JP2019108531A - Polymer, curable resin composition containing polymer, and application thereof - Google Patents

Abstract

To provide a polymer capable of sufficiently suppressing yellow discoloration during heating, and applicable to high coloring, and a curable resin composition containing the polymer.SOLUTION: There is provided a polymer having a vinyl monomer unit containing a monomer unit represented by the following general formula (I), -COOR, where Rrepresents a monovalent organic group, a carbon atom binding to Ois a tertiary carbon atom, and a hydroxyl group-containing monomer unit. Rrepresents a bivalent hydrocarbon group, Rrepresents a bivalent organic group, X represents a carboxyl group or a sulfonic acid group, and n is 0 or 1.SELECTED DRAWING: None

Description

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

Polymers that can be cured by heat or active energy rays are applied to various applications depending on the properties of the polymer. Examples of such applications include, for example, various optical members, electric and electronic devices such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used for liquid crystal display devices and solid-state imaging devices. And the like, and further studies have been conducted on copolymers suitable for these applications.

Among the applications mentioned above, the color filter is a main member constituting a liquid crystal display device, a solid-state imaging device, etc., and in general, at least three primary colors (red (R), green (G), blue (B)) of a substrate. In addition to the pixels and the resin black matrix (BM) separating them, the pixel and the resin black matrix are covered and protected, and a protective film or the like provided to planarize the unevenness thereof.

In general, when forming a pixel of a color filter using a curable resin composition, (1) an application step of applying the curable resin composition to the entire surface of the substrate, and (2) an application step After exposing a resist film to a pattern through a photomask and curing the exposed area, an exposure step of insolubilizing the cured area, and (3) removing the unexposed area with a developer, and exposing it by baking (baking) A method is employed in which development and baking (baking) processing steps for further curing the part are performed and the same steps are repeated for each color. Considering the application of such a color filter, the resin used and the curable resin composition containing the resin have curability, solvent resistance after curing, adhesion to a substrate, heat resistance And various physical properties such as transparency are required.

So far, various resins have been proposed for resins having such various physical properties.
For example, in Patent Document 1, as a polymer excellent in heat resistance, N-substituted maleimide and / or a specific ether dimer, vinyl toluene, and a monomer having an acid group are copolymerized as a monomer component. Polymers have been proposed.
However, in a resin composition containing a maleimide-derived polymer, since the maleimide-based polymer contains a nitrogen atom, the polymer is colored yellow to yellowish brown when heated, and the transparency of the cured film is insufficient. Was a problem. On the other hand, polymers have been proposed which can form a coating film which is excellent not only in heat resistance but also in transparency.

For example, in Patent Document 2, as a polymer capable of forming a coating film excellent in both heat resistance and transparency, a specific monomer which is an ether dimer of 2- (hydroxyalkyl) acrylic acid ester, and a carboxyl group are disclosed. There is proposed a polymer obtained by copolymerizing an unsaturated monomer to be contained and an unsaturated monomer containing a hydroxyl group as a monomer component.
Moreover, in patent document 3, tertiary carbon containing (meth) which can exhibit various physical properties, such as curability and solvent resistance after hardening, adhesiveness with a base material, heat resistance, transparency, etc., stably. A curable resin composition has been proposed which comprises a (meth) acrylate polymer having an acrylate monomer unit and a monomer unit having a hydroxyl group, a polymerizable compound, and a photopolymerization initiator.

JP 2009-40999 A JP 2012-82317 A JP, 2015-42697, A

In recent years, downsizing, thinning and energy saving of optical members, electric machines, electronic devices and the like have been advanced, and along with this, members such as color filters to be used are required to have high quality performance. However, it is difficult to say that conventional polymers can sufficiently meet such demands, and there is still room for improvement.
In color filter applications, in particular, high brightness and high contrast of the display panel are strongly demanded by high quality of color liquid crystal display devices and expansion of applications, and yellowing at the time of heating of polymer is conventionally There is a need for the development of polymers that can be further suppressed and applicable to high coloration.

The present invention has been made in view of the above-mentioned present situation, and provides a polymer which can sufficiently suppress yellowing upon heating and which can be applied to high coloring, and a curable resin composition containing the above-mentioned polymer The purpose is to

The present inventors have variously examined polymers applicable to color filters and the like in order to solve the above-mentioned problems, and a cured product having excellent heat-resistant colorability can be obtained by having at least three specific monomer units. I found that I could get it. In addition, the present inventors found that such a polymer and a curable resin composition containing the polymer are particularly suitable as a polymer and a resin composition for forming a member such as a color filter application. The present invention has been completed.

That is, the present invention relates to a monomer unit represented by the following general formula (I), -COO ^* R ⁴ (R ⁴ represents a monovalent organic group, and a carbon atom bonded to O ^* is a tertiary A polymer comprising a vinyl-based monomer unit containing a carbon atom) and a hydroxyl group-containing monomer unit.

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

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

In the polymer, the content of the monomer unit represented by the general formula (I) is preferably 10 to 60% by mass.

In the polymer, the content of the (meth) acrylic acid unit is preferably less than 5% by mass.

In the said polymer, it is preferable that an acid value is 40-160 mgKOH / g.

The present invention is also a curable resin composition characterized by containing the above-described polymer and a polymerizable compound.

The present invention is also a laminate having a cured product of the above-described polymer or a cured product of the above-described curable resin composition on a substrate.

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

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

Since the polymer of the present invention has the above-mentioned constitution, it can give a cured product excellent in heat-resistant colorability. Such a polymer of the present invention, and a curable resin composition containing the above-mentioned polymer, are color filters used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. Use as optical members and components such as black matrix, photo spacer, black column spacer, ink, printing plate, printed wiring board, semiconductor element, photoresist, insulating film etc. for various uses such as electric and electronic equipment In particular, it can be suitably used for a color filter used for a liquid crystal display device, a solid-state imaging device or the like.

The present invention will be described in detail below.
In addition, what combined two or more of each preferable form of this invention described below is also a preferable form of this invention.
Furthermore, in the present specification, "(meth) acrylate" means "acrylate and / or methacrylate", and "(meth) acrylic acid" means "acrylic acid and / or methacrylic acid".

1. Polymer The polymer of the present invention is a monomer unit represented by the following general formula (I), -COO ^* R ⁴ (R ⁴ represents a monovalent organic group, and a carbon atom bonded to O ^* is And a tertiary carbon atom)) having a vinyl-based monomer unit containing a group and a hydroxyl group-containing monomer unit.

