JP2019044193A - Polymer and use thereof - Google Patents

Abstract

To provide a polymer capable of forming a coating film extremely excellent in heat resistance, transparency and curability, and a laminate using the polymer.SOLUTION: The polymer has a ring structure in the main chain and contains, as essential components, (a) a constituent unit derived from an unsaturated monomer having an acid group, (b) a constituent unit derived from an unsaturated monomer having a hydroxyl group, and (c) a constituent unit derived from an unsaturated monomer having an amino group. Further, the laminate comprises a cured layer, obtained by curing the polymer, disposed on a substrate.SELECTED DRAWING: None

Description

  The present invention relates to polymers and their uses. More particularly, the invention relates to a polymer and a laminate.

  Conventionally, as a polymer having a photopolymerizable property excellent in heat resistance, for example, a polymer obtained by polymerizing a monomer component containing maleimide is disclosed in Patent Document 1, and a polymer disclosed in Patent Document 2 is A polymer obtained by polymerizing a compound having a specific structure which is an ether dimer of hydroxyalkyl) acrylic acid ester, and a polymer obtained by polymerizing a monomer component containing N-substituted maleimide and vinyl toluene are disclosed in Patent Document 3 Proposed. Further, Patent Document 4 proposes a polymer obtained by polymerizing N-substituted maleimide, a carboxyl monomer and a hydroxy monomer.

  In a resin composition containing a maleimide-derived polymer (maleimide polymer), since the maleimide polymer contains a nitrogen atom, the polymer is colored in yellow to yellowish brown, and the transparency of the cured film is There was a problem of becoming insufficient. This problem of transparency is particularly remarkable when the thickness of the cured film is thick, and furthermore, it may be further colored when heat treatment is performed. On the other hand, a resin composition containing a polymer obtained by polymerizing a compound having a specific structure, which is an ether dimer of 2- (hydroxyalkyl) acrylic acid ester, together with a curing component has a coating film excellent in both heat resistance and transparency. Although it can be formed, there has been a case where improvement is required because the demand for coloring level after heat treatment is increasing year by year.

JP, 2003-201316, A (page 3 etc.) JP-A-2004-300204 (page 3 etc.) JP, 2009-040999, A (page 3 etc.) JP-A-2004-302293 (page 3 etc.)

  An object of the present invention is to provide a polymer capable of forming a coating film extremely excellent in heat resistance and transparency as well as curability, and a laminate using the polymer, in view of the above-mentioned present situation. is there.

  The present inventors have variously examined polymers, and it is a polymer having a ring structure in the main chain, and has (a) a structural unit derived from an unsaturated monomer having an acid group, and (b) a hydroxyl group. It has been found that a polymer comprising, as essential components, a structural unit derived from an unsaturated monomer and a structural unit derived from an unsaturated monomer having an amino group (c) can solve the problem.

  Preferably, the copolymer is copolymerized with (a) an unsaturated monomer having a carboxyl group, (b) an unsaturated monomer having a hydroxyl group, and (c) an unsaturated monomer having an amino group as essential components. It has been found that polymers can solve the problem, and the present invention has been achieved.

  More preferably, (a) a structural unit derived from an unsaturated monomer having an acid group, (b) a structural unit derived from an unsaturated monomer having a hydroxyl group, and (c) an unsaturated monomer having an amino group A polymer containing a constituent unit derived from the polymer as an essential component, wherein the content ratio of the unsaturated monomer having the acid group is 0.5 to 50 with respect to the total of all the monomer components constituting the polymer The content of the unsaturated monomer having a hydroxyl group is 0.5 to 50% by mass, and the content of the unsaturated monomer having an amino group is 0.5 to 55% by mass It is said that.

Particularly preferably, (a) an unsaturated monomer having a carboxyl group, (b) an unsaturated monomer having a hydroxyl group, and (c) an unsaturated monomer having an amino group as monomer components. A polymer formed by polymerization as an essential component, wherein the content ratio of the unsaturated monomer having a carboxyl group is 0.5 to 50% by mass, based on the total of all the monomer components constituting the polymer Characterized in that the content ratio of the unsaturated monomer containing is 0.5 to 50% by mass, and the content ratio of the unsaturated monomer having an amino group is 0.5 to 55% by mass. is there.
The polymer of the present invention has a ring structure in the main chain.
A particularly preferred form for introducing a ring structure into the main chain is (d) the following general formula (1) as a monomer component:

(In formula (1), R ¹ and R ² each independently represent a hydrocarbon group selected from methyl, ethyl, cyclohexyl and benzyl.)
A monomer (constituent unit derived from a monomer), (e) N-substituted maleimide monomer (constituent unit derived from a monomer), and (f) α- (unsaturated alkoxyalkyl) acrylate type It is a polymer characterized by further including at least one monomer (constituent unit) selected from monomers (constituent units derived from a monomer).

  And this invention is also a laminated body in which the cured layer which hardens the said polymer is provided on a board | substrate.

  The polymer of the present invention can form a coating film which is extremely excellent in both heat resistance and transparency as well as curability, and is preferably used, for example, in applications such as resist materials, various coating agents, and paints. Can. Further, according to the present invention, it is possible to provide a laminate used for a display device with high display quality with high luminance and color purity and no color unevenness and the like.

