed component volatilizes and the amount of the resin in the cured product is relatively reduced. It is assumed that

The monomer units constituting the polymer of the present invention will be described in detail. In addition, in this invention, "monomer unit" means the 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 general formula (I) (hereinafter also referred to as “monomer unit (A)”).

In the said general formula (I), R< ¹ > represents a hydrogen atom or a methyl group. Moreover, a methyl group is preferable at the point which heat resistance and the water nonuniformity suppression effect become favorable.

In the present invention, "water non-uniformity" means that the cured product comes into contact with an aqueous solution such as a developer, and after the aqueous solution is removed, discoloration occurs such that the contacted portion is cloudy, and the cured product has shading unevenness. means that

R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms.

Examples of the divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group include an alkylene group, an arylene group, and a divalent hydrocarbon group having an alicyclic structure, and among them, an alkylene group is preferable. Examples of the alicyclic structure include a cyclohexane skeleton, an adamantane skeleton, and a norbornene skeleton. Moreover, these may have a substituent.

As R< ² >, Preferably, they are alkylene groups, such as a methylene group, an ethylene group, a propylene group, a butylene group, a heptylene group, an octylene group, and a dodecylene group; Arylene groups, such as a phenylene group, a tolylene group, and a naphthylene group; Group by which these groups were substituted with functional groups, such as a hydroxyl group; and the like.

Especially, as R< ² >, a C1-C10 alkylene group is preferable and a C1-C5 alkylene group is more preferable.

R ³ represents a divalent organic group. The divalent organic group preferably includes a divalent chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a divalent chain type having 1 to 5 carbon atoms. Or a branched saturated hydrocarbon group or an unsaturated hydrocarbon group is mentioned. The said organic group may have a substituent.

As R< ³ >, For example, alkylene groups, such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, an ethylethylene group, a hexylene group, an octylene group, and a dodecylene group; Alkenylene groups, such as a vinylene group, a propenylene group, an isopropenylene group, a butenylene group, a pentenylene group, and a hexenylene group; Cycloalkylene groups, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornylene group, and an adamantylene group; Arylene groups, such as a phenylene group, a tolylene group, a naphthylene group, and a fluorene group; Alkyl ether groups, such as an ethyl ether group and a propyl ether group; and groups containing a bond such as -O-, -S-, -SO-, -SO ₂ - with these groups.

Especially, since it is further excellent in heat-resistant coloring property, as R< ³ >, an alkylene group is preferable, a C1-C10 alkylene group is more preferable, A C1-C5 alkylene group is still more preferable.

X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid anhydride group, or a phosphoric acid group. Especially, it is preferable that X is a carboxyl group at the point which is further excellent in heat-resistant coloring property.

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

n is 0 or 1, preferably 1.

The monomer providing the monomer unit (A) is preferably β-carboxyethyl (meth) acrylate, monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl). unsaturated monocarboxylic acids in which a chain is extended between unsaturated groups, such as carboxyl groups, etc. are mentioned, More preferably, β-carboxyethyl (meth)acrylate, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), More preferably, monosuccinate (2-methacryloyloxyethyl) is mentioned. By superposing|polymerizing the monomer component containing such a compound, the polymer which has the said monomeric unit (A) can be obtained.

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

Content of the said monomeric unit (A) in the said polymer is 10-60 mass % with respect to 100 mass % of all the monomer units of the said polymer. The content of the monomer unit (A) is preferably 15 mass % or more, more preferably 20 mass % or more, and more preferably 50 mass %, based on 100 mass % of all monomer units of the polymer, from the viewpoint of further excellent heat-resistant colorability. % or less is preferable.

Specifically, it is preferable that it is 20-60 mass % with respect to 100 mass % of all the monomer units of the said polymer, and, as for content of the said monomeric unit (A), it is more preferable that it is 20-50 mass %.

Moreover, it is preferable that it is 15 mass % or more with respect to 100 mass % of all the monomeric units of the said polymer, and, as for content of the said monomeric unit (A), it is more preferable that it is 20 mass % or more from a viewpoint of the water nonuniformity suppression effect.

<-COO ^* Vinyl-based monomer unit containing R ⁴ group (B)>

The polymer of the present invention further comprises -COO ^{* R4} ( ^R4 represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom.) A vinyl monomer unit containing a group (hereinafter , also referred to as a "vinyl-based monomer unit (B).").

In the vinyl monomer unit (B), R ⁴ of the -COO ^* R ⁴ group represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom. A tertiary carbon atom means the carbon atom which has 3 other carbon atoms couple|bonded with the carbon atom.

The monovalent organic group preferably includes a monovalent chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 91 carbon atoms. The said organic group may have a substituent.

The carbon number of ^R4 becomes like this. More preferably, it is C1-C50, More preferably, it is C1-C35, Especially preferably, it is C1-C20.

It is preferable that R< ⁴ > is the same monovalent organic group as A in Formula (a) mentioned later.

As a vinylic monomer, the monomer which has a polymerizable carbon-carbon double bond in a molecule|numerator is mentioned, Especially, (meth)acrylate-type monomer is preferable. That is, the vinyl-based monomer unit (B) is preferably a tertiary carbon-containing (meth)acrylate-based monomer unit.

The polymer having the 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.

It is preferable that the said tertiary carbon-containing (meth)acrylate-type monomer has a structure in which the oxygen atom adjacent to the (meth)acryloyl group couple|bonded with the tertiary carbon atom.

The tertiary carbon-containing (meth)acrylate-based monomer is a compound having one polymerizable carbon-carbon double bond in a molecule, that is, a (meth)acryloyl group (CH ₂ =C(R ⁵ )-C( =O)-) is preferably a compound having one, for example, the following general formula (a):

CH ₂ =C(R ⁵ )-C(=O)-OA (a)

(wherein, R ⁵ represents a hydrogen atom or a methyl group. A represents a monovalent organic group including a structure having a tertiary carbon atom on the oxygen atom side.)

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

The number of carbon atoms of the organic group represented by A is an oxygen atom adjacent to the (meth)acryloyl group (CH ₂ =C(R ⁵ )-C(=O)-) and a tertiary carbon atom in A adjacent thereto It is preferable that it is 12 or less, and it is more preferable that it is 9 or less at the point which volatilizes easily the new compound produced|generated by the OC bond between them being cut|disconnected. Moreover, the organic group represented by said A may have a branched structure.

Here, in the tertiary carbon-containing (meth)acrylate-based monomer, in the tertiary carbon atom bonded to an oxygen atom adjacent to the (meth)acryloyl group, at least one of the adjacent carbon atoms is bonded to a hydrogen atom It is preferable to do For example, when the tertiary carbon-containing (meth)acrylate-based monomer is a compound represented by the general formula (a), and A is a group represented by -C(R ⁶ )(R ⁷ )(R ⁸ ), It is preferable that at least one of R ⁶ , R ⁷ and R ⁸ contains a carbon atom having one or more hydrogen atoms, and the carbon atom is bonded to a tertiary carbon atom. In such a form, the OC bond between the oxygen atom adjacent to the (meth)acryloyl group and the tertiary carbon atom adjacent to it is cut|disconnected by heating, and (meth)acrylic acid is produced|generated, and while the said 3rd A double bond (C=C) is formed between a primary carbon atom and a carbon atom adjacent to it, resulting in a more stable formation of a new compound.

It is preferable that the new compound produced|generated as mentioned above volatilizes. In this case, the film thickness of the cured product (cured film) is reduced due to volatilization of the new compound in the cured product. increases after heating. Therefore, while being able to implement|achieve further thinning, it becomes possible to achieve higher color purity and higher light-shielding rate of the black matrix. In consideration of this point, R ⁶ , R ⁷ and R ⁸ are the same or different and are preferably a saturated hydrocarbon group having 1 to 15 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, still more preferably is a saturated hydrocarbon group having 1 to 5 carbon atoms, particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

The tertiary carbon-containing (meth)acrylate-based monomer is preferably (meth)acrylic acid t-butyl or (meth)acrylic acid t-amyl.

From the viewpoint of developability and water non-uniformity suppression effect, the tertiary carbon-containing (meth)acrylate-based monomer is preferably a tertiary carbon-containing methacrylate-based monomer, and t-butyl methacrylate or methacrylic acid It is more preferable that it is t-amyl.

The said polymer may have only 1 type among those mentioned above as said vinylic monomeric unit (B), and may have 2 or more types.

Content of the said vinylic monomeric unit (B) in the said polymer is 5-80 mass % with respect to 100 mass % of all the monomer units of the said polymer. The content of the vinyl monomer unit (B) is preferably 10 mass % or more, more preferably 15 mass % or more, still more preferably 20 mass % or more, based on 100 mass % of all monomer units of the polymer, and , It is preferable that it is 70 mass % or less, It is more preferable that it is 65 mass % or less, It is more preferable that it is 60 mass % or less.

From the viewpoint of further excellent heat-resistant colorability, the content of the vinyl monomer unit (B) is more preferably from 10 to 70 mass%, more preferably from 20 to 60 mass%, based on 100 mass% of all monomer units. .

Moreover, since it is excellent also in developability and the water non-uniformity suppression effect, it is preferable that content of the said vinyl type monomeric unit (B) is 5-70 mass % with respect to 100 mass % of all the monomer units of the said polymer, and it is 10 mass % or more. It is more preferable, it is more preferable that it is 15 mass % or more, It is more preferable that it is 65 mass % or less, It is still more preferable that it is 60 mass % or less.

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

It is preferable that the polymer of this invention is a ring structure containing polymer which has a ring structure in a principal chain. By further including a ring structure in the main chain, the heat resistance of the polymer can be further improved.

Examples of the ring structure include an imide ring, a tetrahydrofuran ring, and a lactone ring. Since it has these ring structures, it is preferable that the said ring structure containing polymer has a monomeric unit (henceforth "monomer unit (C)") which has a ring structure in a principal chain.

As the monomer providing the monomer unit (C), for example, a monomer having a double bond-containing ring structure in the molecule, a monomer that is subjected to cyclization polymerization to form a polymer having a ring structure in the main chain, and a ring structure after polymerization The monomers to be formed, etc. are mentioned. Among them, N-substituted maleimide-based monomers, dialkyl-2,2'-(oxydimethylene)diacrylate-based monomers, and α-(unsaturated alkoxyalkyl) At least one type of monomer selected from the group consisting of acrylate-based monomers is preferable, and N-substituted maleimide-based monomers, and dialkyl-2,2'-(oxydimethylene)di, from the viewpoint of further excellent heat-resistant colorability At least one type of monomer selected from the group consisting of acrylate-based monomers is more preferable. Moreover, an N-substituted maleimide-type monomer is preferable at the point which can improve the water nonuniformity suppression effect.

Examples of the N-substituted maleimide-based monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and Nt-butylmaleimide. , N-dodecyl maleimide, N-benzyl maleimide, N-naphthyl maleimide, etc. are mentioned, and these 1 type, or 2 or more types can be used. Among them, from the viewpoint of transparency, N-phenylmaleimide, N-benzylmaleimide and N-cyclohexylmaleimide are preferable, and N-cyclohexylmaleimide is particularly preferable. Moreover, N-phenylmaleimide and/or N-cyclohexylmaleimide are preferable and N-phenylmaleimide is more preferable at the point which improves heat-resistant colorability and the inhibitory effect of water nonuniformity.

As said N-benzyl maleimide, For example, benzyl maleimide; Alkyl-substituted benzyl maleimide, such as p-methylbenzyl maleimide and p-butylbenzyl maleimide; Phenolic hydroxyl group-substituted benzyl maleimide, such as p-hydroxybenzyl maleimide; halogen-substituted benzylmaleimides such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide, and p-dichlorobenzylmaleimide; and the like.

Examples of the dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl- 2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(iso propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate; di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(t-butyl)-2,2'-[oxybis(methylene)]bis-2-pro Phenoate, di(t-amyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(stearyl)-2,2'-[oxybis(methylene)]bis- 2-propenoate, di(lauryl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)] )] bis-2-propenoate and the like. Among these, from the viewpoints of transparency, dispersibility, industrial availability, etc., dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate is more preferable.

Examples of the α-(unsaturated alkoxyalkyl)acrylate-based monomer include an α-(allyloxymethyl)acrylate-based monomer.