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

Since the polymer of the present invention is constituted as described above, yellowing upon heating can be suppressed, that is, a cured product excellent in heat-resistant colorability can be provided.
The reason why the above-mentioned polymer can give a cured product excellent in heat-resistant colorability is that when the above-mentioned polymer is heated, part of the monomer unit represented by the above-mentioned general formula (I) is eliminated And a hydroxyl group is formed, and the hydroxyl group and the hydroxyl group of the hydroxyl group-containing monomer unit capture a radical present in the reaction system to reduce the influence of the radical, and when the polymer is heated, The above-mentioned -COO ^* R ⁴ (R ⁴ represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom.) Third of vinyl-based monomer units containing a group It is surmised that a class carbon atom is eliminated to form an acid group, and the acid group and the above-mentioned hydroxyl group crosslink to form a strong film (cured product).

The polymer of the present invention is also excellent in curability, hardness of the cured product, solvent resistance, heat resistance, transparency, and adhesion to a substrate. Furthermore, when the above-mentioned polymer is applied to a resin composition containing a coloring material, the concentration of the coloring material in the obtained cured product can be increased, so that further thin film formation can be realized, and the above-mentioned resin composition can be colored When applied to a filter application, it is possible to achieve higher color purification and higher blocking ratio of the black matrix.

The above-mentioned polymer can improve the curability and the properties of the cured product because, as described above, when the above-mentioned polymer is heated, the hydroxyl group of the above-mentioned polymer and the single component constituting the above-mentioned polymer It is speculated that crosslinking of the hydroxyl group generated from the monomer unit with the acid group and that the hydroxyl group captures radicals present in the reaction system. Furthermore, while it is possible to increase the color material concentration in the cured product, as described above, while the crosslinking reaction proceeds due to the elimination of tertiary carbon atoms, the eliminated components are volatilized and the amount of resin in the cured product is It is speculated to be due to relative decrease.

The monomer units constituting the polymer of the present invention will be described in detail. In the present invention, "monomer unit" means a structural unit derived from a monomer.
<Monomer Unit (A) Represented by General Formula (I)>
The polymer of the present invention has a monomer unit represented by the above general formula (I) (hereinafter, also described as "monomer unit (A)").
In the above general formula (I), 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.
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 an alkylene group is preferred. Examples of the alicyclic structure include a cyclohexane skeleton, an adamantane skeleton, and a norbornene skeleton. Moreover, these may have a substituent.
R ² is preferably an alkylene group such as methylene group, ethylene group, propylene group, butylene group, heptylene group, octylene group or dodecylene group; an arylene group such as phenylene group, tolylene group or naphthylene group; A group substituted by a functional group such as a hydroxy group; and the like.
Among them, as R ² , an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is more preferable.

R ³ represents a divalent organic group. As said bivalent organic group, Preferably a C1-C10 bivalent chain-like, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group is mentioned, More preferably, it is C1-C5 And a divalent linear or branched saturated hydrocarbon group or unsaturated hydrocarbon group. The organic group may have a substituent.

As R ³ , for example, an alkylene group such as methylene, ethylene, propylene, trimethylene, butylene, ethylethylene, hexylene, octylene, dodecylene and the like; vinylene, propenylene, isopropenylene and the like And alkenylene groups such as butenylene group, pentenylene group and hexenylene group; cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, norbornylene group, adamantylene group etc. cycloalkylene group; phenylene group, tolylene group, naphthylene Arylene groups such as fluorene group; alkyl ether groups such as ethyl ether group and propyl ether group; and groups including bonds such as -O-, -S-, -SO-, -SO _2- together with these groups Be
Among them, R ³ is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 5 carbon atoms, from the viewpoint of further excellent heat resistant colorability.

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

As a monomer which gives the said monomer unit (A), Preferably, unsaturated groups, such as a succinic-acid mono (2-acryloyl oxyethyl), succinic-acid mono (2- methacryloyl oxy ethyl), etc., and a carboxyl group are preferable. The unsaturated monocarboxylic acids etc. which are chain-extended between are mentioned.
The said polymer may have only 1 type in what was mentioned above as said monomer unit (A), and may have 2 or more types.

The content of the monomer unit (A) in the polymer is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, with respect to 100% by mass of all the monomer units of the polymer. is there.

<-Vinyl-based monomer unit (B) containing a -COO ^* R ⁴ group>
The above-mentioned polymer is a vinyl single monomer further containing —COO ^* R ⁴ (R ⁴ represents a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom). It has a monomer unit (hereinafter, also described as "vinyl-based monomer unit (B)").

In the vinyl-based monomer unit (B), ^{R 4} a -COO ^* R ⁴ represents a monovalent organic group, the carbon atom bonded to ^{O *} is a tertiary carbon atom. The tertiary carbon atom means a carbon atom in which three other carbon atoms are bonded to the carbon atom.
As said monovalent organic group, Preferably a C1-C91 monovalent | monohydric chain | strand-shaped, branched or cyclic saturated or unsaturated hydrocarbon group is mentioned. The organic group may have a substituent.
The carbon number of R ⁴ is more preferably 1 to 50 carbon atoms, still more preferably 1 to 35 carbon atoms, and particularly preferably 1 to 20 carbon atoms.
R ⁴ is preferably the same monovalent organic group as A in formula (a) described later.

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

The polymer which has the said tertiary carbon containing (meth) acrylate type monomer unit can be obtained by superposing | polymerizing the monomer component containing a tertiary carbon containing (meth) acrylate type monomer.
It is preferable that the said tertiary carbon containing (meth) acrylate type monomer is a thing which has a structure which the oxygen atom adjacent to the (meth) acryloyl group couple | bonded with the tertiary carbon atom.

The above-mentioned tertiary carbon-containing (meth) acrylate monomer is a compound having one polymerizable carbon-carbon double bond in the molecule, that is, a (meth) acryloyl group (CH ₂ = C (R ⁵ ) in the molecule It is preferable that it is a compound which has one -C (= O)-), for example, the following general formula (a):
^{_{CH 2 = C (R 5)}} -C (= O) -O-A (a)
(Wherein, R ⁵ represents a hydrogen atom or a methyl group. A represents a monovalent organic group containing a structure having a tertiary carbon atom on the oxygen atom side.) Is preferred.

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

The carbon number of the organic group represented by A is an oxygen atom adjacent to a (meth) acryloyl group (CH ₂ CC (R ⁵ ) -C (= O)-), and the third of the A adjacent to it. The number of carbon atoms is preferably 12 or less, more preferably 9 or less, from the viewpoint that new compounds formed by cleavage of the O-C bond with the class carbon atom are easily volatilized. Further, the organic group represented by A may have a branched structure.