The present invention will be described in detail below.

The polymer of the present invention is a polymer having a ring structure in the main chain, and is derived from (a) a structural unit derived from an unsaturated monomer having an acid group, (b) derived from an unsaturated monomer having a hydroxyl group It is a polymer which contains a structural unit and the structural unit derived from the unsaturated monomer which has (c) amino group as an essential component.
The structural unit derived from the unsaturated monomer corresponds to, for example, a structure (structural unit) in which a polymerizable double bond of each unsaturated monomer is opened by a polymerization reaction. The structure in which the polymerizable double bond is open is, for example, a structure in which a carbon-carbon double bond (C 間 の C) becomes a single bond (—C—C—). The acid group contained in the unsaturated monomer having an acid group is not particularly limited as long as it is a functional group that exhibits acidity in water, but a carboxyl group is preferable. (A) A unsaturated monomer having a carboxyl group, (b) an unsaturated monomer having a hydroxyl group, and (c) an unsaturated monomer having an amino group are copolymerized as essential components. And polymers thereof. More preferably, the content of the unsaturated monomer having a carboxyl group is 0.5 to 50% by mass, and the unsaturated monomer having a hydroxyl group with respect to the total of all the monomer components constituting the polymer. And the content of the unsaturated monomer having an amino group is 0.5 to 55% by mass. In addition, you may form the structural unit which has an acidic radical by making the acid anhydride react after superposition | polymerization of the unsaturated monomer which has a hydroxyl group.

  Although the use of the polymer of the present invention is not particularly limited, it is preferably used as a binder resin for color resist, a resin for solder resist, and the like. The polymer of the present invention is a photosensitive alkali-soluble resin and exhibits good developability.

  Among the acid groups which are essential components of the polymer of the present invention, examples of unsaturated monomers having a carboxyl group include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (Meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, etc. may be mentioned, among which (meth) acrylics are particularly preferred. Acids are preferred. The content ratio of the unsaturated monomer having a carboxyl group is preferably in the range of 0.5 to 50% by mass, more preferably 2 to 50% by weight, and still more preferably 5 to 45% in all the monomer components. It is good to be%. If the content of the unsaturated monomer containing a carboxyl group is less than 0.5% by mass, there is a possibility that the solubility may not be sufficient when the solubility by the alkali substance is required. On the other hand, if the amount is more than 50% by mass, the solubility in a solvent may be reduced, or the viscosity of the polymer may be increased to deteriorate the handleability. In the present specification, “(meth) acrylic acid” is a notation expressing both methacrylic acid and acrylic acid.

  Moreover, as the unsaturated monomer having a hydroxyl group, which is an essential component of the polymer of the present invention, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylate Although 2-hydroxybutyl, (meth) acrylic acid mono (poly) ethylene glycol, (meth) acrylic acid mono (poly) propylene glycol, etc. may be mentioned, among these, 2-hydroxyethyl (meth) acrylate, (meth 2.) 2-hydroxypropyl acrylate is preferred. The content ratio of the unsaturated monomer containing a hydroxyl group is preferably in the range of 0.5 to 50% by mass, more preferably 2 to 40% by mass, still more preferably 5 to 30% by mass, based on all the monomer components. It is good. If the content of the unsaturated monomer containing a hydroxyl group is less than 0.5% by mass, the heat resistance may be insufficient. On the other hand, if the amount is more than 50% by mass, the solubility in a solvent may be reduced, or the viscosity of the polymer may be increased to deteriorate the handleability.

  As the unsaturated monomer having an amino group, which is an essential component of the polymer of the present invention, for example, a compound represented by the general formula (2)

（式（２）中、Ｒ^３は水素原子又はメチル基を有し、Ｒ^４〜Ｒ^５は、それぞれ独立して、水素原子、又は置換基を有していてもよく鎖状もしくは環状の炭化水素基を表し、Ｒ^４及びＲ^５が互いに結合して環状構造を形成してもよい。Ｚは単結合又は２価の連結基を表す。）
で示される単量体（単量体由来の構成単位）を有することを特徴とするものでもある。

(In formula (2), R ³ has a hydrogen atom or a methyl group, and R ^{4 to} R ⁵ may each independently have a hydrogen atom or a substituent, and may have a chain or cyclic carbonization R ⁴ and R ⁵ may be bonded to each other to form a cyclic structure, and Z represents a single bond or a divalent linking group.
It is also characterized by having a monomer (constituent unit derived from a monomer) represented by

In the above formula (2), R ³ is preferably a methyl group among a hydrogen atom and a methyl group. In the above formula (2), R ⁴ and R ⁵ are independently of each other, represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Here, in the present invention, “hydrocarbon group” is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and it may be any of linear, branched and cyclic. It may be in the form. The aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and the unsaturated bond may have any position. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 (preferably 1 to 12) carbon atoms, and more specifically, an alkyl having 1 to 20 (preferably 1 to 12) carbon atoms Groups, alkenyl groups having 2 to 20 (preferably 2 to 12) carbon atoms, and alkynyl groups having 2 to 20 (preferably 2 to 12) carbon atoms. Specifically, as the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, ter-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group And octyl, decyl, dodecyl and the like. Also, as an alkenyl group, for example, ethenyl group, 1-propenyl group, 1-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-ethyl-2-yl group Examples thereof include a butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like, and examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, 1- A pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl 2- butynyl group, 2-octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group etc. can be mentioned.