Specific examples of the α-(allyloxymethyl)acrylate-based monomer include, for example, α-allyloxymethylacrylic acid; α-allyloxymethyl methyl acrylate, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl acrylate n-propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxy s-butyl methyl acrylate, α-allyloxymethyl acrylate t-butyl, α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxy Methyl acrylic acid n-hexyl, α-allyloxymethyl acrylic acid s-hexyl, α-allyloxymethyl acrylic acid n-heptyl, α-allyloxymethyl acrylic acid n-octyl, α-allyloxymethyl acrylic acid s-octyl, α-allyloxy t-octyl methyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, capryl α-allyloxymethyl acrylate, nonyl α-allyloxymethyl acrylate, α-allyloxymethyl decyl acrylate, α-allyloxymethyl undecyl acrylate , α-allyloxymethyl acrylate lauryl, α-allyloxymethyl acrylate tridecyl, α-allyloxymethyl acrylate myristyl, α-allyloxymethyl acrylate pentadecyl, α-allyloxymethyl acrylate cetyl, α-allyloxy Heptadecyl methylacrylate, α-allyloxymethyl stearyl acrylate, α-allyloxymethyl acrylate nonadecyl, α-allyloxymethyl acrylic acid eicosyl, α-allyloxymethyl acrylic acid seryl, α-allyloxymethyl acrylate melicyl, etc. alkyl-(α-allyloxymethyl)acrylate monomers; α-Allyloxymethylacrylate methoxyethyl, α-allyloxymethylacrylate methoxyethoxyethyl, α-allyloxymethylacrylate methoxyethoxyethoxyethyl, α-allyloxymethylacrylate 3-methoxybutyl, α- Alkoxyalkyl-(α-allyl), such as ethoxyethyl allyloxymethylacrylate, α-allyloxymethylacrylate ethoxyethoxyethyl, α-allyloxymethylacrylate phenoxyethyl, and α-allyloxymethylacrylate phenoxyethoxyethyl oxymethyl) acrylate-based monomer; α-allyloxymethyl acrylate hydroxyethyl, α-allyloxymethyl acrylate hydroxypropyl, α-allyloxymethyl acrylate hydroxybutyl, α-allyloxymethyl acrylate fluoroethyl, α-allyloxymethyl acrylate difluoroethyl , α-allyloxymethyl acrylate chloroethyl, α-allyloxymethyl acrylate dichloroethyl, α-allyloxymethyl acrylate bromoethyl, α-allyloxymethyl acrylate dibromoethyl, α-allyloxymethyl acrylate vinyl, α- Allyl allyloxymethyl acrylate, α-allyloxymethyl methallyl acrylate, α-allyloxymethyl acrylate crotyl, α-allyloxymethyl acrylate propargyl, α-allyloxymethyl acrylate cyclopentyl, α-allyloxymethyl acrylate cyclohexyl , α-allyloxymethyl acrylic acid 4-methylcyclohexyl, α-allyloxymethyl acrylic acid 4-t-butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-allyloxymethyl acrylate isobornyl, α- Allyloxymethyl acrylate adamantyl, α-allyloxymethyl acrylate dicyclopentadienyl, α-allyloxymethyl acrylate phenyl, α-allyloxymethyl acrylate methylphenyl, α-allyloxymethyl acrylate dimethylphenyl, α-allyloxymethyl Trimethylphenyl acrylate, α-allyloxymethyl acrylate 4-t-butylphenyl, α-allyloxymethyl acrylate benzyl, α-allyloxymethyl acrylate diphenylmethyl, α-allyloxymethyl acrylate diphenylethyl, α-allyloxymethyl triphenylmethyl acrylate, α-allyloxymethyl cinnamyl acrylate, α-allyloxymethyl naphthyl acrylate, α-allyloxymethyl acrylate anthranyl; and the like. Among them, an alkyl-(α-allyloxymethyl)acrylate-based monomer is preferable. The alkyl-(α-allyloxymethyl)acrylate monomer is α-allyloxymethylmethylacrylate (methyl-(α-allyloxymethyl)acryl) from the viewpoint of transparency, dispersibility, industrial availability, and the like. rate) is particularly preferred.

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

As a monomer which provides the said monomeric unit (C), 2-(hydroxyalkyl) acrylic acid alkylester is mentioned further preferably. 2-(hydroxyalkyl) acrylic acid alkyl ester can react with (meth)acrylic acid to form a lactone ring structure in the main chain. Examples of the lactone ring structure include a ring structure represented by the following general formula (II).

[Formula 3]

In the 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 each the same as R ⁹ and R ¹⁰ in General Formula (III) described later.

As said 2-(hydroxyalkyl) acrylic acid alkylester, the compound represented by the following general formula (III) is mentioned.

[Formula 4]

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

In the said general formula (III), R< ⁹ > represents a C1-C20 alkyl group. Linear may be sufficient as the said alkyl group, and branched form may be sufficient as it.

From the viewpoint of the solubility of a monomer, carbon number of R< ⁹ > becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

R ⁹ is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, or a 2-ethylhexyl group. and the like. Preferably, it is a methyl group.

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

As said C1-C20 organic residue, For example, C1-C20 alkyl groups, such as a methyl group, an ethyl group, and a propyl group; C1-C20 unsaturated aliphatic hydrocarbon groups, such as an ethenyl group and a propenyl group; C1-C20 aromatic hydrocarbon groups, such as a phenyl group and a naphthyl group; In the alkyl group, the unsaturated aliphatic hydrocarbon group, and the aromatic hydrocarbon group, one or more hydrogen atoms are substituted with at least one group selected from a hydroxyl group, a carboxyl group, an ether group, and an ester group, and the like. Among them, as R ¹⁰ , a hydrogen atom is preferable from the viewpoint of the hydrophilicity of the lactone ring.

As said 2-(hydroxyalkyl) acrylic acid alkylester, 2-(1-hydroxyalkyl) acrylic acid alkyl ester and 2-(2-hydroxyalkyl) acrylic acid alkylester are mentioned, Specifically, For example, For example, 2-(1-hydroxymethyl)methyl acrylate, 2-(1-hydroxymethyl)ethyl acrylate, 2-(1-hydroxymethyl)isopropyl acrylate, 2-(1-hydroxymethyl)acrylic acid n- butyl, t-butyl 2-(1-hydroxymethyl) acrylate, 2-ethylhexyl 2-(1-hydroxymethyl) acrylate, etc. are mentioned. Especially, 2-(1-hydroxymethyl) methyl acrylate and 2-(1-hydroxymethyl) ethyl acrylate are preferable. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

The content of the monomer unit (C) in the polymer is preferably 2 mass% or more, and more preferably 5 mass% or more, based on 100 mass% of all monomer units of the polymer, from the viewpoint of further improving heat-resistant colorability. Preferably, it is more preferably 10 mass % or more, particularly preferably 15 mass % or more, and more preferably 80 mass % or less, more preferably 70 mass % or less, still more preferably 60 mass % or less, and 50 mass % or less % or less, and particularly preferably 40 mass% or less.

Specifically, the content of the monomer unit (C) is preferably 2 to 60 mass%, more preferably 5 to 50 mass%, still more preferably 5 to 60 mass% with respect to 100 mass% of all monomer units of the polymer. It is 40 mass %.

From the viewpoint that the developability of the polymer and the effect of suppressing water non-uniformity can be improved, the content of the monomer unit (C) is preferably 10 to 70 mass%, more preferably 10 to 70 mass%, based on 100 mass% of all monomer units of the polymer. Preferably, it is 15-60 mass %.

<hydroxyl group-containing monomer unit (D)>

The polymer of the present invention may further include a hydroxyl group-containing monomer unit (hereinafter, also referred to as "monomer unit (D)"). By further including a hydroxyl-containing monomeric unit, heat-resistant coloring property can be improved further. This is because the hydroxyl group captures radicals in the reaction system to reduce the influence of the radicals, and reacts with an acid group formed by detachment of the tertiary carbon atom of the vinyl-based monomer unit (B) to form a crosslinked structure, It is estimated that it is based on the formation of one film|membrane (hardened|cured material).

Although it will not specifically limit if it is a compound which has a hydroxyl group and a polymerizable double bond in a molecule|numerator as said hydroxyl-containing monomer, For example, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth) Acrylic acid 3-hydroxypropyl, (meth)acrylic acid 2-hydroxybutyl, (meth)acrylic acid 3-hydroxybutyl, (meth)acrylic acid 4-hydroxybutyl, (meth)acrylic acid 2,3-hydroxypropyl, etc. Hydroxyalkyl (meth)acrylate is mentioned preferably, More preferably, 2-hydroxyethyl (meth)acrylate is mentioned. By superposing|polymerizing the monomer component containing such a hydroxyl-containing monomer, the polymer which has the said monomeric unit (D) can be obtained.

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

The content of the monomer unit (D) in the polymer is preferably 1 mass % or more, and more preferably 5 mass % or more, based on 100 mass % of all monomer units of the polymer, from the viewpoint of further improving heat-resistant colorability. Preferably, it is more preferably 10 mass % or more, more preferably 60 mass % or less, more preferably 55 mass % or less, still more preferably 50 mass % or less, particularly preferably 30 mass % or less, and 20 mass % or less % or less is most preferable.

To be specific, content of the said monomeric unit (D) becomes like this with respect to 100 mass % of all the monomer units of the said polymer. Preferably it is 1-30 mass %, More preferably, it is 5-20 mass %.

From the viewpoint that the developability of the polymer and the effect of suppressing water non-uniformity can be improved, the content of the monomer unit (D) is preferably 1 to 60 mass%, more preferably 1 to 60 mass%, based on 100 mass% of all monomer units of the polymer. Preferably it is 5-55 mass %, More preferably, it is 10-50 mass %.

<Aromatic vinyl monomer unit (E)>

The polymer of the present invention may further have an aromatic vinyl-based monomer unit (hereinafter also referred to as “monomer unit (E)”.). By further having an aromatic vinylic monomer unit, in addition to heat-resistant coloring property, developability and the water nonuniformity suppression effect can be improved.

The said aromatic vinylic monomeric unit is a structural unit derived from an aromatic vinylic monomer, The structural unit derived from the monomer which has an aromatic group and a vinyl group is mentioned preferably.

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

The said aromatic group may have a substituent. As said substituent, a C1-C5 alkyl group, a C1-C5 alkoxy group, etc. are mentioned, for example.

Specific examples of the aromatic vinyl-based monomer include styrene, vinyltoluene, α-methylstyrene, xylene, methoxystyrene, and ethoxystyrene. Among them, thermal decomposition resistance is improved, Preferably, styrene and vinyltoluene are mentioned, More preferably, vinyltoluene is mentioned from the point of the dissolution rate with respect to an organic solvent and alkali is high. By superposing|polymerizing the monomer component containing such an aromatic vinylic monomer, the polymer which has the said monomeric unit (E) can be obtained.

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

The content of the monomer unit (E) in the polymer is preferably 1 mass % or more, and more preferably 2 mass % or more, based on 100 mass % of all monomer units, from the viewpoint of further improving the heat-resistant colorability of the polymer. Preferably, it is more preferably 3 mass% or more, even more preferably 5 mass% or more, particularly preferably 10 mass% or more, most preferably 15 mass% or more, and preferably 80 mass% or less, It is more preferable that it is 70 mass % or less, It is still more preferable that it is 60 mass % or less, It is especially preferable that it is 50 mass % or less, It is most preferable that it is 40 mass % or less.

Specifically, the content of the monomer unit (E) is preferably 1 to 60 mass%, more preferably 2 to 50 mass%, still more preferably 3 to 40 mass%, based on 100 mass% of all monomer units. am.

From the viewpoint that the developability of the polymer and the effect of suppressing water non-uniformity can be improved, the content of the monomer unit (E) is preferably from 5 to 80 mass% with respect to 100 mass% of all monomer units, more preferably It is 10 mass % or more, More preferably, it is 15 mass % or more, More preferably, it is 70 mass % or less, More preferably, it is 60 mass % or less.

<Other monomer units (F)>

The polymer of the present invention may contain other polymerizable monomer units (hereinafter, also referred to as "monomer unit (F)") as needed other than the above-mentioned monomer units.

Examples of the other polymerizable monomer unit include a monomer unit derived from an acid group-containing monomer, a (meth)acrylic acid ester-based monomer other than the monomer providing the vinyl-based monomer unit (B), and other copolymerizable monomers. there is.