Here, in the above-mentioned tertiary carbon-containing (meth) acrylate monomer, at least one of the adjacent carbon atoms of the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth) acryloyl group is bonded to a hydrogen atom Is preferred. For example, a tertiary carbon-containing (meth) acrylate monomer is a compound represented by the above general formula (a), and A is represented by -C (R ⁶ ) (R ⁷ ) (R ⁸ ) Group, 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 heating cleaves the O-C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent to it to simultaneously generate (meth) acrylic acid. A double bond (C = C) is formed between the tertiary carbon atom and the carbon atom adjacent to the tertiary carbon atom, and a new compound is more stably generated.

Preferably, the new compounds produced as described above are volatile. In this case, at the same time the film thickness of the cured product (cured film) is reduced due to the new compound volatilizing out of the cured product, a curable resin composition containing, for example, the above-mentioned polymer and a coloring material In the case of using an object, the color material concentration increases after heating. Therefore, it is possible to realize further thinning of the film, and to achieve high color purification and a high light blocking ratio of the black matrix. When this point is considered, it is preferable that said R < ⁶ >, R < ⁷ > and R < ⁸ > are the same or different, and are a C1-C15 saturated hydrocarbon group. More preferably, it is a C1-C10 saturated hydrocarbon group, More preferably, it is a C1-C5 saturated hydrocarbon group, Most preferably, it is a C1-C3 saturated hydrocarbon group.

The tertiary carbon-containing (meth) acrylate monomer is preferably t-butyl (meth) acrylate or t-amyl (meth) acrylate.
The said polymer may have only 1 type in what was mentioned above as said vinyl-type monomer unit (B), and may have 2 or more types.

The content of the vinyl-based monomer unit (B) in the polymer is preferably 5 to 80% by mass, more preferably 10 to 70% by mass with respect to 100% by mass of all the monomer units of the polymer. %, More preferably 20 to 60% by mass.

<Hydroxyl group-containing monomer unit (C)>
The polymer further contains a hydroxyl group-containing monomer unit (hereinafter also referred to as "monomer unit (C)"). The polymer having a hydroxyl group-containing monomer unit can be obtained by polymerizing a monomer component containing a hydroxyl group-containing monomer.
The above hydroxyl group-containing monomer is not particularly limited as long as it is a compound having a hydroxyl group and a polymerizable double bond in the molecule, and examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxy (meth) acrylate Propyl, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3 (meth) acrylate Preferred are hydroxyalkyl (meth) acrylates such as -hydroxypropyl, and more preferred is 2-hydroxyethyl (meth) acrylate.
The said polymer may have only 1 type in what was mentioned above as said monomer unit (C), and may have 2 or more types.

The content of the monomer unit (C) in the polymer is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, with respect to 100% by mass of all the monomer units of the polymer. is there.

<Monomer unit (D) having a ring structure in the main chain>
The polymer is preferably a ring structure-containing polymer having a ring structure in the main chain. By having a ring structure in the main chain, the heat resistant colorability can be further improved.
Examples of the ring structure include imide ring, tetrahydropyran ring, tetrahydrofuran ring, lactone ring and the like. In order to have these ring structures, the polymer preferably has a monomer unit having a ring structure in the main chain (hereinafter, also described as "monomer unit (D)").

Examples of the monomer giving a monomer unit having a ring structure in the main chain include a monomer having a double bond-containing ring structure in the molecule, and a ring structure in the main chain after cyclopolymerization. The monomer which forms a polymer, the monomer which forms a ring structure after superposition | polymerization, etc. are mentioned. Among them, N-substituted maleimide monomers, dialkyl-2,2 '-(oxydimethylene) diacrylate monomers, and α- (-) from the viewpoint of good heat resistance, hardness, colorant dispersibility and the like. At least one selected from the group consisting of unsaturated alkoxyalkyl) acrylate monomers is preferable, and in terms of further excellent heat resistant colorability, dialkyl-2, 2'- (oxydimethylene) diacrylate monomer amount Body and / or N-substituted maleimide monomers are more preferred.

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, from the viewpoint of transparency, N-phenyl maleimide, N-benzyl maleimide, and N-cyclohexyl maleimide are preferable, and in particular, N-cyclohexyl maleimide is preferable.

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.

Examples of the above-mentioned dialkyl-2,2 '-(oxydimethylene) diacrylate monomers include, for example, 2,2'-[oxybis (methylene)] bisacrylic acid, dialkyl-2,2 '-[oxybis (methylene) ]] The compound etc. in which at least one of the ester site | parts, such as a bis- 2-propenoate and a dialkyl 2, 2'- [oxy bis (methylene)] bis- 2-propenoate, contains a tertiary carbon etc. are mentioned.
Examples of the dialkyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate 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 (isopropyl) -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-propenoate, di (t-amyl) -2,2'-[oxy (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, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate is more preferable from the viewpoint of transparency, dispersibility, industrial availability and the like.