  Moreover, as said alicyclic hydrocarbon group, a C3-C20 (preferably 3-12) alicyclic hydrocarbon group is preferable, and, specifically, a C3-C20 (preferably 3-12) And a cycloalkyl group, and more specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group and the like. Here, in the present invention, the term "alicyclic hydrocarbon group" is a generic term for the carbocyclic compounds having a structure in which carbon atoms are cyclically bonded, excluding aromatic compounds, and the above-mentioned aliphatic carbonization It also includes those having a hydrogen group as a substituent or a linking group to a nitrogen atom or the like. Furthermore, as said aromatic hydrocarbon group, a C6-C20 (preferably 6-10) aromatic hydrocarbon group is preferable, and, more specifically, a C6-C20 (preferably 6-14) And an aryl group of Here, in the present invention, the term "aryl group" means a monocyclic to tricyclic aromatic hydrocarbon group, and specific examples thereof include phenyl group, naphthyl group, anthryl group, phenanthryl group, azulenyl group and the like. Can.

  As a substituent in a hydrocarbon group, a halogen atom, a hydroxyl group, a C1-C6 alkoxy group, etc. can be mentioned. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As a specific example of a C1-C6 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a phenoxy group etc. can be mentioned.

In the above formula (2), examples of the single bond or divalent linking group (Z) include an alkanediyl group having 1 to 10 (preferably 1 to 6) carbon atoms, and 6 to 20 (preferably 6 to 6) carbon atoms. The arylene group of 14), -CONH-R < ⁶ >-(* 1) group, -COO-R < ⁷ >-(* 1) group etc. are mentioned. Here, R ⁶ and R ⁷ each independently represent a single bond, an alkanediyl group having 1 to 10 (preferably 1 to 6) carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms, * 1) indicates that it is a bond that bonds to N. As the alkanediyl group, for example, methylene group, ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, Propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane-1,5 -Diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group etc. can be mentioned. Moreover, as an arylene group, a phenylene group, a naphthylene group, a biphenylene group, an anthrylene group etc. can be mentioned, for example. As a C2-C10 alkylene oxy alkylene group, ethylene oxy ethylene group, ethylene oxy propylene group, propylene oxy propylene group, ethylene oxy butylene group etc. can be mentioned, for example. Among them, as Z, a -COO-R ⁷ -(* 1) group is preferable, and as R ⁷ , an alkanediyl group having 2 to 6 carbon atoms is preferable.

  Further, as the unsaturated monomer containing an amino group, which is an essential component of the polymer of the present invention, for example, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate are more preferable.

  The content ratio of the unsaturated monomer having an amino group is preferably in the range of 0.5 to 55% by mass, more preferably 1 to 35% by weight, and still more preferably 1 to 15% by weight in all the monomer components. It is good to be%. If the content of the amino group-containing unsaturated monomer is less than 0.5% by mass, the dispersibility and the stability of the colorant may be insufficient. If the amount is more than 55% by mass, the viscosity of the polymer may be increased to deteriorate the handleability or the heat resistance may be insufficient.

  The monomer component for obtaining the polymer (A) is an unsaturated monomer having an acid group (preferably a carboxyl group) which is an essential component, an unsaturated monomer having a hydroxyl group, an unsaturated group having an amino group. In addition to the saturated monomer, a monomer (d) represented by the following general formula (1) may be contained, if necessary.

(In formula (1), R ¹ and R ² each independently represent a hydrocarbon group selected from methyl, ethyl, cyclohexyl and benzyl.)
In the above general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, but methyl and ethyl From the viewpoint of heat resistance, a primary or secondary carbon substituent which is difficult to be eliminated by an acid such as cyclohexyl, benzyl or the like or heat is preferred. R ¹ and R ² may be substituents of the same type or different substituents.

  The monomer represented by the general formula (1) (hereinafter sometimes referred to as "ether dimer" or "dialkyl-2,2 '-(oxydimethylene) diacrylate monomer") is polymerized. It is inferred that the ether dimer undergoes a cyclization reaction to form a tetrahydropyran ring structure in the constituent units of the polymer.

(D) The constituent unit derived from the monomer represented by the general formula (1) is considered to have the above tetrahydropyran ring structure.
In the above general formula (1), it may have a substituent represented by R ¹ and R ² , and, for example, a linear or branched alkyl group such as methyl, ethyl etc .; Formula group; an alkyl group substituted with an aryl group such as benzyl; and the like. Acids such as methyl, ethyl, cyclohexyl and benzyl and primary or secondary carbon substituents which are not easily released by heat are preferred from the viewpoint of heat resistance. R ¹ and R ² may be substituents of the same type or different substituents.