As said acidic radical containing monomer, compounds other than the said monomeric unit (A) which have an acidic radical and a polymerizable double bond in a molecule|numerator are mentioned.

Examples of the acid group include a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group. there may be Especially, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable.

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 unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; unsaturated polyhydric carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; Unsaturated acid anhydrides, such as maleic anhydride and itaconic anhydride; Phosphoric acid group-containing unsaturated compounds, such as light ester P-1M (made by Kyoeisha Chemicals); and the like. Among these, it is preferable to use a carboxylic acid-type monomer (unsaturated monocarboxylic acids, unsaturated polyhydric carboxylic acids, unsaturated acid anhydrides) from viewpoints, such as versatility and availability. From the viewpoints of reactivity, suppression of water nonuniformity, heat resistance, and the like, more preferably unsaturated monocarboxylic acids, and still more preferably (meth)acrylic acid (ie, acrylic acid and/or methacrylic acid).

Examples of (meth)acrylic acid ester-based monomers other than the monomer providing the vinyl-based monomer unit (B) include (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid n-propyl, (meth) ) acrylic acid i-propyl, (meth)acrylic acid n-butyl, (meth)acrylic acid s-butyl, (meth)acrylic acid n-amyl, (meth)acrylic acid s-amyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid 2-ethylhexyl, (meth) acrylate isodecyl, (meth) acrylate tridecyl, (meth) acrylate octyl, (meth) acrylate isooctyl, (meth) acrylic acid lauryl, (meth) acrylate stearyl, (meth) acrylic acid Cyclohexyl, (meth)acrylic acid dicyclopentanyl, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid tetrahydrofurfuryl, (meth)acrylic acid N,N-dimethylamino Ethyl, 1,4-dioxaspiro [4,5] deca-2-yl methacrylic acid, (meth) acryloyl morpholine, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl- 1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl -2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, etc. are mentioned.

As said other copolymerizable monomer, 1 type, or 2 or more types, such as the following compound, are mentioned, for example.

(meth)acrylamides, such as N,N- dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; macromonomers having a (meth)acryloyl group at one end of a polymer molecular chain, such as polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam; conjugated dienes such as 1,3-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, ethoxyethyl vinyl ether , vinyl ethers such as methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether; N-vinyl compounds, such as N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinylimidazole, N-vinyl morpholine, and N-vinyl acetamide; Unsaturated isocyanates, such as (meth)acrylic-acid isocyanatoethyl and allyl isocyanate; and the like.

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

When the said polymer has the said monomeric unit (F), as content of the said monomeric unit (F), it is preferable that it is 1 mass % or more with respect to 100 mass % of all the monomer units of the said polymer, and it is more preferable that it is 2 mass % or more. and more preferably 3 mass % or more, particularly preferably 5 mass % or more, most preferably 10 mass % or more, more preferably 60 mass % or less, more preferably 55 mass % or less, and more preferably 50 mass % or more. % or less is more preferable, and it is particularly preferable that it is 40 mass% or less.

From the viewpoint of further improving the heat-resistant colorability of the polymer, the content of the monomer unit (F) is preferably 1 to 60 mass%, more preferably 2 to 50 mass%, based on 100 mass% of all monomer units of the polymer. It is mass %, More preferably, it is 3-40 mass %.

From the viewpoint of improving the developability of the polymer and the effect of suppressing water non-uniformity, the content of the monomer unit (F) is preferably 1 to 60 mass%, more preferably 1 to 60 mass%, based on 100 mass% of all monomer units of the polymer. Preferably it is 5-55 mass %, More preferably, it is 10-50 mass %.

In the polymer, the content of the acid group-containing monomer unit (preferably (meth)acrylic acid unit) is preferably less than 5 mass%, more preferably less than 3 mass%, based on 100 mass% of all monomer units of the polymer. and less than 1 mass % is more preferable. When content of an acidic radical containing monomeric unit is less than 5 mass %, the hardened|cured material further excellent in heat-resistant coloring property 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, and preferably 180 mgKOH/g or less, and 170 mgKOH or more. It is more preferable that it is /g or less, It is still more preferable that it is 160 mgKOH/g or less, It is especially preferable that it is 150 mgKOH/g or less.

From a viewpoint of heat-resistant coloring property, it is preferable that the acid value of the said polymer is 40-180 mgKOH/g, It is more preferable that it is 40-160 mgKOH/g, It is more preferable that it is 50-150 mgKOH/g, It is 60-140 It is particularly preferred that it is mgKOH/g.

From a viewpoint of developability and suppression of water nonuniformity, it is preferable that the acid value of the said polymer is 40-180 mgKOH/g, It is more preferable that it is 50-170 mgKOH/g, It is more preferable that it is 60-160 mgKOH/g .

The said acid value is a value obtained by measuring by the neutralization titration method using potassium hydroxide (KOH) solution.

Although the weight average molecular weight of the polymer of this invention is not specifically limited, Preferably it is 2000 or more, More preferably, it is 3000 or more, More preferably, it is 4000 or more, More preferably, it is 5000 or more, Especially preferably, it is 6000 or more, Most preferably, it is 7000 or more, More preferably, it is 1000000 or less, More preferably, it is 80000 or less, More preferably, it is 50000 or less, Especially preferably, it is 40000 or less, Most preferably, it is 35000 or less.

From a viewpoint of heat-resistant coloring property, 2000-1000000 are preferable, as for the weight average molecular weight of the said polymer, 3000-80000 are more preferable, 4000-50000 are still more preferable.

From a viewpoint of developability and water nonuniformity suppression, 5000-50000 are preferable, as for the weight average molecular weight of the said polymer, it is more preferable that it is 6000-40000, It is still more preferable that it is 7000-35000.

The weight average molecular weight of the said polymer is a value obtained by measuring by the method as described in an Example by the gel permeation chromatography method (GPC).

The polymer is prepared by coating a resin composition containing the polymer on a glass substrate to form a coating film, and drying the laminate at 100 ° C. for 3 minutes, followed by heat treatment at 250 ° C. for 3 hours. In this case, it is preferable that the b ^* value calculated|required according to JIS Z 8729 of the coating-film side surface of the said laminated body is 6 or less. The b ^* value is expressed as a chromaticity indicating saturation based on the L ^* a ^* b ^* color space standardized by CIE and adopted by JIS Z 8729 in Japan.

The 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 said b ^* value is performed using the laminated body which apply|coated the resin composition containing the said polymer on the glass substrate, and formed the coating film.

Specifically, the resin composition is applied on a glass substrate in an application 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, whereby a coating film of the resin composition is formed on a glass substrate. get a sieve And after heat-processing the obtained laminated body at 250 degreeC for 3 hours further, it cools to normal temperature, and the b ^* value of the coating-film side surface is measured using the color difference meter. About the said resin composition, it measures using at least two laminated bodies, and prepares the approximate straight line of the application amount (x) and b ^* value (y) from these results as a calibration curve. Using the above-mentioned calibration curve, the b ^* value in the case of an application amount of 0.6 mg/cm 2 is calculated, and this is the b ^* value in the present invention.

As said glass substrate, what is necessary is just to use soda-lime glass AS-2K (made by Toshin Ricoh), for example.

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

As said color difference meter, what is necessary is just to use ZE6000 (made by Nippon Denshoku Industries Co., Ltd.), for example.

<Forms (2) and (3)>

Moreover, as another aspect of the preferable polymer excellent in heat-resistant coloring property, the following aspects (2) and (3) are mentioned. In particular, aspect (3) is excellent in developability in addition to heat-resistant coloring property, and can provide the hardened|cured material by which water nonuniformity was suppressed. The polymers of these aspects (2) and (3) are also one of the present inventions.

Form (2):

As a ring structure-containing polymer having a ring structure in the main chain, the ring structure-containing polymer is a monomer unit represented by the following general formula (I), -COO ^* R ⁴ (R ⁴ represents a monovalent organic group, O ^* to The carbon atom to be bonded is a tertiary carbon atom.) A ring structure-containing polymer having a group-containing vinyl monomer unit and a hydroxyl group-containing monomer unit.

[Formula 5]

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms. R ³ is 2 represents an organic group of valence.X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid 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 1 or more It is a number, where n is 0 or 1.)

Form (3):

An aromatic vinylic monomer unit, and the polymer which has an acidic radical in a side chain part, and has the vinylic monomeric unit (X) in which the said acidic radical is located 5 or more atoms away from a main chain.

The "cyclic structure-containing polymer having a ring structure in the main chain" in aspect (2) has the same monomer unit as the monomer unit (C) in aspect (1) described above, and is represented by "general formula (I)" The monomer unit" is the same as the monomer unit (A) of the aspect (1) described above, and "-COO ^{* R4} ( ^R4 represents a monovalent organic group, and the carbon atom couple|bonded with O ^* is a tertiary It is a carbon atom.) The vinyl-based monomer unit containing a group” is the same as the vinyl-based monomer unit (B) of the above-described aspect (1), and the “hydroxyl group-containing monomer unit” is the above-mentioned aspect (1) The same thing as the monomer unit (D) is preferable.

In the aspect (2), a cured product excellent in heat color resistance can be provided, when the cyclic structure-containing polymer is heated, a part of the monomer unit represented by the general formula (I) is detached to form a hydroxyl group, , This hydroxyl group and the hydroxyl group of the hydroxyl group-containing monomer unit capture radicals in the reaction system to reduce the influence of radicals, and when the ring structure-containing polymer is heated, -COO ^* R ⁴ (R ⁴ is, represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom.) The tertiary carbon atom of the vinyl-based monomer unit containing the group is released to form an acid group, and the acid group and the hydroxyl group described above It is estimated that it depends on the formation of a strong film|membrane (hardened|cured material) by bridge|crosslinking.

The polymer of aspect (2) may have further arbitrary monomeric units, and the monomeric unit described in aspect (1) is mentioned as said arbitrary monomeric units. It is preferable that content of each monomeric unit is the same as that of aspect (1).

Moreover, it is preferable that the acid value of the polymer of aspect (2), a weight average molecular weight, and b ^* value are the same as those of the polymer of aspect (1) mentioned above.

It is preferable that the "aromatic vinylic monomeric unit" in aspect (3) is the same as that of the monomeric unit (E) of aspect (1) mentioned above.

In aspect (3), it is estimated that the hardened|cured material with which water nonuniformity was suppressed can be provided because the hydrophobicity of the hardened|cured material obtained becomes high when the said polymer has an aromatic vinyl monomer unit. Moreover, the thing excellent in developability is that since the said polymer has the said vinyl monomer unit (X), the carboxyl group which expresses alkali developability can be arrange|positioned at a position far from the main chain of a polymer with high hydrophobicity, and, thereby, a developing solution It is presumed that this is because the probability of contact with the

In the polymer of aspect (3), "the vinyl-type monomeric unit (X) which has an acidic radical in a side chain part and the said acidic radical is in the position away from the principal chain by 5 atoms or more" is demonstrated.

Examples of the acid group include a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group. may have Especially, as said acidic radical, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable.

The acid group is located at a position 5 or more atoms away from the main chain. In the present invention, when the acid group is located at a position 5 or more atoms away from the main chain, the position of the carbon atom on the main chain of the polymer to which the side chain is bonded is 0 (zero), and the fifth position of the side chain from that position A state in which an acid group exists after an atom. An atom or a substituent other than carbon may be sufficient as the atom on a side chain. Specifically, for example, in the case of the following formula (b), the acid group X in the formula is at a position 5 atoms away from the main chain, and in the case of the formula (c), the acid group X is at a position 7 atoms away from the main chain can be said to be in

[Formula 6]

In the above-mentioned vinylic monomer unit (X) in the polymer of the aspect (3), from the viewpoint of further excellent developability, the acid group is preferably located at a position 5 atoms or more away from the main chain. In addition, the acid group is preferably located at a position not more than 18 atoms apart, more preferably at a position 16 atoms or less apart, and still more preferably at a position 14 atoms or less away from the viewpoint of maintaining adequate solubility in the developer. Do.

As said vinylic monomeric unit (X), the thing similar to the monomeric unit (A) of aspect (1) mentioned above is mentioned preferably.