Examples of the α- (unsaturated alkoxyalkyl) acrylate monomers include α- (allyloxymethyl) acrylate monomers.
Specific examples of the above α- (allyloxymethyl) acrylate monomers include, for example, α-allyloxymethyl acrylic acid; methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyl N-propyl oxymethyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-α-allyloxymethyl acrylate Butyl, α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate n-hexyl, α-allyloxy Methyl acrylic acid s-hexyl, α-allyloxy methyl acrylic acid n-hexane Ethyl, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, α-allyloxy Capryl methyl acrylate, nonyl α-allyloxy methyl acrylate, decyl α-allyloxy methyl acrylate, undecyl α-allyloxy methyl acrylate, lauryl α-allyloxy methyl acrylate, tridecyl α-allyloxy methyl acrylate, Myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, α-aryl Alkyl- (α-allyloxymethyl) acrylate monomers such as nonadecyl acrylate, α-allyloxymethyl acrylate eicosyl, α-allyloxymethyl acrylate ceryl, α-allyloxymethyl acrylate melicyl; α-allyloxymethyl acrylate methoxyethyl, α-allyloxymethyl acrylate methoxyethoxyethyl, α-allyloxymethyl acrylate methoxyethoxyethoxyethyl, α-allyloxymethyl acrylate 3-methoxybutyl, α-allyloxymethyl Alkoxy alkyls such as ethoxyethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, phenoxyethoxyethyl α-allyloxymethyl acrylate (.Alpha.-allyloxymethyl) acrylate monomers; .alpha.-allyloxymethylacrylate, .alpha.-allyloxymethylacrylate, .alpha.-allyloxymethylacrylate, .alpha.-allyloxymethylacrylate Fluoroethyl, difluoroethyl α-allyloxymethyl acrylate, chloroethyl α-allyloxymethyl acrylate, dichloroethyl α-allyloxymethyl acrylate, bromoethyl α-allyloxymethyl acrylate, dibromoethyl α-allyloxymethyl acrylate Α-allyloxymethyl vinyl acrylate, allyl α-allyloxymethyl acrylate, methallyl α-allyloxymethyl acrylate, crotyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate Propyl lactate, cyclopentyl α-allyloxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, 4-methylcyclohexyl α-allyloxymethyl acrylate, 4-tert-butylcyclohexyl α-allyloxymethyl acrylate, α- Allyloxymethyl acrylate tricyclodecanyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyloxymethyl acrylate dicyclopentadienyl, α-allyloxymethyl acrylate, methylphenyl α-allyloxymethyl acrylate, dimethylphenyl α-allyloxymethyl acrylate, trimethylphenyl α-allyloxymethyl acrylate, 4-tert-butyl α-allyloxymethyl acrylic acid , Benzyl α-allyloxymethyl acrylate, diphenylmethyl α-allyloxymethyl acrylate, diphenylethyl α-allyloxymethyl acrylate, triphenylmethyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid cinnamyl , Naphthyl .alpha.-allyloxymethyl acrylate, anthranyl .alpha.-allyloxymethyl acrylate; and the like. Among them, alkyl- (α-allyloxymethyl) acrylate monomers are preferable. As the above alkyl- (α-allyloxymethyl) acrylate monomer, methyl α-allyloxymethylacrylate (methyl- (α-allyl) is preferable from the viewpoints of transparency, dispersibility, industrial availability and the like. Particular preference is given to oxymethyl) acrylates).

The above α- (unsaturated alkoxyalkyl) acrylate can be produced, for example, by the production method disclosed in WO 2010/114077.

As a monomer which gives a monomer unit which has ring structure to the above-mentioned principal chain, 2- (hydroxy alkyl) acrylic acid alkyl ester is mentioned preferably. The 2- (hydroxyalkyl) acrylic acid alkyl ester can be reacted with (meth) acrylic acid to form a lactone ring structure in the main chain. As said lactone ring structure, the ring structure represented by the following general formula (II) is mentioned, for example.

In the above general formula (II), R ⁹ represents an alkyl group having 1 to 20 carbon atoms, R ¹⁰ represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and R ¹¹ represents a hydrogen atom or a methyl group. Represent. n is 1 or 2;
R ⁹ and R ¹⁰ are respectively the same as R ⁹ and R ¹⁰ in the general formula (III) described later.

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

(In general formula (III), 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. N is 1 or 2)

In the above general formula (III), R ⁹ represents an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched.
The carbon number of R ⁹ is preferably 1 to 10, more preferably 1 to 6 in view of the solubility of the monomer.
As R ⁹ , for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, etc. Can be mentioned. Preferably it is a methyl group.

In the above 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, C1-C20 alkyl groups, such as a methyl group, an ethyl group, a propyl group, for example; C1-C20 unsaturated fats, such as an ethenyl group and a propenyl group Hydrocarbon group; an aromatic hydrocarbon group having 1 to 20 carbon atoms such as phenyl group and naphthyl group; one of hydrogen atoms in the above alkyl group, the above unsaturated aliphatic hydrocarbon group and the above aromatic hydrocarbon group The above groups include groups substituted with at least one group selected from a hydroxyl group, a carboxyl group, an ether group and an ester group. Among them, a hydrogen atom is preferable as R ¹⁰ from the viewpoint of the hydrophilicity of the lactone ring.

Examples of the 2- (hydroxyalkyl) acrylic acid alkyl ester include 2- (1-hydroxyalkyl) acrylic acid alkyl ester and 2- (2-hydroxyalkyl) acrylic acid alkyl ester. Specifically, for example, Methyl 2- (1-hydroxymethyl) acrylate, ethyl 2- (1-hydroxymethyl) acrylate, isopropyl 2- (1-hydroxymethyl) acrylate, n-butyl 2- (1-hydroxymethyl) acrylate, Examples include t-butyl 2- (1-hydroxymethyl) acrylate and 2-ethylhexyl 2- (1-hydroxymethyl) acrylate. Among them, methyl 2- (1-hydroxymethyl) acrylate and ethyl 2- (1-hydroxymethyl) acrylate are preferable. These may be used alone or in combination of two or more.

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

The content of the monomer unit (D) in the polymer is preferably 2 to 60% by mass, more preferably 5 to 50% by mass, with respect to 100% by mass of all monomer units of the polymer. 5-40 mass% is still more preferable.

<Other monomer unit>
The polymer of the present invention may contain other polymerizable monomer units (E) as necessary, in addition to the above-mentioned monomer units.
Examples of the other polymerizable monomer unit include an acid group-containing monomer, a (meth) acrylic acid ester monomer other than a monomer giving the vinyl monomer unit (B), and an aroma. And monomer units derived from group vinyl monomers, other copolymerizable monomers, and the like.

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

Examples of the acid group include a functional group which is neutralized with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, a sulfonic acid group, etc. You may have, and you may have 2 or more types. Among these, a carboxyl group and a carboxylic acid anhydride group are preferable, and a carboxyl group is more preferable.
As said polymeric 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, vinylbenzoic acid, etc .; maleic acid, fumaric acid, itaconic acid, Unsaturated polyhydric carboxylic acids such as citraconic acid and mesaconic acid; unsaturated acid anhydrides such as maleic anhydride and itaconic acid; phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); Etc. Among these, it is preferable to use a carboxylic acid monomer (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility, availability, and the like. From the viewpoint of reactivity, suppression of water unevenness, heat-resistant colorability, etc., unsaturated monocarboxylic acids are more preferable, and (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid) is more preferable.

Examples of (meth) acrylic acid ester-based monomers other than monomers giving the above vinyl-based monomer unit (B) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate and (meth) acrylic acid Acid n-propyl, (meth) acrylate i-propyl, (meth) acrylate n-butyl, (meth) acrylate s-butyl, (meth) acrylate n-amyl, (meth) acrylate s-amyl, (Meth) acrylic acid n-hexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isodecyl, (meth) acrylic acid tridecyl, (meth) acrylic acid octyl, (meth) acrylic acid isooctyl, (meth) acrylic acid Acid lauryl, stearyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth Tetrahydrofurfuryl acrylate, N, N-dimethylaminoethyl (meth) acrylate, 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid, (meth) acryloyl morpholine, 4- (meth) acryloyl Oxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2 And -methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane and the like.

Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methylstyrene, methoxystyrene and the like.

As said other copolymerizable monomer, 1 type (s) or 2 or more types, such as the following compound, are mentioned, for example.
(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, etc .; heavy weight such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam, etc. Macromonomers having (meth) acryloyl group at one end of united molecular chain; 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 Vinyl ethers such as methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, methoxy ethoxy ethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole And N-vinyl compounds such as N-vinylmorpholine and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate; and the like.
The said polymer may have only 1 type among what was mentioned above as said other polymerizable monomer unit (E), and may have 2 or more types.

When the polymer has the other polymerizable monomer unit (E), the content of the other polymerizable monomer unit (E) is 100% by mass of all the monomer units of the polymer 1 to 60 mass% is preferable, 2 to 50 mass% is more preferable, and 3 to 40 mass% is further preferable.

The content of the acid group-containing monomer unit in the polymer is preferably less than 5% by mass with respect to 100% by mass of all the monomer units of the polymer. When the content of the acid group-containing monomer unit is less than 5% by mass, it is possible to obtain a cured product having further excellent heat resistant colorability. The content of the acid group-containing monomer unit is more preferably less than 3% by mass, and still more preferably less than 1% by mass with respect to 100% by mass of all the monomer units of the polymer.

The acid value of the polymer is preferably 40 to 160 mg KOH / g, more preferably 50 to 150 mg KOH / g, and still more preferably 60 to 140 mg KOH / g.
The said acid value is a value obtained by measuring by the neutralization titration method using a KOH solution.

The weight average molecular weight of the polymer is not particularly limited, but is preferably 2,000 to 100,000, more preferably 3,000 to 8,000, and still more preferably 4,000 to 50,000.
The weight average molecular weight of the polymer is a value obtained by measurement according to the method described in the examples by gel permeation chromatography (GPC).

The above polymer is coated on a glass substrate with a resin composition containing the above polymer to prepare a laminate having a coating film formed thereon, the laminate is dried at 100 ° C. for 3 minutes, and then 3 ° C. at 250 ° C. When heat-treated for a time, it is preferable that b ^* value calculated | required according to JISZ 8729 of the coating film side surface of the said laminated body is 5 or less. The b ^* value is standardized as CIE, and expressed as a chromaticity representing saturation based on the L ^* a ^* b ^* color system adopted in JIS Z 8729 in Japan.
The b ^* value is more preferably 1.5 or less, still more preferably 1.0 or less, and particularly preferably 0.5 or less.

The measurement of the b ^* value is performed using a laminate in which a resin composition containing the above-mentioned polymer is coated on a glass substrate to form a coating film.
Specifically, the resin composition is applied on a glass substrate in a coating amount (solid content equivalent) of 0.4 to 1.2 mg / cm ² , and dried at 100 ° C. for 3 minutes, The laminated body by which the coating film of the said resin composition was formed on the glass substrate is obtained. And after heat-processing the obtained laminated body at 250 degreeC for 3 hours, it cools to normal temperature and measures b <^*> value of the coating film side surface using a color-difference meter. About the said resin composition, it measures using at least 2 laminated body, From these results, the approximate straight line of application quantity (x) and b <^*> value (y) is created as a calibration curve. Using the above calibration curve, the b ^* value in the case of a coating amount of 0.6 mg / cm ² is determined, and this is taken as the above b ^* value.

As the glass substrate, for example, soda lime glass AS-2K (manufactured by Toshin Riko Co., Ltd.) may be used.
The above resin composition was prepared by adding an antioxidant Irganox 1010 (manufactured by BASF Corporation) to the polymer solution obtained by the production of the above polymer so as to be 0.5% by mass with respect to 100% by mass of resin solid content. It is prepared by adding.
For example, ZE6000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) may be used as the color difference meter.

<Method of producing polymer>
As a method for producing the polymer of the present invention, a polymer having at least the monomer unit (A), the vinyl monomer unit (B), and the monomer unit (C) described above can be obtained. The method is not particularly limited as long as it is a method, and a monomer giving the above mentioned monomer units (A) to (C), a monomer giving the monomer unit (D) and the above mentioned as required The method of polymerizing the monomer component containing the monomer which gives another polymerizable monomer unit (E) by a well-known method is mentioned.

The method for polymerizing the above-mentioned monomer component is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization, emulsion polymerization and the like can be used. Among them, solution polymerization is preferable in that it is industrially advantageous and the structure adjustment such as molecular weight is easy. Moreover, although the polymerization mechanism of the said monomer component can use the polymerization method based on mechanisms, such as radical polymerization, anion polymerization, cationic polymerization, coordination polymerization, The radical polymerization mechanism is an industrially advantageous point. The polymerization method based on is preferred.

The compounding amount of the above-mentioned monomer component at the time of polymerization is not particularly limited as long as a polymer excellent in heat-resistant colorability can be obtained, and it may be appropriately designed, for example, the above-mentioned monomer unit (A) A monomer to give (10 to 60% by mass), a monomer to give the vinyl monomer unit (B) (5 to 80% by mass), and the above hydroxyl group-containing monomer (1 to 30% by mass) Preferably, a monomer (10 to 60% by mass) giving the monomer unit (A), a monomer (5 to 80% by mass) giving the vinyl monomer unit (B), the above-mentioned hydroxyl group-containing monomer The monomer (1 to 30% by mass) and the monomer (2 to 60% by mass) giving the monomer unit (D) are more preferable, and the monomer (20 to give the monomer unit (A) 50% by mass), a monomer (10 to 70% by mass) giving the above vinyl monomer unit (B), the above hydroxyl group containing monomer ( To 20% by mass), monomers (5 to 50% by mass) giving monomer units (D), and other polymerizable monomers (2 to 50% by mass) are more preferable, and the above-mentioned monomer units Monomer (20 to 50% by mass) giving (A), Monomer (20 to 60% by mass) giving above vinyl-based monomer unit (B), Monomer containing above hydroxyl group (5 to 20%) %), Monomers (5 to 40% by weight) giving monomer units (D), and (meth) acrylic acid (less than 5% by weight) are particularly preferred.

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

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

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

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

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

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, and t-butyl peroxy- 2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis ( Examples thereof include peroxides and azo compounds which are usually used as a polymerization initiator such as 2-methyl propionate), hydrogen peroxide and persulfate. These may be used singly or in combination of two or more.