  In addition to the above-mentioned constituent units derived from the ether dimer, it is selected from constituent units derived from (e) N-substituted maleimide monomers and (f) constituent units derived from α- (unsaturated alkoxyalkyl) acrylate monomers. And at least one structural unit.

  The above (d) ether dimer, (e) N-substituted maleimide monomer, and (f) α- (unsaturated alkoxyalkyl) acrylate monomer can be a single monomer capable of introducing a ring structure into the main chain skeleton of the polymer. It is a mer. (E) N-substituted maleimide monomer is a monomer having a double bond-containing ring structure in the molecule, and (f) α- (unsaturated alkoxyalkyl) acrylate monomer is cyclopolymerized It is a monomer that forms a polymer having a ring structure in its main chain.

  A polymer containing an N-substituted maleimide-based monomer unit and / or a dialkyl-2,2 ′-(oxydimethylene) diacrylate-based monomer unit has heat resistance and dispersibility (for example, colorant dispersion) ), Hardness and the like can be further improved. In addition, polymers containing α- (unsaturated alkoxyalkyl) acrylate monomer units have performance contributing to plate-making properties such as adhesion, curability, dry re-dissolvability, etc., colorant dispersion, heat resistance, It is possible to provide a cured film with improved transparency and the like. In addition, as above-mentioned, the polymer containing a monomer unit means the polymer which contains the structural unit derived from the said monomer by the polymerization reaction and crosslinking reaction of a monomer, for example.

  Examples of the N-substituted maleimide monomer include N-cyclohexyl maleimide, N-phenyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, N-t-butyl maleimide, N-dodecyl maleimide, N-benzyl maleimide, N-naphthyl maleimide, etc. are mentioned, These 1 type (s) or 2 or more types can be used. Among them, N-cyclohexyl maleimide, N-phenyl maleimide, and N-benzyl maleimide are preferable, and N-benzyl maleimide is particularly preferable, from the viewpoint of less coloring and excellent dispersibility.

  Examples of the N-benzyl maleimide include: benzyl maleimide; alkyl-substituted benzyl maleimides such as p-methylbenzyl maleimide, p-butyl benzyl maleimide, etc .; phenolic hydroxyl-substituted benzyl maleimides such as p-hydroxybenzyl maleimide; o-chlorobenzyl maleimide , Halogen-substituted benzyl maleimides such as o-dichlorobenzyl maleimide, p-dichlorobenzyl maleimide and the like; and the like.

  As the above-mentioned dialkyl-2,2 '-(oxydimethylene) diacrylate monomer, for example, dimethyl-2,2'-[dimer] is preferable from the viewpoint of little coloring, dispersibility, industrial availability and the like. It is preferable to use oxybis (methylene)] bis-2-propenoate and the like.

Examples of the α- (unsaturated alkoxyalkyl) acrylate monomers include α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, and α-allyloxymethyl. N-propyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, n-amyl α-allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate n -Hexyl, α-allyloxymethyl acrylic acid s-hexene , N-heptyl α-allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, α-allyloxy 2-ethylhexyl methyl acrylate, capryl α-allyloxymethyl acrylate, nonyl α-allyloxymethyl acrylate, decyl α-allyloxymethyl acrylate, undecyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid Lauryl, tridecyl α-allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-aryl Linear saturated hydrocarbon groups such as stearyl yloxy methyl acrylate, nonadecyl α-allyloxy methyl acrylate, eicosyl α-allyloxy methyl acrylate, ceryl α-allyloxy methyl acrylate, melic α-allyloxy methyl acrylate Containing α- (allyloxymethyl) acrylate is preferred. In addition, alkyl- (α-methallyloxymethyl) acrylate monomers and the like are also preferable. Among them, methyl α-allyloxymethyl acrylate (also referred to as α- (allyloxymethyl) methyl acrylate) is particularly preferable.
The α- (unsaturated alkoxyalkyl) acrylate monomer can be produced, for example, by the production method disclosed in WO 2010/114077.

  The proportion of the above (d) ether dimer is not particularly limited with respect to the total of all the monomer components constituting the above-mentioned polymer, but 2 to 60% by mass, preferably 5 to 55% by mass in all the monomer components More preferably, it is 5 to 50% by mass. If the amount of ether dimer is too large, it may be difficult to obtain low molecular weight ones during polymerization, or it may be easily gelled. On the other hand, if it is too small, such as transparency and heat resistance There is a possibility that the coating film performance may be insufficient.

  The proportions of the (e) N-substituted maleimide monomer and the (f) α- (unsaturated alkoxyalkyl) acrylate monomer are not particularly limited as in the case of the ether dimer, but 2 to 2 of all the monomer components 60% by mass, preferably 5 to 55% by mass, more preferably 5 to 50% by mass.