In the aspect (3), the content of the monomer unit (A) is more preferably 10 mass % or more, more preferably 15 mass % or more, particularly preferably 20 mass % or more, based on 100 mass % of all monomer units. Moreover, it is more preferable that it is 65 mass % or less, and it is still more preferable that it is 60 mass % or less.

It is preferable that the polymer of aspect (3) contains the N-substituted maleimide-type monomeric unit (Y) further. When the polymer has an N-substituted maleimide-based monomer unit, it is possible to provide a cured product having an even more excellent water non-uniformity suppression effect, and a cured product excellent in heat color resistance as well.

When the polymer of aspect (3) further has an N-substituted maleimide-type monomeric unit (Y), it is estimated that the inhibitory effect of water nonuniformity improves further for the following reasons. That is, when the polymer has an N-substituted maleimide-based monomer unit (Y), the polymer, together with a monomer providing the monomer unit (E) and the vinyl-based monomer unit (X), is an N-substituted maleimide-based monomer unit. It is obtained by polymerizing a monomer. At the time of this polymerization, the aromatic vinylic monomer and the N-substituted maleimide-based monomer providing the monomer unit (E) have good alternating copolymerizability, so that they are easily introduced adjacent to each other in the polymer. Therefore, in the polymer, a portion having a large proportion of the hydrophobic monomer unit (E) and the N-substituted maleimide-based monomer unit (Y) and a hydrophilic vinyl monomer unit (X) having a large proportion are produced. It is estimated that developability can also be improved still further while the inhibitory effect of water nonuniformity is exhibited further by becoming.

As the N-substituted maleimide-based monomer unit (Y) in the aspect (3), a monomer unit derived from the same monomer as the N-substituted maleimide-based monomer of the monomer providing the monomer unit (C) in the aspect (1). is preferably mentioned, and at least one selected from the group consisting of N-phenyl maleimide monomer units and N-cyclohexyl maleimide monomer units is more preferable.

The polymer of aspect (3) may have further arbitrary monomeric units. As said arbitrary monomeric unit, the monomeric unit described in aspect (1) is mentioned. It is preferable that content of each monomeric unit is the same as that of aspect (1) except having described in particular.

In the polymer of aspect (3), it is preferable that the content ratio (E)/(X) of the said monomeric unit (E) and the said vinylic monomeric unit (X) is 10/60-60/10 in molar ratio. It becomes the thing excellent in the inhibitory effect of water nonuniformity and developability as the said content rate is the above-mentioned range. As for the said content ratio (E)/(X), it is more preferable that it is 13/55 - 55/13, It is still more preferable that it is 15/50 - 50/15.

In the polymer of aspect (3), when it has the said monomeric unit (E), the said vinylic monomeric unit (X), and the said N-substituted maleimide-type monomeric unit (Y), suppression of water nonuniformity irrespective of another component It is preferable that these content ratios [(E)+(Y)]/(X) in the said polymer are 15/60-70/10 in molar ratio from the point which can fully exhibit an effect, and 20/55 It is more preferable that it is -65/13, and it is still more preferable that it is 25/50 - 60/15.

In the polymer of aspect (3), when it has the said monomeric unit (E), the said N-substituted maleimide-type monomeric unit (Y), the said vinyl-type monomeric unit (X), and the said monomeric unit (B), the said polymer The content ratio of these monomer units in [(E) + (Y)]/[(X) + (B)] is preferably 20/80 to 70/30 in molar ratio, and 25/75 to 65/ It is more preferable that it is 35, and it is still more preferable that it is 30/70 - 60/40.

Moreover, in the polymer of aspect (3), it is preferable that the total amount of the said monomeric unit (A) and the said vinylic monomeric unit (X) is 80 mol% or less with respect to 100 mol% of all the monomer components of a polymer. The inhibitory effect of water nonuniformity is further excellent that the said total amount is the above-mentioned range. As for the said total amount, it is more preferable that it is 70 mol% or less with respect to 100 mol% of all the monomer components. Moreover, from a developable viewpoint, it is preferable that it is 20 mol% or more with respect to 100 mol% of all the monomer components, and, as for the said total amount, it is more preferable that it is 25 mol% or more.

It is preferable that the acid value, weight average molecular weight, and b ^* value of the polymer of aspect (3) are the same as those of the polymer of aspect (1) mentioned above.

<Method for producing polymer>

As a method for producing the polymer of the present invention, for example, in the case of the polymer of aspect (1), if it is a method capable of obtaining a polymer having at least the above-mentioned monomer unit (A) and vinyl-based monomer unit (B) It is not particularly limited, and a monomer component comprising a monomer providing the above-mentioned monomer units (A) and (B) and, if necessary, a monomer providing the above-mentioned monomer units (C) to (F), The method of superposing|polymerizing by a well-known method is mentioned. Also in aspect (2) and aspect (3), similarly, what is necessary is just to superpose|polymerize the monomer component which contains at least the monomer which provides an essential monomeric unit by a well-known method.

The method of superposing|polymerizing the said monomer component is not specifically limited, A commonly used method, such as bulk polymerization, solution polymerization, emulsion polymerization, can be used. Especially, solution polymerization is preferable at the point which is industrially advantageous and structural adjustment, such as molecular weight, is easy. Moreover, polymerization method based on mechanisms, such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization, can be used for the polymerization mechanism of the said monomer component, From an industrially advantageous point, a polymerization method based on a radical polymerization mechanism This is preferable.

The compounding quantity of the said monomer component at the time of superposition|polymerization will not be specifically limited, if it is a polymer which is excellent in heat-resistant colorability, further excellent in developability, and provides the hardened|cured material in which water nonuniformity was suppressed, Each monomer in a polymer What is necessary is just to design suitably so that content of a unit may become the above-mentioned range.

For example, in the case of the polymer of aspect (1), as a monomer component, the monomer which provides the said monomeric unit (A) (10-60 mass %), and the monomer which provides the said vinylic monomeric unit (B) ( 5 to 80 mass%) is preferable, the monomer providing the monomer unit (A) (20 to 60 mass%), the monomer providing the vinyl monomer unit (B) (5 to 80 mass%), and the above It is more preferable to contain the monomer (2 to 60 mass %) providing the monomer unit (C), the monomer (20 to 50 mass %) providing the monomer unit (A), and the vinyl monomer unit (B) More preferred are a monomer (10 to 70 mass%) providing the above monomer unit (C) (5 to 50 mass%), and (meth)acrylic acid (less than 5 mass%).

Moreover, for example, in the case of the polymer of the said aspect (2), as a monomer component, the monomer which provides the said monomeric unit (A) (10-60 mass %), and the monomer which provides the said vinylic monomeric unit (B). (5 to 80 mass%), a monomer (1 to 30 mass%) providing the monomer unit (D), and a monomer (2 to 60 mass%) providing the monomer unit (C) , a monomer providing the monomer unit (A) (20 to 50 mass%), a monomer providing the vinyl monomer unit (B) (10 to 70 mass%), a monomer providing the monomer unit (D) ( 5 to 20 mass%), the monomer providing the monomer unit (C) (5 to 50 mass%), and other polymerizable monomers (2 to 50 mass%) are more preferably included, and the monomer unit (A) ) providing a monomer (20 to 50 mass%), a monomer providing the vinyl monomer unit (B) (20 to 60 mass%), and a monomer providing the monomer unit (D) (5 to 20 mass%) , a monomer that provides the monomer unit (C) (5 to 40 mass%), and (meth)acrylic acid (less than 5 mass%) more preferably.

The polymerization initiation method in the polymerization reaction may be a method capable of supplying the monomer component with the energy required for polymerization initiation from an active energy source such as heat, electromagnetic waves (for example, infrared, ultraviolet, X-ray, etc.) or electron beam, Moreover, when a polymerization initiator is used together, since the energy required for polymerization initiation can be reduced significantly and reaction control becomes easy, it is preferable. The molecular weight of the polymer obtained by superposing|polymerizing the said monomer component can be controlled by adjustment of the quantity and type of a polymerization initiator, polymerization temperature, the type and quantity of a chain transfer agent, etc.

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

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

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

When superposing|polymerizing the said monomer component by a radical polymerization mechanism, it is industrially advantageous and preferable to use the polymerization initiator which generate|occur|produces a radical by heat|fever. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy, and may be appropriately selected according to polymerization conditions such as polymerization temperature, solvent, and type of monomer to be polymerized. Moreover, you may use together reducing agents, such as a transition metal salt and amines, with a polymerization initiator.

As the polymerization initiator, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t -Butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) , dimethyl 2,2'-azobis(2-methylpropionate), hydrogen peroxide, and peroxides, azo compounds, etc. which are normally used as polymerization initiators, such as a persulfate, are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

In the said polymerization, you may use a chain transfer agent further as needed. Preferably, a polymerization initiator and a chain transfer agent are used together. When a chain transfer agent is used at the time of polymerization, there exists a tendency which can suppress the increase of molecular weight distribution and gelatinization.

As said chain transfer agent, the thing similar to the solvent of Unexamined-Japanese-Patent No. 2015-157909 is mentioned, These 1 type, or 2 or more types can be used. Among them, from the viewpoint of availability, crosslinking prevention ability, and a small degree of polymerization rate decrease, preferably mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans, mercapto alcohols, and compounds having a mercapto group, such as aromatic mercaptans and mercaptoisocyanurates, and more preferably alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, and more Preferably, n-dodecyl mercaptan and mercaptopropionic acid are mentioned.

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

Regarding the polymerization conditions, the polymerization temperature may be appropriately set depending on the type and amount of the monomer to be used, the type or amount of the polymerization initiator, etc. For example, 50 to 150°C is preferable, and 70 to 120°C is more preferably. Moreover, although polymerization time can also be set suitably similarly, for example, 1 to 5 hours are preferable and 2 to 4 hours are more preferable.

2. Curable resin composition

The polymer mentioned above can be further set as curable resin composition by combining with a polymeric compound. Since the said curable resin composition contains the said polymer, it can provide the hardened|cured material excellent in heat-resistant coloring property. Moreover, it is excellent in the inhibitory effect of water nonuniformity and developability, and can provide the hardened|cured material excellent also in sclerosis|hardenability, adhesiveness to a base material, surface hardness, heat resistance, solvent resistance, etc.

Thus, the curable resin composition containing the said polymer and a polymeric compound is also one of this invention.

In the curable resin composition of the present invention, the content of the polymer is not particularly limited, and may be appropriately designed according to the use or blending of other components, for example, 5 mass% with respect to 100 mass% of the total solid content of the curable resin composition % or more is preferable, 7 mass % or more is more preferable, 10 mass % or more is still more preferable, 15 mass % or more is especially preferable, 20 mass % or more is most preferable, and 80 mass % or less is preferable. and 70 mass % or less is more preferable, 60 mass % or less is still more preferable, 55 mass % or less is especially preferable, and 50 mass % or less is the most preferable.

When the polymer of the said aspect (1) or (2) is included, as for content of the said polymer, 5-80 mass % is preferable with respect to 100 mass % of solid content total amount of curable resin composition, and 7-70 mass % is more It is preferable, and 10-60 mass % is still more preferable.

When the polymer of the aspect (3) is included, the content of the polymer is preferably 10 to 60 mass%, more preferably 15 to 55 mass%, and more preferably 20 to 100 mass% of the total solid content of the curable resin composition. -50 mass % is more preferable.

In addition, the "total amount of solid content" means the total amount of components (excluding the solvent etc. which volatilize at the time of formation of hardened|cured material) which form hardened|cured material.

<Polymerizable compound>

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

As said monofunctional compound, For example, N-substituted maleimide-type monomer; (meth)acrylic acid esters; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polyhydric carboxylic acids; Unsaturated monocarboxylic acids in which the chain between the unsaturated group and the carboxyl group is extended; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; and the like. Moreover, the monomer etc. which have an active methylene group or an active methine group can also be used.