The amount of the polymerization initiator to be used is not particularly limited, and may be appropriately set according to the kind and amount of monomers to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and molecular weight of the target polymer. Although it is good, for example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the above-mentioned monomer component.

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

As said chain transfer agent, the thing similar to the solvent as described in Unexamined-Japanese-Patent No. 2015-157909 is mentioned, 1 type (s) or 2 or more types of them can be used. Among them, mercapto carboxylic acids, mercapto carboxylic esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercapto are preferable in view of availability, crosslink preventing ability, degree of decrease in polymerization rate and the like. The compound which has mercapto groups, such as isocyanurate, is mentioned, More preferably, alkyl mercaptans, mercapto carboxylic acids, mercapto carboxylic acid esters, More preferably, n-dodecyl mercaptan and mercapto propionic acid are mentioned.

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

The polymerization temperature may be appropriately set according to the type and amount of the monomer used, the type and amount of the polymerization initiator, etc., for example, 50 to 150 ° C. is preferable, and 70 to 70 ° C. 120 ° C. is more preferred. Also, the polymerization time can be set appropriately as well, but 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 made into curable resin composition by combining with a polymeric compound. Since the said curable resin composition contains the said polymer, the cured | curing material excellent in heat-resistant colorability can be given. In addition to the heat-resistant colorability, the cured product of the resin composition is excellent in addition to the heat resistant colorability by further containing a polymerizable compound, and the cured product is further excellent in adhesion to the substrate, surface hardness, heat resistance, solvent resistance, etc. Can be given.
Such a curable resin composition containing the above-described polymer and a polymerizable compound is also one of the present invention.

In the curable resin composition of the present invention, the content of the polymer is not particularly limited and may be appropriately set according to the application, the blending of other components, etc. For example, the solid content of the curable resin composition 5-80 mass% is preferable with respect to 100 mass% of total amounts, 7-70 mass% is more preferable, 10-60 mass% is still more preferable.
In addition, "solid content total amount" means the total amount of the component (except the solvent etc. which volatilize at the time of formation of hardened | cured material) which forms hardened | cured material.

<Polymerizable compound>
The polymerizable compound can be polymerized by irradiation of active energy rays such as free radicals, electromagnetic waves (eg, infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc., polymerizable unsaturated bonds (also referred to as polymerizable unsaturated groups) It is a low molecular weight compound having For example, monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more are mentioned.

Examples of the monofunctional compounds include N-substituted maleimide monomers; (meth) acrylic esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids; unsaturated groups and carboxyls Unsaturated monocarboxylic acids which are chain-extended between groups; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates etc. Can be mentioned. Further, a monomer having an active methylene group or an active methine group can also be used.

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

Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide adducted trimethylolpropane tri (meth) acrylate, ethylene oxide adducted ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexamer (Meth) Acrylate, .EPSILON.-caprolactone added trimethylolpropane tri (meth) acrylate, .EPSILON.-caprolactone added ditrimethylolpropane tetra (meth) acrylate, .EPSILON.-caprolactone added pentaerythritol tetra (meth) acrylate, .epsilon.-caprolactone added dipentaerythritol Hexa (meth) acrylate, dipentaerythritol pentaacrylate succinic acid modified , Pentaerythritol triacrylate succinic acid modified product, dipentaerythritol pentaacrylate phthalic acid modified product, pentaerythritol triacrylate phthalic acid modified product, the following formula:

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

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditriol Methylolpropane tetravinyl ether, glycerine trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide adducted trimethylolpropane trivinyl ether, ethylene oxide adducted ditrimethyene Lumpur propane tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, polyfunctional vinyl ethers such as ethylene oxide adduct of dipentaerythritol hexavinyl ether;

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

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

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

Among the above-described polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of enhancing the curability of the curable resin composition. The functional number of the polyfunctional polymerizable compound is preferably 3 or more, and more preferably 4 or more. Moreover, ten or less are preferable and, as for the said functional number, eight or less are more preferable.
Further, the molecular weight of the polymerizable compound is not particularly limited, but from the viewpoint of handling, for example, 2000 or less is preferable.

Among the above-mentioned polyfunctional polymerizable compounds, from the viewpoint of reactivity, economy, availability, etc., polyfunctional (meth) acrylate compounds, polyfunctional urethane (meth) acrylate compounds, (meth) acryloyl group-containing isocyanates The compound which has a (meth) acryloyl group, such as a nurate compound, is preferable, and a polyfunctional (meth) acrylate compound is more preferable. By including a compound having a (meth) acryloyl group, the curable resin composition becomes more excellent in photosensitivity and curability, and a cured product with higher hardness and higher transparency can be obtained. It is more preferable to use a trifunctional or higher polyfunctional (meth) acrylate compound as the polyfunctional polymerizable 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 above-mentioned polymerizable compound is not particularly limited as long as the effects of the present invention can be exhibited, and may be appropriately set, but the curable resin composition is suitably used. The content is preferably 2 to 80% by mass, more preferably 5 to 70% by mass, still more preferably 10% by mass, based on 100% by mass of the total solid content of the curable resin composition of the present invention. 60 mass%.

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

The photopolymerization initiator is not particularly limited. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE 907”, manufactured by BASF), 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ("IRGACURE 369", manufactured by BASF Corporation), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4) Alkylphenone compounds such as -morpholin-4-yl-phenyl) -butan-1-one ("IRGACURE 379", manufactured by BASF Corp.); 2,2-dimethoxy-1,2-diphenylethane-1-one (" IRGACURE 651 ", BASF AG), phenylglyoxylic acid methyl ester (" DAROCUR MBF ", BA Benzil ketal compounds such as F), 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE 184”, manufactured by BASF Corp.), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (“DAROCUR 1173”) “BASF”), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE 2959”, BASF), 2-hydroxy -1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (“IRGACURE 127”, manufactured by BASF Corp.), [1-hydroxy -Cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE 500", B Hydrophenoid compounds such as SF Co., Ltd., etc .; and alkylphenone compounds exemplified in paragraphs [0084] to [0086] of JP 2013-227485 A; 1,2-octanedione, 1- [1] 4- (phenylthio) phenyl]-, 2- (O-benzoyloxime)] ("OXE01", manufactured by BASF AG), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl]-, 1- (0-acetyloxime) ("OXE 02", manufactured by BASF AG), 1,2-octanedione, 1- [4- (phenylthio)-, 2-, (O-benzoyloxime) ], Etanone ("OXE03", manufactured by BASF AG), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Ximes) ("OXE 04", manufactured by BASF Corporation) and the like; oxime ester compounds such as benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; biimidazole compounds; Examples include titanocene compounds; benzoate compounds; acridine compounds etc .; phosphine oxide compounds; and the like. Among them, alkylphenone compounds are preferable.
The said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the photopolymerization initiator is not particularly limited as long as the effects of the present invention can be exhibited, and may be appropriately designed. For example, the total solid content 100 of the curable resin composition of the present invention Preferably it is 0.1-30 mass% with respect to mass%, More preferably, it is 0.5-25 mass%, More preferably, it is 1-20 mass%.