  The monomer component for obtaining the polymer (A) is an unsaturated monomer containing an acid group (preferably a carboxyl group) which is an essential component, an unsaturated monomer containing a hydroxyl group, a general formula If necessary, other copolymerizable monomers may be contained in addition to the ether dimer shown in 1). As another copolymerizable monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n (meth) acrylate n -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylic acid esters such as (meth) acrylic acid 1-adamantyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyl oxyethyl, and (meth) acrylic acid dicyclopentanyl. Also, aromatic vinyl compounds such as styrene, vinyl toluene, α-methylstyrene and the like to the extent that heat resistance is not affected; alkyl-substituted maleimides such as N-methyl maleimide, N-isopropyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N Maleimide having an aromatic group such as benzyl maleimide; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; vinyl esters such as vinyl acetate; It may be polymerized. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate and benzyl (meth) acrylate are preferable in that they have good transparency and are less likely to impair heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

  In addition, the polymer of the present invention may further contain a polymerizable double bond in the side chain. It can be cured by heat or light by providing a polymerizable double bond in the side chain. Therefore, the sensitivity to light when it is formed into a photocurable resin composition is improved, the curing is performed with a smaller amount of light, and the mechanical strength after curing is also enhanced. As a method of introducing a polymerizable double bond into a side chain, a method of adding a compound containing a polymerizable unsaturated double bond to at least one selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group can be mentioned. . As a polymerizable unsaturated double bond, the double bond which a (meth) acryloyl group has is preferably mentioned from the reactive point of the polymer obtained.

  Specific examples of the compound containing at least one member selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group and a polymerizable unsaturated double bond include 2-hydroxyethyl (meth) acrylate and (meth) acryl. A compound having a hydroxyl group and a double bond such as 2-hydroxypropyl acid or allyl alcohol; a glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, an epoxy group such as allyl glycidyl ether and a double bond Compounds having a double bond with an oxazoline group such as vinyl oxazoline, isopropenyl oxazoline, etc .; among these, among these, the reactivity is high, the reaction can be easily controlled, and it is easy to obtain, and Not only radically polymerizable double bonds but also hydroxyl groups can be introduced at the same time From the point, glycidyl (meth) acrylate and (meth) acrylic acid 3, 4-epoxycyclohexyl methyl.

  The polymer of the present invention may further contain an epoxy group. Thereby, it can be cured by heat or light. In order to introduce an epoxy group into a polymer, for example, a monomer having an epoxy group may be polymerized as a monomer component. As a monomer which has an epoxy group, glycidyl meta) acrylate and (meth) acrylic acid 3, 4- epoxycyclohexyl are mentioned, for example. The monomer for introducing these epoxy groups may be only one type or two or more types.

  When polymerizing the monomer component, a commonly used polymerization initiator may be added, if necessary. The polymerization initiator is not particularly limited. For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane) Azo compounds such as carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methyl propionate) and the like; These polymerization initiators may be used alone or in combination of two or more. The amount of the initiator used may be appropriately set according to the combination of monomers to be used, reaction conditions, molecular weight of the target polymer, etc., and is not particularly limited, but weight average molecular weight without gelation It is good to set it as 0.1-15 mass%, more preferably 0.5-10 mass% with respect to all the monomer components in that several thousands-tens of thousands of polymers can be obtained.

  When polymerizing the monomer component, a chain transfer agent that is usually used may be added as needed for molecular weight control. Examples of chain transfer agents include mercaptan-based chain transfer agents such as n-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer, etc. Preferably, the chain transfer effect is high. Preferred are n-dodecyl mercaptan and mercapto propionic acid which can reduce residual monomers and are easily available. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, molecular weight of target polymer, etc., and is not particularly limited, but gelation Of 0.1 to 15% by mass, more preferably 0.5 to 10% by mass with respect to all the monomer components in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained. Is preferred.

  Although the weight average molecular weight in particular of the said polymer is not restrict | limited, Preferably it is 2000-20000, More preferably, it is 5000-100000. When the weight average molecular weight exceeds 200,000, the viscosity becomes too high to form a coating film easily, and when it is less than 2,000, it tends to be difficult to develop sufficient heat resistance. The acid value of the polymer is preferably 20 to 300 mg KOH / g, more preferably 30 to 200 mg KOH / g. More preferably, it is 40 to 180 mg KOH / g. When the acid value of the polymer is less than 20 mg KOH / g, there is a risk that the solubility will not be sufficient if solubility by an alkaline substance is required. When it exceeds 300 mg KOH / g, it tends to be too viscous to form a coating film. The amine value of the polymer is preferably 1 to 200 mg KOH / g, more preferably 1 to 150 mg KOH / g. More preferably, it is 2 to 100 mg KOH / g. When the acid value of the polymer is less than 1 mg KOH / g, the dispersibility of the colorant may be sufficient. When it exceeds 200 mg KOH / g, it may become too viscous to form a coated film, or the heat resistant colorability of the resin may be lowered.

  In the case of the introduction of the above-mentioned double bond, the double bond equivalent, which is the molecular weight per double bond of the polymer, is 350 to 4500 g / mol. 400-4000 are more preferable, and 500-3800 are the most preferable. If the double bond equivalent is too high, the sensitivity to light may be lowered and the developability may be reduced, and if the double bond equivalent is too low, coloring may occur upon curing, or storage stability may deteriorate, The solubility in solvents may be reduced.