As said polyfunctional compound, the following compound 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, hexanediol di Bifunctional (meth)acrylate compounds such as (meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, and bisphenol F alkylene oxide di(meth)acrylate ;

Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide addition trimethylol propane tri (meth)acrylate, ethylene oxide addition ditrimethylolpropane tetra(meth)acrylate, ethylene oxide addition pentaerythritol tetra(meth)acrylate, ethylene oxide addition dipentaerythritol hexa(meth)acrylate, propylene oxide addition Trimethylolpropane tri(meth)acrylate, propylene oxide addition ditrimethylolpropane tetra(meth)acrylate, propylene oxide addition pentaerythritol tetra(meth)acrylate, propylene oxide addition dipentaerythritol hexa(meth)acrylate , ε-caprolactone addition trimethylolpropane tri(meth)acrylate, ε-caprolactone addition ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone addition pentaerythritol tetra(meth)acrylate, ε-capro Lactone addition dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinic acid modified product, pentaerythritol triacrylate succinic acid modified product, dipentaerythritol pentaacrylate phthalic acid modified product, pentaerythritol triacrylic acid Late phthalic acid modified product, the following formula:

[Formula 7]

polyfunctional (meth)acrylate compounds having more than trifunctionality, such as modified products of dipentaerythritol hexaacrylate represented by ;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkyl Renoxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene polyfunctional vinyl ethers such as oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition ditrimethylolpropane tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, and ethylene oxide addition dipentaerythritol hexavinyl ether;

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

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkyl Lenoxide diallyl ether, trimethylol propane triallyl ether, ditrimethylol propane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene Polyfunctional allyl ethers, such as oxide addition trimethylol propane triallyl ether, ethylene oxide addition ditrimethylol propane tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, and ethylene oxide addition dipentaerythritol hexaallyl ether;

Allyl group-containing (meth)acrylic acid esters, such as (meth)acrylic acid allyl; Tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide addition tri (acryloyloxyethyl) isocyanurate, alkylene oxide addition tri ( polyfunctional (meth)acryloyl group-containing isocyanurates, such as methacryloyloxyethyl) isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylic acid polyfunctional urethane (meth)acrylates obtained by polyfunctional aromatic vinyls such as divinylbenzene; etc. These polymeric compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable to use a polyfunctional polymeric compound from a viewpoint of improving more sclerosis|hardenability of curable resin composition among the said polymeric compound. As a functional number of the said polyfunctional polymeric compound, 3 or more are preferable and 4 or more are more preferable. Moreover, 10 or less are preferable and, as for the said functional number, 8 or less are more preferable.

Moreover, although it does not specifically limit as molecular weight of the said polymeric compound, From a viewpoint of handling, for example, 2000 or less are preferable.

Among them, the polyfunctional polymerizable compound is preferably a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate compound, or (meth) acryloyl from the viewpoint of reactivity, economy, availability, etc. The compound which has a (meth)acryloyl group, such as a diyl-containing isocyanurate compound, is mentioned, More preferably, a polyfunctional (meth)acrylate compound is mentioned. By including the compound which has a (meth)acryloyl group, a resin composition becomes the thing more excellent in photosensitivity and sclerosis|hardenability, and can obtain the hardened|cured material of still higher hardness and high transparency. As said polyfunctional polymeric compound, it is more preferable to use a trifunctional or more than trifunctional polyfunctional (meth)acrylate compound.

The said polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.

In the curable resin composition of the present invention, the content of the polymerizable compound is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately set. With respect to 100 mass % of the total solid content of the curable resin composition, preferably 2 mass % or more, more preferably 5 mass % or more, still more preferably 10 mass % or more, and preferably 80 mass % or less, more preferably Preferably it is 70 mass % or less, More preferably, it is 60 mass % or less, Especially preferably, it is 55 mass % or less, Most preferably, it is 50 mass % or less.

From a viewpoint of heat-resistant coloring property, content of the said polymeric compound becomes like this with respect to 100 mass % of solid content of the said curable resin composition, Preferably it is 2-80 mass %, More preferably, it is 5-70 mass %, More preferably, 10 - 60 mass %.

Moreover, from a viewpoint of developability and the water nonuniformity inhibitory effect, content of the said polymeric compound becomes like this with respect to 100 mass % of solid content total amount of the said curable resin composition, Preferably 2-60 mass %, More preferably, 5-55 mass %, more preferably 10 to 50 mass%.

<Photoinitiator>

It is preferable that the said curable resin composition contains a photoinitiator further. By including a photoinitiator, sclerosis|hardenability of curable resin composition can be improved, and the performance of the hardened|cured material obtained can be improved.

As said photoinitiator, Preferably, a radically polymerizable photoinitiator is mentioned. A radically polymerizable photoinitiator generates a polymerization initiation radical by irradiation with active energy rays, such as an electromagnetic wave and an electron beam.

Examples of the photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (“IRGACURE369”, manufactured by BASF), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4 Alkylphenone compounds, such as -morpholin-4-yl-phenyl)-butan-1-one ("IRGACURE379", the BASF company make); Benzyl ketal compounds such as 2,2-dimethoxy-1,2-diphenylethan-1-one (“IRGACURE651”, manufactured by BASF) and methyl phenylglyoxylate (“DAROCUR MBF”, manufactured by BASF) ; 1-Hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR1173", manufactured by BASF), 1 -[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE2959", manufactured by BASF), 2-hydroxy-1-{ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one ("IRGACURE127", manufactured by BASF), [1-hydroxyl- Hydroketone compounds, such as cyclohexyl-phenyl- ketone + benzophenone] ("IRGACURE500", the BASF make); et. 1,2-octanedione,1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime)] (“OXE01”, manufactured by BASF), ethanone, 1-[9-ethyl-6 -(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) ("OXE02", manufactured by BASF), 1,2-octanedione, 1-[4-( Phenylthio)-,2-, (O-benzoyloxime)], ethanone ("OXE03", manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -yl]-,1-(O-acetyloxime) ("OXE04", BASF company make)), such as an oxime ester type compound; benzophenone compounds; benzoin compounds; thioxanthone-based compounds; halomethylated triazine-based compounds; halomethylated oxadiazole compounds; biimidazole-based compounds; titanocene-based compounds; benzoic acid ester compounds; acridine-based compounds; phosphine oxide-based compounds; and the like. Among them, an alkylphenone-based compound is preferable.

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

Content of the said photoinitiator will not be restrict|limited in particular as long as the effect of this invention is exhibited, Although it may design suitably, For example, with respect to 100 mass % of solid content of curable resin composition of this 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, Moreover, Preferably it is 35 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 25 mass % or less, Especially preferably, it is 20 mass % or less.

From a viewpoint of more favorable heat-resistant coloring property, content of the said photoinitiator becomes like this with respect to 100 mass % of solid content total amount of curable resin composition, Preferably it is 0.1-30 mass %, More preferably, it is 0.5-25 mass %, More preferably Preferably, it is 1-20 mass %.

From a viewpoint of developability and the water nonuniformity suppression effect, content of the said photoinitiator becomes like this with respect to 100 mass % of solid content total amount of curable resin composition, Preferably it is 2-35 mass %, More preferably, it is 3-30 mass %, , More preferably, it is 5-25 mass %.

Moreover, you may use together 1 type, or 2 or more types, such as a photosensitizer, a radical photopolymerization accelerator, etc. as needed. With a photoinitiator, a sensitivity and sclerosis|hardenability improve more by using a photosensitizer and/or a radical photopolymerization accelerator together with a photoinitiator. It does not restrict|limit especially as a photosensitizer and a radical photopolymerization accelerator, What is necessary is just to select suitably from the well-known thing generally used in curable resin composition.

As a photosensitizer and photoradical polymerization accelerator which may be used together with the said photoinitiator, For example, Dye-type compounds, such as a xanthene dye, a coumarin dye, 3-ketocoumarin-type compound, and a pyromethene dye; dialkylaminobenzene-based compounds such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate; Mercaptan-type hydrogen donors, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzoimidazole, etc. are mentioned.

In the case of using the photosensitizer and the radical photopolymerization accelerator, the content is 0.001 to 20 mass% with respect to 100 mass% of the total solid content of the curable resin composition from the viewpoint of the balance of curability, the influence of decomposition products, and economical efficiency. It is preferable, More preferably, it is 0.01-15 mass %, More preferably, it is 0.05-10 mass %.

＜Other ingredients＞

The curable resin composition of this invention may contain the other component as needed other than the polymer mentioned above, a polymeric compound, and a photoinitiator. As another component, For example, a solvent; colorant (it is also called a colorant); dispersant; heat resistance improver; leveling agent; development aid; inorganic fine particles such as silica fine particles; Coupling agents, such as a silane type, an aluminum type, and a titanium type; Thermosetting resins, such as a filler, an epoxy resin, a phenol resin, and polyvinyl phenol; Hardening aids, such as a polyfunctional thiol compound; plasticizer; polymerization inhibitor; UV absorbers; antioxidants; polish remover ; antifoam; antistatic agent; slip agent; surface modifiers; thixotropic agent; thixotropic supplements; quinonediazide compound; polyhydric phenol compound; cationic polymerizable compound; acid generator; and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type. What is necessary is just to select and use a well-known thing suitably for these other components, and the usage-amount can also be designed suitably.

For example, when using the said curable resin composition for a color filter use, it is preferable that the said curable resin composition contains a color material.

(solvent)

As said solvent, what is used normally in curable resin composition can be used, What is necessary is just to select suitably according to the objective and a use, Although it does not specifically limit, For example, The thing similar to that described in Unexamined-Japanese-Patent No. 2015-157909 can be used. can be used These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

(color material)

As said color material, a pigment, dye, etc. are mentioned, for example. As said color material, either a pigment or dye may be used and you may use it combining a pigment and dye. For example, when forming the red, blue, and green pixels of a color filter, a well-known method in which the color characteristic requested|required by combining suitably color materials, such as fruits and vegetables, purple, green and yellow, may be used may be used. Moreover, when forming a black matrix, what is necessary is just to use a black color material.

Among color materials, a pigment is preferable from a durable point, and dye is preferable from the point of brightness improvement, such as a panel. These can be appropriately selected according to the required characteristics. In the curable resin composition of this invention, a pigment is preferable at the point which the solvent resistance in hardened|cured material and heat-resistant coloring property can improve further. As a pigment, the thing similar to that described in Unexamined-Japanese-Patent No. 2015-157909 can be used.

As said dye, the organic dye described in Unexamined-Japanese-Patent No. 2010-9033, Unexamined-Japanese-Patent No. 2010-211198, Unexamined-Japanese-Patent No. 2009-51896, and Unexamined-Japanese-Patent No. 2008-50599, for example. can be used Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable.

These color materials may be used individually by 1 type, and may be used in combination of 2 or more type.

Content of the said color material is not specifically limited, Although it can set suitably according to the objective and a use, Preferably it is 0.1 mass % or more with respect to 100 mass % of solid content of the said curable resin composition, More preferably, it is 1 mass % or more. , more preferably 2 mass% or more, particularly preferably 5 mass% or more, most preferably 10 mass% or more, and preferably 80 mass% or less, more preferably 70 mass% or less, still more preferably Preferably it is 60 mass % or less, More preferably, it is 20 mass % or less, Especially preferably, it is 15 mass % or less, Most preferably, 12 mass % or less is mentioned.

From a viewpoint of more favorable heat-resistant coloring property, content of the said color material is 2-80 mass % with respect to 100 mass % of solid content total of curable resin composition, More preferably, 5-70 mass %, More preferably, 10-60 mass % am.

From the viewpoint of developability and water non-uniformity suppression effect, the content of the color material is preferably 0.1 to 20 mass%, more preferably 1 to 15 mass%, still more preferably 0.1 to 20 mass% with respect to 100 mass% of the total solid content of the curable resin composition. is 2-12 mass %.

(dispersant)

When the curable resin composition of the present invention contains the color material, it is preferable to further contain a dispersant. By including a dispersing agent, dispersion|distribution to the dispersion medium of a color material can be stabilized. It does not restrict|limit especially as said dispersing agent, A well-known thing is mentioned, For example, a resin type dispersing agent, surfactant, a pigment derivative, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As said resin type dispersing agent, For example, polycarboxylic acid ester, such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, polycarboxyl Acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydrogen group-containing polycarboxylic acid esters, amides or salts thereof formed by reaction of poly (lower alkyleneimine) with free polyester having a carboxyl group, (meth ) acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester-based, modified polyacrylate, ethylene oxide/poly A propylene oxide adduct etc. are mentioned. As a commercial item of the said resin type dispersing agent, the thing similar to what was described in Unexamined-Japanese-Patent No. 2015-157909 is mentioned.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalinesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, Anionic surfactants, such as ammonium lauryl sulfate, sodium stearate, and sodium lauryl sulfate; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; Cationic surfactants, such as an alkyl quaternary ammonium salt and those ethylene oxide addition products; Amphoteric surfactants, such as alkyl betaines, such as alkyl dimethyl amino acetate betaine, and alkyl imidazoline; and the like.