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

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

In the case of using the photosensitizer and the photoradical polymerization accelerator, the content thereof is 100% by mass of the total solid content of the curable resin composition from the viewpoint of the balance between the curability, the influence of the decomposition product and the economy. The amount is preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, and still more preferably 0.05 to 10% by mass.

<Other ingredients>
The curable resin composition of the present invention may contain other components as needed in addition to the polymer, the polymerizable compound, and the photopolymerization initiator described above. Other components include, for example, solvents; coloring materials (also referred to as colorants); dispersants; antioxidants; heat resistance improvers; leveling agents; developing assistants; inorganic fine particles such as silica fine particles; silanes, aluminums, Coupling agents such as titanium type; thermosetting resins such as filler, epoxy resin, phenol resin, and polyvinyl phenol; curing assistant such as polyfunctional thiol compound; plasticizer; polymerization inhibitor; ultraviolet absorber; Antifoaming agents, antistatic agents, slip agents, surface modifiers, thixotropic agents, thixotropic assistants, quinone diazide compounds, polyhydric phenol compounds, cationically polymerizable compounds, acid generators, and the like. These may be used alone or in combination of two or more. For example, when using the said curable resin composition for a color filter use, it is preferable that the said curable resin composition contains a coloring material.

(solvent)
As the above-mentioned solvent, one which is usually used in a curable resin composition can be used, and it may be appropriately selected according to the purpose and application, and it is not particularly limited, but for example, it is described in JP-A-2015-157909. The same ones as those described above can be used. These may be used alone or in combination of two or more.

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

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

Among the coloring materials, pigments are preferable in terms of durability, and dyes are preferable in terms of improving the brightness of panels and the like. These can be suitably selected according to the characteristic calculated | required. In the curable resin composition of the present invention, a pigment is preferable in that the solvent resistance and heat resistant colorability of the cured product can be further improved. As a pigment, the thing similar to the thing as described in Unexamined-Japanese-Patent No. 2015-157909 can be used.

As the above-mentioned dye, for example, it is possible to use the organic dye described in JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599. it can. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable.
These colorants may be used alone or in combination of two or more.

The content of the coloring material is not particularly limited, and can be appropriately set depending on the purpose and application, but preferably, it is 2 to 2 with respect to the total solid content 100% by mass of the curable resin composition. 80 mass%, More preferably, 5-70 mass%, More preferably, 10-60 mass% is mentioned.

(Dispersant)
When the curable resin composition of the present invention contains the above-mentioned colorant, it is preferable to further contain a dispersant.
The dispersant has an interaction site with the color material and an interaction site with the dispersion medium (for example, a solvent and a binder resin), and has a function to stabilize the dispersion of the color material in the dispersion medium. Generally, they are classified into resin type dispersants (for example, high molecular weight dispersants), surfactants (for example, low molecular weight dispersants), and dye derivatives. These may be used alone or in combination of two or more.

Examples of the resin type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, and polysiloxane A long chain polyaminoamide phosphate, a hydrogen group-containing polycarboxylic acid ester, an amide or a salt thereof formed by the reaction of poly (lower alkyleneimine) and a polyester having a free carboxyl group, (meth) acrylic acid-styrene Copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, polyesters, modified polyacrylates, ethylene oxide / polypropylene oxide adducts, etc. E It is. As a commercial item of the said resin type dispersing agent, the thing similar to the thing as described in Unexamined-Japanese-Patent No. 2015-157909 is mentioned.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate, sodium lauryl sulfate, etc .; nonionics such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate etc. Cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts Alkyl betaines such as alkyl dimethylamino acetic acid betaine, and amphoteric surfactants such as alkyl imidazolines; active agents.

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

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

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

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

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

In the dispersion processing step of the color material, for example, a predetermined amount of each of the color material (preferably an organic pigment), a dispersant and a solvent are weighed, and the color material is dispersed in fine particles using a disperser to make a liquid color material A method of obtaining a dispersion (also called mill base) may be mentioned. Examples of the disperser include a paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender and the like. As the above-mentioned dispersion treatment process, preferably, a method of carrying out fine dispersion treatment with a media mill such as a bead mill filled with beads of 0.01 to 1 mm after kneading and dispersion treatment with a roll mill, a kneader, a blender or the like is preferable. . A composition (preferably a transparent liquid) containing the above-mentioned polymer, a polymerizable compound, a photopolymerization initiator, and, if necessary, a solvent, a leveling agent, etc., separately stirred and mixed in the obtained mill base ) Can be mixed to form a uniform dispersion solution, and a curable resin composition can be obtained.
In addition, it is preferable to filter the obtained curable resin composition with a filter etc., and to remove fine refuse.

3. Laminate As described above, the polymer of the present invention and the curable resin composition give a cured product excellent in heat-resistant colorability. Moreover, the said hardened | cured material is excellent also in performances, such as surface hardness, adhesiveness with a base material, heat resistance, and transparency. A laminate having a cured product of such a polymer or a cured product of the curable resin composition on a substrate (substrate) is also one of the present invention.

As for the film thickness, when the said hardened | cured material is a cured film, Preferably 0.1-20 micrometers is mentioned. When the film thickness is in the above-mentioned range, excellent heat-resistant colorability can be exhibited. In addition, various performances such as surface hardness, adhesion to a substrate, heat resistance and transparency can be sufficiently exhibited. The film thickness is more preferably 0.5 to 10 μm, still more preferably 0.5 to 8 μm.

It does not specifically limit as a method of obtaining a laminated body, What is necessary is just to use a well-known method, For example, the polymer mentioned above or the curable resin composition mentioned above is apply | coated on the base material, and what was apply | coated is dried. There is a method of curing by heating or irradiation with energy rays such as ultraviolet rays to obtain a cured product.
The substrate is not particularly limited and may be appropriately selected depending on the purpose or application. Examples thereof include substrates made of various materials such as a glass plate and a plastic plate.