  The double bond equivalent is a measure of the amount of double bonds contained in the molecule, and for compounds of the same molecular weight, the larger the value of the double bond equivalent, the smaller the amount of double bonds introduced. Become. It can be calculated from the amount of the polymer and the compound introducing the double bond. Moreover, it can measure using various analysis, such as titration and elemental analysis, NMR, IR, or a differential scanning calorimeter method.

  In addition, in the curable resin composition containing (A) the polymer and (B) the polyfunctional (meth) acrylate, the polymer component of the (A) is referred to as “(A) component”, the above ((A)) The polyfunctional (meth) acrylate of B) may also be called "(B) component". Although the application is not limited, it is suitably used as a material for forming a protective film of a color filter, a liquid crystal display device, an integrated circuit device, a solid-state imaging device or the like.

  In the above curable resin composition, examples of (B) polyfunctional (meth) acrylates include (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylol. Propane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, di Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethytri) ) A polyfunctional (meth) acrylate of tri- (meth) acrylate of isocyanurate. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

  In the curable resin composition, light or a thermal polymerization initiator may be used when curing the curable resin composition. As the photopolymerization initiator, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2) -Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-) Morphorinophenyl) butanone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-) Acetophenones such as methylppyonyl) benzyl] phenyl} -2-methylpropan-1-one; benzoin Benzoines such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ' 4,4,4'-Tetra (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) Benzophenones such as ethyl] benzenemethaminium bromide and (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone Thioxanthones such as 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one meso chloride, and the like And phenylglyoxylic methyl ester, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like. Among these, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone are preferable.

  For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butylperoxyisopropyl carbonate, tert-amylperoxy-2-ethylhexanoate, Organic peroxides such as t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis Azo compounds such as (2,4-dimethyl valeronitrile), dimethyl 2,2′-azobis (2-methyl propionate) and the like; These light and heat polymerization initiators may be used alone or in combination of two or more.

  The said curable resin composition (preferably negative curable resin composition) may contain the solvent as a diluent as needed. As the solvent, it is possible to uniformly dissolve the components of the polymer (A), the polyfunctional (meth) acrylate (B), and the polymerization initiator to be contained as required, and do not react with the components. There is no particular restriction. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform, dimethyl sulfoxide Etc. In addition, what is necessary is just to set content of a solvent suitably according to the optimal viscosity at the time of using a resin composition. For example, it is 900 parts by mass or less, more preferably 500 parts by mass or less, with respect to 100 parts by mass of the resin. As a preferable lower limit, it is 30 mass parts or more with respect to 100 mass parts of resin, More preferably, it is 60 mass parts or more. By controlling to the said numerical range, the handling property of a composition, storage stability, and the efficiency at the time of coating operation improve.

  In addition to the polymer (A), the polyfunctional (meth) acrylate (B), the polymerization initiator, and the solvent, the curable resin composition may be, for example, hydroxylated as long as the effects of the present invention are not impaired. Fillers such as aluminum, talc, clay and barium sulfate, dyes, pigments, antifoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers, antioxidants, UV absorbers, light It may contain known additives such as stabilizers, flame retardants, polymerization inhibitors, polymerization retarders, polymerization accelerators, thickeners, dispersants, surfactants and the like. As the pigment, one or more of various organic or inorganic colorants can be used. As the organic coloring agent, dyes, organic pigments, natural dyes and the like can be used.

  The present invention is also a laminate in which a cured layer obtained by curing the polymer is provided on a substrate. Examples of the material used as the substrate of the present invention include glass, acrylic resin, polycarbonate resin, polyester resin such as PET, transparent material such as polystyrene resin, and metal material such as aluminum, copper, iron, stainless steel and the like.

  The polymer of the present invention is excellent in transparency and heat resistance, and can be used, for example, in applications such as resist materials, various coating agents, and paints, and since it has a carboxyl group in the polymer, colored pixels of color filters It can be suitably used as an alkali-developable negative resist material for producing a black matrix, an overcoat, a photo spacer, an optical waveguide and the like. Since the polymer of the present invention also has good pigment dispersibility when it has a tetrahydropyran ring structure in its structure, it can also be suitably used for a colored curable resin composition for color filters.

  EXAMPLES The present invention will be described in more detail by way of the following examples, but the present invention is not limited to these examples. The analysis in each synthesis example and comparative synthesis example was performed as follows.

<Weight average molecular weight>
It measured by polystyrene conversion using the gel permeation chromatograph measuring apparatus ("Shodex GPC System-21H" product made in Showa Denko).

<Polymer concentration in polymer solution>
A solution obtained by adding 4 g of acetone to 1 g of the polymer solution was naturally dried at room temperature, further dried under reduced pressure (160 ° C./5 mmHg) for 5 hours, and allowed to cool in a desiccator to measure its weight. And the non volatile matter of the polymer solution was computed from the amount of weight reduction, and this was made into the polymer concentration.

<Acid number>
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the polymer solution, stirred and uniformly dissolved, and an aqueous solution of 0.1 mol / L KOH is used as a titration solution to make an automatic titrator ("COM-555" Hiranuma Sangyo Made to measure the acid value of the solution. And the acid value of the polymer was calculated from the acid value and the polymer concentration of the solution.