The dye derivative is a compound having a structure in which a functional group is introduced into a dye, and the functional group includes, for example, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, and a phthalimide. and the like. Examples of the structure of the matrix dye include azo-based, anthraquinone-based, quinophthalone-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindoline-based, dioxazine-based, indanthrene-based, Perylene type, diketopyrrolopyrrole type, etc. are mentioned.

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

(Antioxidant)

Curable resin composition of this invention can further improve the heat-resistant coloring property of hardened|cured material by containing antioxidant.

It does not specifically limit as antioxidant which can be used in this invention, Although a well-known antioxidant may be selected and used suitably, Among them, a hindered phenol type antioxidant and a phosphite type antioxidant are preferable. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

<Preparation of curable resin composition>

A method for preparing the curable resin composition is not particularly limited, and a known method may be used, for example, a method of mixing and dispersing each of the above-described components using various mixers or dispersers is mentioned. . The mixing/dispersing step is not particularly limited, and may be carried out by a known method. Moreover, you may further include the other process normally performed. Moreover, when the said curable resin composition contains a color material, it is preferable to prepare through the dispersion processing process of a color material.

In the dispersing treatment step of the color material, for example, first, each predetermined amount of the color material (preferably an organic pigment), a dispersing agent and a solvent is weighed, and the color material is dispersed into fine particles using a disperser to disperse a liquid color material dispersion (mill Also referred to as a base) can be mentioned. As said disperser, a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, a blender, etc. are mentioned. As the dispersion treatment step, there is preferably a method of kneading and dispersing treatment with a roll mill, kneader, blender, etc., followed by fine dispersion treatment with a media mill such as a bead mill filled with 0.01 to 1 mm beads. . To the obtained mill base, the above polymer, polymerizable compound, and a photopolymerization initiator, separately stirred and mixed, and, if necessary, a composition (preferably a clear liquid) containing a solvent or a leveling agent is added and mixed; It is set as a uniform dispersion solution, and curable resin composition can be obtained.

Moreover, it is preferable that the obtained curable resin composition carries out a filtration process with a filter etc., and removes fine dust.

3. Laminate

As above-mentioned, the polymer of this invention and curable resin composition provide the hardened|cured material excellent in heat-resistant coloring property, and it is excellent in developability, and also provides the hardened|cured material by which water nonuniformity was suppressed. Moreover, the said hardened|cured material is excellent also in performance, such as surface hardness, adhesiveness with a base material, heat resistance, and transparency. A laminate having such a cured product of the polymer or a cured product of the curable resin composition on a substrate (substrate) is also one of the present inventions.

When the said hardened|cured material is a cured film, as the film thickness, Preferably 0.1-20 micrometers is mentioned. The excellent heat-resistance coloring property as a film thickness is the above-mentioned range can be exhibited. Moreover, various performances, such as surface hardness, adhesiveness with a base material, heat resistance, and transparency, can also fully be exhibited. The said film thickness becomes like this. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.

Moreover, from a viewpoint of favorable developability and the inhibitory effect of water nonuniformity, the said film thickness becomes like this. More preferably, it is 1-15 micrometers, More preferably, it is 1-10 micrometers.

It does not specifically limit as a method of obtaining a laminated body, A well-known method may just be used, For example, the above-mentioned polymer or the above-mentioned curable resin composition is apply|coated on a base material, The coated thing is dried, The method of hardening by heating or irradiating energy rays, such as an ultraviolet-ray, to obtain hardened|cured material is mentioned.

It does not specifically limit as said base material, What is necessary is just to select suitably according to the objective and a use, For example, the base material which consists of various materials, such as a glass plate and a plastic plate, is mentioned.

The laminate is, for example, a color filter, a black matrix, a photospacer, a black column spacer, an ink used in a liquid crystal/organic EL/quantum dot/micro LED liquid crystal display device, a solid-state image sensor, a touch panel type display device, etc. It is suitably used for uses, such as various optical members, electric/electronic devices, such as a printing board, a printed wiring board, a semiconductor element, a photoresist, and an insulating film. Especially, it is preferable to use for a color filter.

Thus, the color filter which has the hardened|cured material of the said curable resin composition is also one of this invention. Hereinafter, a color filter is demonstrated.

3-1. color filter

The color filter of this invention consists of an aspect which has the hardened|cured material of the said curable resin composition on a board|substrate.

The said color filter WHEREIN: Although the hardened|cured material formed of the said curable resin composition is especially preferable as a segment which requires coloring like each pixel, such as a black matrix and red, green, blue, yellow, for example, a photospacer , a protective layer, a rib for orientation control, etc. are preferable also as a segment which does not necessarily require coloring.

As a board|substrate used for the said color filter, For example, Glass substrates, such as white plate glass, blue plate glass, alkali-strengthened glass, silica-coated blue plate glass; Sheet, film, or board|substrate which consist of thermoplastic resins, such as polyester, polycarbonate, polyolefin, polysulfone, a ring-opened polymer of a cyclic olefin, and its hydrogenated substance; Sheet, film, or board|substrate which consists of thermosetting resins, such as an epoxy resin and an unsaturated polyester resin; Metal substrates, such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate; ceramic substrate; A semiconductor substrate having a photoelectric conversion element; a member composed of various materials such as a glass substrate having a color material layer on its surface (eg, color filter for LCD); and the like. Especially, a glass substrate and the sheet|seat, film, or board|substrate which consist of a heat resistant resin from a heat resistant point are preferable. Moreover, it is preferable that the said board|substrate is a transparent board|substrate.

Moreover, you may give corona discharge treatment, ozone treatment, chemical treatment by a silane coupling agent, etc. to the said board|substrate as needed.

<The manufacturing method of a color filter>

In order to obtain the said color filter, for example, for one pixel color (that is, for each pixel of one color), on a board|substrate, the process of arrange|positioning the said curable resin composition (it is also called arrangement|positioning process), and on the said board|substrate A method comprising a step of irradiating the arranged curable resin composition with light (also referred to as a light irradiation step), a step of developing with a developer (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step). It is preferable to employ|adopt and employ|adopt the manufacturing method which repeats the method similar to this for each color. In addition, the formation order of the pixel of each color is not specifically limited.

(batch process (preferably application process))

It is preferable to implement the said arrangement|positioning process by application|coating. As a method of apply|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 preferably.

In the said arrangement|positioning process, after apply|coating the said curable resin composition on a board|substrate further, it is preferable to dry a coating film. Drying of a coating film can be performed using a hot plate, IR oven, a convection oven, etc., for example. Although drying conditions are suitably selected according to the boiling point of the solvent component contained, the kind of hardening component, film thickness, the performance of a dryer, etc., it is preferable to carry out for 10 second - 300 second at the temperature of normally 50-160 degreeC.

(Light irradiation process)

In the light irradiation step, examples of the light source of the actinic light used include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp. Lamp light sources, such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, laser light sources, such as a semiconductor laser, etc. are used. Moreover, although a proximity system, a mirror projection system, and a stepper system are mentioned as a system of an exposure machine, a proximity system is used preferably.

In addition, in the irradiation process of an active energy ray, depending on a use, it is good also as irradiating an active energy ray through a predetermined|prescribed mask pattern. In this case, the exposed part hardens|cures, and the hardened|cured part becomes insoluble or poorly soluble with respect to a developing solution.

(developing process)

The said developing process is a process of developing with a developing solution after the above-mentioned light irradiation process, removing an unexposed part, and forming a pattern. Thereby, a patterned cured film can be obtained. Developing treatment is normally 10-50 degreeC of image development temperature, and can be implemented by methods, such as immersion image development, spray image development, brush image development, and ultrasonic image development.

Although it will not specifically limit if the developing solution used in the said image development process melt|dissolves curable resin composition of this invention, Usually, an organic solvent and alkaline aqueous solution are used, and these mixtures may be used. In addition, when using alkaline aqueous solution as a developing solution, it is preferable to wash with water after image development.

As an organic solvent preferable as said developing solution, an ether solvent, an alcohol solvent, etc. are mentioned, for example. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkylphenyl ethers, aralkyl Phenyl ethers, diaromatic ethers, isopropanol, benzyl alcohol, etc. are mentioned.

The said alkaline aqueous solution can contain surfactant, organic solvent, a buffer, dye, a pigment, etc. as needed other than an alkali agent. As an organic solvent in this case, the organic solvent etc. suitable as a developing solution mentioned above are mentioned.

As said alkali agent, For example, inorganic alkali agents, such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium trisodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate; and amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide. may be used or may be used in combination of two or more types.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinates; Amphoteric surfactants, such as alkylbetaines and amino acids, etc. are mentioned, These may be used independently and may be used in combination of 2 or more type.

(heating process)

The said heating process is a process (it is also called a post-hardening process) of further hardening an exposure part (hardened part) by baking after the above-mentioned image development process. For example, using a light source such as a high-pressure mercury lamp, for example, a step of post-exposure with a light quantity of 0.5 to 5 J/cm 2 , or post-heating at a temperature of 60 to 260° C. for 10 seconds to 120 minutes. process etc. are mentioned. By implementing such a post-curing process, it becomes possible to make the hardness and adhesiveness of the patterned cured film still stronger. In addition, by this heating step, in the polymer of the present invention, a part of the monomer unit (A) is detached to form a hydroxyl group at the terminal, and the hydroxyl group and the acid group of the monomer unit (A) not detached The acid group of other arbitrary monomer units reacts to form a crosslinked structure, and the curable resin composition of the present invention has more excellent curing properties, solvent resistance and heat color resistance of the resulting cured product. In addition, in the vinyl-based monomer unit (B) of the polymer, the tertiary carbon-containing moiety is detached to generate a carboxyl group, and the carboxyl group and the hydroxyl group react to form a crosslinked structure, so that the cured product has solvent resistance and curability It will be better than this.

It is preferable that the film thickness of the cured film obtained by the said heating process (that is, the cured film obtained by thermosetting the said curable resin composition) is 0.1-20 micrometers. By using the curable resin composition of this invention, the cured film by which the film thickness was fully reduced can be provided. Moreover, since a film thickness is reduced, the density|concentration of the color material per unit volume of a cured film can increase and the brightness|luminance of a color filter can be improved. The said film thickness becomes like this. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.

Moreover, when the film thickness of the coating film (namely, cured film) obtained by the said heating process makes the film thickness of the coating film before a heating 100 %, it is preferable that it is 90 % or less. More preferably, it is 80 % or less, More preferably, it is 70 % or less.

Said heating process WHEREIN: It is preferable that heating temperature is 150 degreeC or more. Thereby, the part derived from a part of the said vinylic monomeric unit (B) decomposes|disassembles more effectively, and sclerosis|hardenability and solvent resistance can be improved further. The heating temperature is more preferably 160°C or higher, still more preferably 170°C or higher, and particularly preferably 180°C or higher. Moreover, it is preferable to set it as 270 degrees C or less, More preferably, it is 260 degrees C or less, More preferably, it is 250 degrees C or less.

Although the heating time in the said heating process is not specifically limited, For example, it is preferable to set it as 5 to 60 minutes. Moreover, the heating method is also although it does not specifically limit, For example, it can implement using heating apparatuses, such as a hot plate, a convection oven, and a high frequency heater.

4. Display device

This invention is also provided with the color filter mentioned above, It is also a display apparatus characterized by the above-mentioned.

Moreover, the member for display apparatuses and display apparatus which have hardened|cured material formed from the said curable resin composition are also contained in preferable embodiment of this invention. The cured product (cured film) formed of the curable resin composition is stable, has excellent adhesion to a substrate, etc., has high hardness, exhibits high smoothness, and has high transmittance. Therefore, it is particularly useful as a transparent member. It is preferable, and it is useful also as a protective film and insulating film in various display apparatuses.

As said display device, a liquid crystal display device, a solid-state image sensor, a touch panel type display device etc. are preferable, for example.

Further, when the cured product (cured film) is used as a member for a display device, the member may be a film-like single or multi-layer member composed of the cured film, or a layer other than the single-layer or multi-layer member. This combined member may be sufficient, and the member included in the structure of the said cured film may be sufficient.

As above-mentioned, the polymer of this invention and curable resin composition containing the said polymer can provide the hardened|cured material excellent in heat-resistant coloring property. Moreover, the hardened|cured material obtained using the polymer and curable resin composition of this invention is excellent also in adhesiveness with a board|substrate, transparency, heat resistance, etc. The polymer and curable resin composition of this invention are liquid crystal, organic EL, quantum dot, micro LED liquid crystal display device, a solid-state image sensor, a color filter used for a touch panel type display device, etc., a black matrix, a photo-spacer, a black column spacer , inks, printing plates, printed wiring boards, semiconductor devices, photoresists, insulating films, etc., are very useful for various uses in the optical field and the electric/electronic field.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited only to these Examples. In addition, unless otherwise indicated, "part" shall mean "part by mass" and "%" shall mean "mass %".

In this Example, measurement conditions such as various physical properties are as follows.

<Weight Average Molecular Weight>

It measured by the gel permeation chromatography method using HLC-8220GPC (made by Tosoh Corporation), tetrahydrofuran as an eluent, and TSK-gel SuperHZM-M (made by Tosoh Corporation) as a column, and calculated in conversion of standard polystyrene.

<Solid content>

About 1 g of the copolymer solution was precisely weighed in an aluminum cup, dissolved by adding about 2 g of acetone, and then left to stand at room temperature for about 2 hours and dried naturally. Then, with a vacuum dryer (made by EYELA), after drying at 140 degreeC in vacuum for 1.5 hours, it stood to cool in the desiccator, and the mass of the aluminum cup was measured. The solid content (mass %) of the copolymer solution was calculated from the mass decrease.

＜Mountain value＞

1.5 to 3 g of the copolymer solution is precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and 0.1 N aqueous potassium hydroxide solution is used as a titrant, and an automatic titration device (manufactured by Hiranuma Industrial Co., Ltd., product: COM-1700), the acid value of the copolymer solution was measured, and the acid value per 1 g of the polymer was determined from the acid value and solid content of the solution.

<Heat color resistance (Method A)>

Antioxidant Irganox 1010 (made by BASF) was added to the copolymer solution so that it might become a density|concentration of 0.5 mass %, and the resin composition solution was prepared. This resin composition solution was prepared using a spin coater (manufactured by Mikasa Corporation, 1H-D7) so that the application amount was 0.4 to 1.2 mg/cm 2 in terms of solid content on a 5 cm horizontal and vertical glass substrate (soda-lime glass AS-2K, Toshin). (manufactured by Ricoh Co., Ltd.) was uniformly applied. At this time, about each resin composition, the rotation speed of the spin coater was changed, the application amount (solid content conversion) was changed, and the application plate of 2 sheets with different application amounts was produced. It was made so that the application amount of one of the two sheets was necessarily larger than 0.6 mg/cm 2 and the application amount of the other sheet was necessarily smaller than 0.6 mg/cm 2 .

By drying these application boards at 100 degreeC for 3 minutes, the laminated body in which the coating film was formed on the glass substrate was obtained. After removing the resin adhering to the edge part of a glass substrate, the obtained laminated body was heat-processed at 250 degreeC for 3 hours using the perfect oven thermostat (made by SPEC), and it cooled to room temperature. After cooling, the surface of the coating film of the laminate was measured using colorimetric colorimeter ZE6000 (manufactured by Nippon Denshoku Industries Co., Ltd.) to obtain the b ^* value after the heating test. An approximate straight line (calibration curve) between the application amount (x) and the b ^* value (y) is obtained from the measured values of the two coating films prepared as described above for each coating film, and the b ^* value when the application amount is 0.6 mg/cm 2 was adopted as a result of the heat-resistant colorability of each coating film.

<Heat color resistance (Method B)>

The solvent (propylene glycol monomethyl ether acetate) was added to the copolymer solution so that it might become the compounding shown in Table 4, and the resin composition solution (solid content 35 mass %) was prepared. This resin composition solution was prepared using a spin coater (manufactured by Mikasa Corporation, 1H-D7) so that the application amount was 1.0 to 3.0 mg/cm 2 in terms of solid content on a 5 cm horizontal glass substrate (soda lime glass AS-2K, Toshin). (manufactured by Ricoh Co., Ltd.) was uniformly applied. At this time, about each resin composition solution, the rotation speed of the spin coater was changed, the application amount (solid content conversion) was changed, and the application plate of 2 sheets with different application amounts was produced. The application amount of one sheet out of the two sheets was always set to a value greater than 1.6 mg/cm 2 , and the application amount of the other sheet was always set to a value smaller than 1.6 mg/cm 2 .

After drying these application boards at 140 degreeC for 1 hour, the laminated body in which the coating film was formed on the glass substrate was obtained by further drying at 180 degreeC for 1 hour. After removing the resin adhering to the edge part of a glass substrate, the obtained laminated body was heat-processed at 250 degreeC for 2 hours using the perfect oven thermostat (made by SPEC), and it cooled to room temperature after that. After cooling, the surface of the coating film of the laminate was measured using colorimetric colorimeter ZE6000 (manufactured by Nippon Denshoku Industries Co., Ltd.) to obtain the b ^* value after the heating test. An approximate straight line (calibration curve) between the application amount (x) and the b ^* value (y) is obtained from the measured values of the two coating films prepared as described above for each coating film, and the b ^* value when the application amount is 1.6 mg/cm2 was adopted as a result of the heat-resistant colorability of each coating film.

<Evaluation of water unevenness>

The obtained curable resin composition was coated on an alkali-free glass plate (10 cm × 10 cm, manufactured by Geomatec) using a spin coater so that the thickness of the coating film after drying was 3 µm, and dried at 100° C. for 3 minutes with a hot plate. Then, ultraviolet rays were irradiated using an ultra-high pressure mercury lamp so that the irradiation amount was 100 mJ/cm 2 . After exposure, 0.04 mass % potassium hydroxide aqueous solution was spread|dispersed to the coating film for 60 second with a spin developing machine, and shower development was performed. Next, after washing the exposed part with water for 10 seconds with pure water, the water|moisture content on the surface of a glass plate was removed by air blow.

Water unevenness (shading unevenness) of the coating film was observed using an optical microscope (magnification: 100 times), and the following criteria were evaluated. Based on the following criteria, ○, ○ △, and △ were taken as levels having no practical problems.

○: Water non-uniformity cannot be confirmed with an optical microscope.

○△: Water non-uniformity can be confirmed with an optical microscope.

(triangle|delta): Water nonuniformity can be confirmed visually.

x: A coating film partly peels at the time of image development.

X X: All the coating films peel at the time of image development.

<developability (developing time)>

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

(Synthesis Example 1)

Preparation of copolymer solution 1

As a reaction tank, a separable flask equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dripping tank inlet port was prepared, and, on the other hand, as a monomer dripping tank, dimethyl-2,2'-[oxybis(methylene)]bis -2-propenoate (hereinafter referred to as "MD") 10.0 parts, t-butyl methacrylate (hereinafter referred to as "t-BMA") 29.5 parts, 2-hydroxyethyl methacrylate (hereinafter referred to as "HEMA") 15.0 parts, methyl methacrylate (hereinafter referred to as "MMA") 1.0 parts, mono(2-acryloyloxyethyl succinate) (hereinafter referred to as "HOA-MS") 44.5 parts, t-butylperoxy- 2 parts of 2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by Nichiyu Corporation; hereinafter referred to as "PBO"), 33 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were mixed well with stirring. This was prepared, and as a chain transfer agent dropping tank, 1.6 parts of n-dodecyl mercaptan (n-DM) and 7.7 parts of PGMEA were well stirred and mixed.

After pouring 141 parts of PGMEA into the reaction tank, nitrogen substitution, and heating with the oil bath while stirring, the temperature of the reaction tank was heated up to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 degreeC, dripping was started from the monomer dripping tank and the chain transfer agent dripping tank. The dripping was performed over 2.5 hours, respectively, maintaining temperature at 90 degreeC. After dripping was complete|finished, the temperature rise was started 60 minutes afterward, and the reaction tank was made into 110 degreeC. After hold|maintaining 110 degreeC for 3 hours, the copolymer solution 1 was obtained by cooling to room temperature. Various physical properties are shown in Table 1.

(Synthesis Example 2)

Preparation of copolymer solution 2

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

(Synthesis Example 3)

Preparation of copolymer solution 3

The injection amount of the monomer was 10.0 parts of MD, 26.5 parts of t-BMA, 15.0 parts of HEMA, 1.0 parts of MMA, and 47.5 parts of monosuccinate (2-methacryloyloxyethyl) (hereinafter referred to as “HO-MS”). The monomer dripping tank and the chain transfer agent dripping tank were prepared similarly to the synthesis example 1, the same operation was performed, and the copolymer solution 3 was obtained. Various physical properties are shown in Table 1.

(Synthesis Example 4)

Preparation of copolymer solution 4

In a separable flask equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping tank inlet, 164 parts of PGMEA was poured, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as a monomer dropping tank, 10.0 parts of N-benzylmaleimide (hereinafter referred to as "BzMI"), 28.0 parts of t-BMA, 15.0 parts of HEMA, 1.0 parts of MMA, 46.0 parts of HOA-MS and 2.2 parts of PBO were mixed well with stirring. 2.6 parts of n-DM and 17.4 parts of PGMEA were well stirred and mixed as a chain transfer agent dripping tank was prepared. After the temperature of the reaction tank was stabilized at 90 degreeC, dripping was started from the monomer dripping tank and the chain transfer agent dripping tank. The dripping was performed over 3 hours, respectively, maintaining temperature at 90 degreeC. After completion|finish of dripping, after hold|maintaining 90 degreeC for 30 minutes, it heated up to 115 degreeC, aging was performed for 90 minutes, and the copolymer solution 4 was obtained. Various physical properties are shown in Table 1.

(Synthesis Example 5)

Preparation of copolymer solution 5

A monomer dripping tank and a chain transfer agent dripping tank were prepared with the same monomer injection amount as in Synthesis Example 4 except that N-cyclohexylmaleimide (hereinafter referred to as "CHMI") was used instead of BzMI, and the same operation was performed, and the copolymer solution 5 was obtained. Various physical properties are shown in Table 1.

(Synthesis Example 6)

Preparation of copolymer solution 6

As a reaction tank, a separable flask equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dripping tank inlet was prepared, and, on the other hand, as a monomer dripping tank, MD 10.0 parts, t-BMA 38.8 parts, MMA 2.0 parts, HO -MS 49.2 parts, PBO 2.0 parts, and PGMEA 33.0 parts were well stirred and mixed, and as a chain transfer agent dropping tank, 1.4 parts of n-dodecyl mercaptan (n-DM) and 7.9 parts of PGMEA were well stirred and mixed. .

After pouring 141 parts of PGMEA into the reaction tank, nitrogen substitution, and heating with the oil bath while stirring, the temperature of the reaction tank was heated up to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 degreeC, dripping was started from the monomer dripping tank and the chain transfer agent dripping tank. The dripping was performed over 2.5 hours, respectively, maintaining temperature at 90 degreeC. After dripping was complete|finished, the temperature rise was started 60 minutes afterward, and the reaction tank was made into 110 degreeC. After hold|maintaining 110 degreeC for 3 hours, the copolymer solution 6 was obtained by cooling to room temperature. Various physical properties are shown in Table 2.

(Synthesis Example 7)

Preparation of copolymer solution 7

A monomer dripping tank and a chain transfer agent dripping tank were prepared in the same manner as in Synthesis Example 6 except that the amount of monomer injected 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, and the same operation was performed, A copolymer solution 7 was obtained. Various physical properties are shown in Table 2.

(Synthesis Example 8)

Preparation of copolymer solution 8

A monomer dropping tank and a chain transfer agent dropping tank were prepared in the same manner as in Synthesis Example 6 except that the amount of monomer injected was 10.0 parts of MD, 41.8 parts of t-BMA, 32.2 parts of MMA, and 16.0 parts of HOA-MS, and the same operation was performed, A copolymer solution 8 was obtained. Various physical properties are shown in Table 2.