<Amine value>
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the polymer solution, stirred and uniformly dissolved, and an aqueous 0.1 mol / L HCl aqueous solution is used as a titration solution to make an automatic titrator ("COM-555" Hiranuma Sangyo ) And the amine value of the solution was measured. Then, the amine value of the polymer was calculated from the amine value of the solution and the polymer concentration.

Example 1
A separable flask equipped with a cooling pipe is prepared as a reaction vessel, while 20 mass of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as "MD") is prepared as a monomer dropping vessel. Parts, 15 parts by mass of methacrylic acid (hereinafter referred to as "MAA"), 10 parts by mass of 2-hydroxyethyl methacrylate (hereinafter referred to as "HEMA"), dimethylaminoethyl methacrylate (hereinafter referred to as "DAM") 2.9 Parts by mass, 40 parts by mass of cyclohexyl methacrylate (hereinafter referred to as "CHMA"), 12.1 parts by mass of methyl methacrylate (hereinafter referred to as "MMA"), t-butylperoxy-2-ethylhexanoate (trade name) 3 parts by mass of “Perbutyl O”, manufactured by NOF Corporation; hereinafter referred to as “PBO”), propylene glycol monomethyl ether acetate Prepare well stirred and mixed 40 parts by weight of tate (hereinafter referred to as "PGMEA"), and as a chain transfer agent dropping tank, 4 parts by weight of n-dodecanethiol (hereinafter referred to as "n-DM"), 32 parts by weight of PGMEA Were well mixed by stirring. 71 parts by mass of PGMEA was charged into the reaction vessel, and after replacing with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C. After 60 minutes from the end of the dropping, the temperature rising was started and the reaction vessel was heated to 110 ° C. After maintaining the temperature at 110 ° C. for 3 hours, the solution was cooled to room temperature to obtain a polymer solution 1 having a concentration of 40% by mass. The weight average molecular weight of the polymer was 10000, the acid value was 100 mg KOH / g, and the amine value was 10 mg KOH / g.

Example 2
A separable flask equipped with a cooling pipe is prepared as a reaction vessel, while 20 mass parts of MD, 15 mass parts of MAA, 20 mass parts of HEMA, 5.8 mass parts of DAM, 35 mass parts of CHMA, 4.2 mass parts of MMA as a monomer dropping tank. A well-stirred mixture of 3 parts by mass of PBO and 40 parts by weight of PGMEA was prepared, and a well-stirred mixture of 4 parts by mass of n-DM and 32 parts by weight of PGMEA was prepared as a chain transfer agent dropping tank.
71 parts by mass of PGMEA was charged into the reaction vessel, and after replacing with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C. After 60 minutes from the end of the dropping, the temperature rising was started and the reaction vessel was heated to 110 ° C. After maintaining at 110 ° C. for 3 hours, the solution was cooled to room temperature to obtain a polymer solution 2 having a concentration of 40% by mass. The weight average molecular weight of the polymer was 10000, the acid value was 100 mg KOH / g, and the amine value was 20 mg KOH / g.

Comparative Example 1
A separable flask equipped with a cooling pipe was prepared as a reaction vessel, and on the other hand, 20 parts by mass of MD, 15 parts by mass of MAA, 55 parts by mass of CHA, 10 parts by mass of MMA, 3 parts by mass of PBO, and 40 parts by mass of PGMEA were thoroughly mixed as a monomer dropping vessel. What was prepared, and what stirred and mixed 4 mass parts of n-DM and 32 mass parts of PGMEA well as a chain transfer agent dripping tank was prepared.
71 parts by mass of PGMEA was charged into the reaction vessel, and after replacing with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C. After 60 minutes from the end of the dropping, the temperature rising was started and the reaction vessel was heated to 110 ° C. After maintaining at 110 ° C. for 3 hours, the solution was cooled to room temperature to obtain Comparative Polymer Solution 1 having a concentration of 40% by mass. The weight average molecular weight of the polymer was 10000, and the acid value was 100 mg KOH / g.

Comparative Example 2
A separable flask equipped with a cooling pipe is prepared as a reaction vessel, while 20 mass parts of MD, 15 mass parts of MAA, 5.8 mass parts of DAM, 55 mass parts of CHMA, 4.2 mass parts of MMA, 3 mass parts of PBO as a monomer dropping tank. A well-stirred mixture of 40 parts by mass of PGMEA was prepared, and as a chain transfer agent dropping tank, a well-stirred mixture of 4 parts by mass of n-DM and 32 parts by mass of PGMEA was prepared.
71 parts by mass of PGMEA was charged into the reaction vessel, and after replacing with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C. After 60 minutes from the end of the dropping, the temperature rising was started and the reaction vessel was heated to 110 ° C. After maintaining at 110 ° C. for 3 hours, the solution was cooled to room temperature to obtain Comparative Polymer Solution 2 having a concentration of 40% by mass. The weight average molecular weight of the polymer was 10000, the acid value was 100 mg KOH / g, and the amine value was 20 mg KOH / g.