(Synthesis Example 9)

Preparation of copolymer solution 9

In a separable flask equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping tank inlet, 164 parts of PGMEA was poured, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as a monomer dropping tank, 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 were well stirred and mixed, and as a chain transfer agent dropping tank, 2.2 parts of n-DM, A well-stirred mixture of 17.8 parts of PGMEA was prepared. After the temperature of the reaction tank was stabilized at 90 degreeC, dripping was started from the monomer dripping tank and the chain transfer agent dripping tank. The dripping was performed over 3 hours, respectively, maintaining temperature at 90 degreeC. After completion|finish of dripping, after hold|maintaining 90 degreeC for 30 minutes, it heated up to 115 degreeC, aging was performed for 90 minutes, and the copolymer solution 9 was obtained. Various physical properties are shown in Table 2.

(Synthesis Example 10)

Preparation of copolymer solution 10

Instead of BzMI, except having used CHMI, the monomer dripping tank and the chain transfer agent dripping tank were prepared with the monomer injection amount similar to Synthesis Example 9, the same operation was performed, and the copolymer solution 10 was obtained. Various physical properties are shown in Table 2.

(Synthesis Example 11)

Preparation of copolymer solution 11

A monomer dripping tank and a chain transfer agent dropping tank were prepared with the same monomer injection amount as in Synthesis Example 9 except that N-phenylmaleimide (hereinafter referred to as "PhMI") was used instead of BzMI, and the same operation was performed, and the copolymer solution 11 got Various physical properties are shown in Table 2.

(Synthesis Example 12)

Preparation of copolymer solution 12

A monomer dropping tank and a chain transfer agent dropping tank were prepared in the same manner as in Synthesis Example 6 except that the injection amount of the monomer was 10.0 parts of MD, 41.8 parts of t-BMA, 32.8 parts of MMA, and 15.4 parts of AA. Solution 12 was obtained. Various physical properties are shown in Table 2.

(Examples 1 to 11, Comparative Example 1)

The method A evaluated heat-resistant colorability using the obtained copolymer solutions 1-12. A result is shown in Table 1 and Table 2.

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

MD: Dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate

BzMI: N-benzylmaleimide

CHMI: Cyclohexylmaleimide

PhMI: Phenylmaleimide

t-BMA: t-butyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

MMA: methyl methacrylate

HOA-MS: monosuccinate (2-acryloyloxyethyl)

HO-MS: monosuccinate (2-methacryloyloxyethyl)

AA: acrylic acid

MAA: methacrylic acid

It can be seen from Tables 1 and 2 that the polymers having HOA-MS or HO-MS monomer units and t-BMA monomer units (Examples 1 to 11) are the polymers without HOA-MS or HO-MS monomer units ( Compared with Comparative Example 1), the b ^* value became a very small value, and it was confirmed that it was excellent in heat-resistant coloring property.

(Synthesis Example 13)

Preparation of copolymer solution 13

70 parts of propylene glycol monomethyl ether acetate was poured into the reaction tank provided with the thermometer, a stirrer, a gas introduction tube, a cooling tube, and the dripping tank inlet, After nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dropping tank (A), 20 parts of BzMI, 80 parts of PGMEA, and 2 parts of PBO were prepared by stirring and mixing in a beaker, and 20 parts of vinyltoluene (hereinafter, referred to as “VT”) to the dropping tank (B). , 20 parts of t-BMA, 40 parts of HO-MS, and 4 parts of n-dodecyl mercaptan were prepared by stirring and mixing. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition|polymerization was performed. After hold|maintaining 90 degreeC for 30 minute(s) after completion|finish of dripping, it heated up to 115 degreeC, aging was performed for 90 minutes, and the copolymer solution 13 was obtained. Various physical properties are shown in Table 3. Moreover, the monomer composition of the obtained copolymer was BzMI/VT/t-BMA/HO-MS (molar ratio) =18/29/24/29.

(Synthesis Example 14)

Preparation of copolymer solution 14

The same operation as in Synthesis Example 13 was carried out to obtain a copolymer solution 14, except that the amount of the monomer injected was set to 20 parts of CHMI, 20 parts of VT, 20 parts of t-BMA, and 40 parts of HO-MS. Various physical properties are shown in Table 3. Moreover, the monomer composition of the obtained copolymer was CHMI/VT/t-BMA/HO-MS (molar ratio) =19/28/24/29.

(Synthesis Example 15)

Preparation of copolymer solution 15

The same operation as in Synthesis Example 13 was carried out to obtain a copolymer solution 15, except that the injection amount of the monomer was 20 parts of PhMI, 20 parts of VT, 20 parts of t-BMA, and 40 parts of HO-MS. Various physical properties are shown in Table 3. Moreover, the monomer composition of the obtained copolymer was PhMI/VT/t-BMA/HO-MS (molar ratio) =19/29/23/29.

(Synthesis Example 16)

Preparation of copolymer solution 16

The same operation as in Synthesis Example 13 was carried out to obtain a copolymer solution 16, except that the amount of the monomer to be injected was set to 10 parts of PhMI, 10 parts of VT, 40 parts of t-BMA, and 40 parts of HO-MS. Various physical properties are shown in Table 3. In addition, the monomer composition of the obtained copolymer was PhMI/VT/t-BMA/HO-MS (molar ratio) = 10/14/47/29.

(Synthesis Example 17)

Preparation of copolymer solution 17

A copolymer solution 17 was obtained in the same manner as in Synthesis Example 13 except that the injection amount of the monomer was 20 parts of PhMI, 20 parts of VT, 30 parts of t-BMA, and 30 parts of HO-MS. Various physical properties are shown in Table 3. In addition, the monomer composition of the obtained copolymer was PhMI/VT/t-BMA/HO-MS (molar ratio) = 18/27/34/21.

(Synthesis Example 18)

Preparation of copolymer solution 18

A copolymer solution 18 was obtained in the same manner as in Synthesis Example 13 except that the amount of the monomer to be charged 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. Various physical properties are shown in Table 3. Moreover, the monomer composition of the obtained polymer was BzMI/t-BMA/MMA/HEMA/AA (molar ratio) =6/29/23/18/24.

(Synthesis Example 19)

Preparation of copolymer solution 19

The same operation as in Synthesis Example 13, except that the amount of the monomer injected was 10 parts of CHMI, 35 parts of t-BMA, 19.5 parts of dicyclofentanyl methacrylate (hereinafter referred to as “DCPMA”), 20 parts of HEMA, and 15.5 parts of AA. was carried out to obtain a copolymer solution 19. Various physical properties are shown in Table 3. Moreover, the monomer composition of the obtained polymer was CHMI/t-BMA/DCPMA/HEMA/AA (molar ratio) =7/32/12/20/29.

(Examples 12 to 16, Comparative Example 2)

Method B evaluated heat-resistant colorability using the obtained copolymer solutions 13-18. A result is shown in Table 4.

(Example 17)

In terms of solid content, 20 parts of copolymer solution 13, 50 parts of color material composition (Blue), 20 parts of dipentaerythritol hexaacrylate as a polymerizable compound, and Irgacure 907 (manufactured by BASF) as a photoinitiator Curable resin composition (1-1) was obtained by mixing 10 parts, adding propylene glycol monomethyl ether acetate (PGMEA) as a dilution solvent so that solid content concentration might be set to 20 mass %, and stirring it. The developability of the obtained curable resin composition (1-1) was evaluated. A result is shown in Table 5.

In addition, the said color material composition (Blue) was prepared by the following method.

* Preparation of color material composition (Blue)

Resin solution for dispersion (monomer composition of resin: BzMI/cyclohexyl methacrylate/methyl methacrylate/methacrylic acid = 30/30/30/10 (mass ratio), Mw: 10000, acid value: 65 mgKOH/g, resin Solid content in solution: 42%) 8.3 mass parts, a dispersing agent (The Bikchemi Japan company make, brand name "DISPERBYK-2001", non-volatile matter 1.3g) 2.9 mass parts, a pigment (CI Pigman Blue 15:6) 8.0 mass A portion was weighed in a 225 ml container and diluted with PGMEA so that the nonvolatile matter concentration (solid content concentration) was 20 mass%. 64 g of zirconia beads having a diameter of 1.0 mm were added thereto, shaken with a paint shaker for 3 hours, and after dispersion treatment, the zirconia beads were removed by decantation to obtain a color material composition (Blue).

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

Curable resin compositions (2-1)-(7-1) were obtained by operation similar to Example 17 using the copolymer solutions 14-19 so that it might become the compounding shown in Table 5. The developability of the obtained curable resin composition was evaluated. A result is shown in Table 5.

(Example 22)

In terms of solid content, 45 parts of the copolymer solution 13, 20 parts of the color material composition (Blue), 25 parts of dipentaerythritol hexaacrylate as a polymerizable compound, and Irgacure 907 (manufactured by BASF) as a photoinitiator Curable resin composition (1-2) was obtained by mixing 10 parts, further adding and stirring a dilution solvent (PGMEA) so that solid content concentration might be set to 20 mass %. The water nonuniformity of the obtained curable resin composition (1-2) was evaluated. A result is shown in Table 6.

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

Curable resin compositions (2-2) - (7-2) were obtained by operation similar to Example 22 using the polymer solutions 14-19 so that it might become the compounding shown in Table 6. The water nonuniformity of the obtained curable resin composition was evaluated. A result is shown in Table 6.

In addition, description in Table 3 shows the following.

BzMI: N-benzylmaleimide

CHMI: Cyclohexylmaleimide

PhMI: Phenylmaleimide

VT : Vinyltoluene

CHMA: Cyclohexyl methacrylate

t-BMA: t-butyl methacrylate

MMA: methyl methacrylate

DCPMA: Dicyclofentanyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

AA: acrylic acid

HO-MS: monosuccinate (2-methacryloyloxyethyl)

From Table 4, it can be seen that the polymers having a HO-MS monomer unit and a t-BMA monomer unit (Examples 12 to 16) had a b ^* value compared to the polymer without a HO-MS monomer unit (Comparative Example 2). It became a small value, and it was confirmed that it was excellent in heat-resistant coloring property.

From Tables 5 and 6, it can be seen that the polymers having HO-MS monomer units and t-BMA monomer units (Examples 17 to 26) were compared with polymers not having HO-MS monomer units (Comparative Examples 3 to 6), It was confirmed that it was excellent also in developability and the water nonuniformity inhibitory effect.

Claims (10)

10-60 mass % of monomeric units represented by the following general formula (I), and -COO ^{* R4} ( ^R4 is a monovalent organic group, and the carbon atom couple|bonded with O ^* is a tertiary carbon atom.) It has 5-80 mass % of a vinylic monomer unit containing a group, and further N-substituted maleimide-type monomeric unit, a dialkyl-2,2'- (oxydimethylene) diacrylate-type monomeric unit, alpha-(unsaturated) A polymer containing a ring structure having a ring structure in the main chain having at least one monomer unit selected from the group consisting of an alkoxyalkyl) acrylate-based monomer unit and a unit having a lactone ring structure represented by the general formula (II). Characterized Polymer.

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms. R ³ is 2 represents an organic group of valence.X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid 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 1 or more It is a number, where n is 0 or 1.)

(Wherein, 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. ) The method of claim 1,
N-substituted maleimide monomer units, dialkyl-2,2'-(oxydimethylene) diacrylate monomer units, α-(unsaturated alkoxyalkyl) acrylate monomer units, and lactones represented by the general formula (II) The at least 1 sort(s) of monomeric unit selected from the group which consists of units which has a ring structure is 2-60 mass % with respect to 100 mass % of all monomer units of a polymer, The polymer. The method of claim 1,
The said polymer is a polymer which has a hydroxyl-containing monomeric unit further, The polymer characterized by the above-mentioned. The method of claim 1,
The polymer is, further, a polymer characterized in that it is a polymer having an aromatic vinyl-based monomer unit. The method of claim 1,
A polymer characterized in that the content of (meth)acrylic acid units is less than 5% by mass. The method of claim 1,
A polymer having an acid value of 40 to 160 mgKOH/g. Curable resin composition containing the polymer of any one of Claims 1-6, and a polymeric compound. A cured product of the polymer according to any one of claims 1 to 6, or the polymer according to any one of claims 1 to 6, and a polymerizable compound are contained on a substrate. A laminate comprising a cured product of a curable resin composition comprising: On a board|substrate, it has hardened|cured material of curable resin composition of Claim 7, The color filter characterized by the above-mentioned. A display device comprising the color filter according to claim 9 .