<Heat resistance>
The test piece 1 is heated at 250 ° C. for 3 hours on a hot plate and cooled to room temperature, and then the b ^* value after the heat resistance test is measured using a spectrocolorimeter (“EE-6000” manufactured by Nippon Denshoku Kogyo Co., Ltd.) did.

<Appearance evaluation>
○: no unevenness is observed in the coating on the test piece 1 after the heat resistance test.
X: Irregularities are observed in the coating on the test piece 1 after the heat resistance test.

Example 3
100 parts by mass of the polymer solution 1 obtained in Example 1, 20 parts of dipentaerythritol hexaacrylate (trade name "Light Acrylate DPE-6A", manufactured by Kyoeisha Chemical Co., Ltd .; hereinafter referred to as "DPE-6A") Two parts of a photo initiator (trade name “IRGACURE 907”, manufactured by Ciba-Geigy; hereinafter referred to as “Irg 907”) and 55 parts of PGMEA were stirred and mixed uniformly to obtain a curable resin composition 1.
The resulting curable resin composition 1 is coated on an alkali free glass plate using a spin coater so that the thickness after total drying is 3 μm, and dried at 100 ° C. for 3 minutes on a hot plate, The ultraviolet light was irradiated using an extra-high pressure mercury lamp so that the irradiation amount was 100 mJ / cm ² . After irradiation, the sample was further dried at 230 ° C. for 30 minutes on a hot plate to obtain a test piece 1. And heat resistance was evaluated by said method using this test piece 1. It was 2.7 when b <^*> value after a heat test was measured. As seen from the appearance of the test piece 1 after the heat resistance test, the coating on the glass had no unevenness and was uniformly formed.

Example 4
After a curable resin composition 2 was prepared in the same manner as in Example 1 except that the resin solution 1 was changed to the resin solution 2, a test piece 2 was similarly prepared to evaluate the heat resistance. The b ^* value measured after the heat resistance test was 3.0. As seen from the appearance of the test piece 1 after the heat resistance test, the coating on the glass had no unevenness and was uniformly formed.

Comparative Example 3
After a curable resin composition 3 was prepared in the same manner as in Example 1 except that the resin solution 1 was changed to the resin solution 3, a comparative test piece 1 was similarly prepared to evaluate the heat resistance. The b ^* value was measured after the heat resistance test and was found to be yellowish in comparison with Example 3 at 4.6. As seen from the appearance of the test piece 1 after the heat resistance test, the coating on the glass was found to have irregularities, and a wrinkled film was formed.

Comparative Example 4
After a curable resin composition 4 was prepared in the same manner as in Example 1 except that the polymer solution 1 was changed to the polymer solution 4, a comparative test piece 2 was similarly prepared to evaluate the heat resistance. did. The b ^* value measured after the heat resistance test was 4.9 and was yellowish as compared with Example 4. As seen from the appearance of the test piece 1 after the heat resistance test, the coating on the glass was found to have irregularities, and a wrinkled film was formed.

From these things, (a) unsaturated monomer having a carboxyl group, (b) unsaturated monomer having a hydroxyl group, and (c) unsaturated monomer having an amino group are polymerized as essential components. The b ^* value after heat resistance in the cured product obtained from the polymer was confirmed to be small.
From the above, it is possible, for the first time, to form a coating film excellent in both heat resistance and transparency by using the polymer having the above-mentioned constitution. For example, it is suitable for applications such as resist materials, various coating agents and paints. It can be used for Further, according to the present invention, for example, it is possible to provide a color filter of good quality free from pattern defects and development residues.

The polymer and resin composition of the present invention can form a coating film which is extremely excellent in both heat resistance and transparency as well as curability. For example, in applications such as resist materials, various coating agents, and paints It can be used suitably.

Claims (7)

(A) a structural unit derived from an unsaturated monomer having an acid group, (b) a structural unit derived from an unsaturated monomer having a hydroxyl group, and (c) A polymer comprising, as an essential component, a constituent unit derived from an unsaturated monomer having an amino group. (D) the following general formula (1)

(In formula (1), R ¹ and R ² each independently represent a hydrocarbon group selected from methyl, ethyl, cyclohexyl and benzyl.)
Selected from the structural units derived from the monomers represented by the above, (e) structural units derived from N-substituted maleimide monomers, and (f) structural units derived from α- (unsaturated alkoxyalkyl) acrylate monomers The polymer according to claim 1, comprising at least one structural unit. An acid value is 20-300 mgKOH / g, The polymer of Claim 1 or 2 characterized by the above-mentioned. The polymer according to any one of claims 1 to 3, which has an amine value of 1 to 200 mg KOH / g. The unsaturated monomer having an amino group is represented by the following general formula (2)

(In formula (2), R ³ has a hydrogen atom or a methyl group, and R ^{4 to} R ⁵ each independently represent a hydrogen atom or a chain or cyclic carbonization which may have a substituent R ⁴ and R ⁵ may be bonded to each other to form a cyclic structure, and Z represents a single bond or a divalent linking group.
The polymer according to any one of claims 1 to 4, characterized in that The polymer according to any one of claims 1 to 5, which is a binder resin for color resist. A laminate comprising a substrate and a cured layer formed by curing the polymer according to any one of claims 1 to 6.