The laminate is, for example, a color filter, a black matrix, a photo spacer, a black column spacer, an ink, a printing plate used for liquid crystal, organic EL, quantum dot, micro LED liquid crystal display device, solid-state imaging device, touch panel display device, etc. It is suitably used for various applications of optical members such as printed wiring boards, semiconductor elements, photoresists, insulating films, etc., and electric and electronic devices. Especially, it is preferable to use for a color filter. Thus, a color filter having a cured product of the above curable resin composition is also one of the present invention. The color filters will be described below.

3-1. Color Filter The color filter of the present invention is in the form of having a cured product of the above curable resin composition on a substrate.
In the color filter, a cured product formed of the curable resin composition is particularly suitable as a segment that requires coloring, such as a black matrix or each pixel such as red, green, blue and yellow. It is also suitable as a segment that does not necessarily require coloring, such as a photo spacer, a protective layer, and an orientation control rib.

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

<Production method of color filter>
In order to obtain the color filter, for example, the step of disposing the curable resin composition on a substrate per pixel color (that is, for each pixel of a color) (also referred to as disposing step) is disposed on the substrate Including a step of irradiating the cured resin composition with light (also referred to as a light irradiation step), a step of developing treatment with a developer (also referred to as a development step), and a step of heating treatment (also referred to as a heating step) It is preferable to adopt a method, and to adopt a manufacturing method in which the same method is repeated for each color. In addition, the formation order of the pixel of each color is not specifically limited.

(Placement process (preferably, application process))
The placement step is preferably performed by coating. Examples of the method for applying the curable resin composition on a substrate include spin application, slit application, roll application, and cast application, and any method can be preferably used.
In the disposing step, it is also preferable to dry the coating film after applying the curable resin composition on the substrate. Drying of the coating can be performed using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected depending on the boiling point of the solvent component contained, the type of curing component, the film thickness, the performance of the drier, etc., but it is usually performed at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds. It is suitable.

(Light irradiation process)
As a light source of actinic light used in the light irradiation step, for example, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, super high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp etc. And a laser light source such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser and the like are used. Further, as a method of the exposure machine, a proximity method, a mirror projection method, a stepper method may be mentioned, but a proximity method is preferably used.
In the irradiation step of the active energy ray, depending on the application, the active energy ray may be irradiated through a predetermined mask pattern. In this case, the exposed portion is cured, and the cured portion is insolubilized or poorly dissolved in the developer.

(Development process)
The above-mentioned development process is a process of developing processing 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. The development processing can be carried out usually at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, ultrasonic development and the like.

The developer used in the developing step is not particularly limited as long as it dissolves the curable resin composition, but an organic solvent or an alkaline aqueous solution is usually used, and a mixture of these may be used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development.

As an organic solvent suitable as said developing solution, an ether solvent, 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 And isopropanol, benzyl alcohol and the like.

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

Examples of the alkali agent include inorganic substances such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and the like. Alkaline agents; amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like, which may be used alone And two or more may be used in combination.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, etc .; alkyl benzene sulfonates, alkyl naphthalene sulfonic acid Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid esters salts; amphoteric surfactants such as alkyl betaines and amino acids, etc., which may be used alone or in combination of two You may use combining the above.

(Heating process)
The heating step is a step (also referred to as a post-curing step) of further curing the exposed portion (cured portion) by baking after the above-described developing step. For example, using a light source such as a high pressure mercury lamp, a step of post-exposure with an amount of light of, for example, 0.5 to 5 J / cm ² , a step of post-heating at a temperature of 60 to 260 ° C. for 10 seconds to 120 minutes, It can be mentioned. By performing such a post-curing step, it is possible to make the hardness and adhesion of the patterned cured film even stronger. Moreover, the hydroxyl group-containing monomer which the polymer which the carboxyl group which the tertiary carbon containing site | part of the said vinyl-type monomer unit (B) produced | generated by this heating process and which the tertiary carbon containing site | part of the said polymer produced has. It reacts with a hydroxyl group such as a unit to form a crosslinked structure, and the curability of the curable resin composition and the solvent resistance of the cured product thereof become further excellent.

It is preferable that the film thickness of the cured film obtained by the said heating process (namely, cured film obtained by thermosetting the said curable resin composition) is 0.1-20 micrometers. By using the curable resin composition of the present invention, a cured film with a sufficiently reduced film thickness can be provided. In addition, since the film thickness is reduced, the concentration of the coloring material per unit volume of the cured film can be increased, and the luminance of the color filter can be improved. The film thickness is more preferably 0.5 to 10 μm, still more preferably 0.5 to 8 μm.
In addition, it is preferable that the film thickness of the coating film (namely, cured film) obtained by the said heating process is 90% or less, if the film thickness of the coating film before a heating is made into 100%. More preferably, it is 80% or less, more preferably 70% or less.

In the heating step, the heating temperature is preferably 150 ° C. or more. As a result, the part derived from a part of the vinyl-based monomer unit (B) is more effectively decomposed, and the curability and solvent resistance can be further improved. The heating temperature is more preferably 160 ° C. or more, still more preferably 170 ° C. or more, particularly preferably 180 ° C. or more. Further, the temperature is preferably 270 ° C. or less, more preferably 260 ° C. or less, and still more preferably 250 ° C. or less.

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

4. Display Device The present invention is also a display device comprising the color filter described above.
In addition, the member for display apparatuses which has a hardened | cured material formed with the said curable resin composition, and a display apparatus are also contained in the suitable embodiment of this invention. A cured product (cured film) formed of the above-mentioned curable resin composition is stably excellent in adhesion to a base material and the like, has high hardness, exhibits high smoothness, and has high transmittance. Therefore, it is particularly suitable as a transparent member, and is also useful as a protective film or an insulating film in various display devices.

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

As described above, the polymer of the present invention and the curable resin composition containing the above polymer can give a cured product excellent in heat-resistant colorability. In addition, a cured product obtained by using the polymer and the curable resin composition of the present invention is also excellent in adhesion to a substrate, transparency, heat resistance, and the like. Such polymers and curable resin compositions of the present invention can be used in color filters, black matrices, photo spacers used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. , Black column spacers, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, insulating films, etc., which are very useful in various applications in the field of optics, electrical and electronic fields.

5. Second polymer The above-described polymer essentially comprises the vinyl monomer unit (B), but the third polymer of the vinyl monomer unit (B) is produced by elimination by heating. The leaving group of the class carbon atom and the leaving group remaining in the cured product may act in the direction of reducing the heat resistant colorability. For this reason, the said polymer may be an aspect which does not contain the said vinyl-type monomer unit (B). Such a polymer having no vinyl monomer unit (B), that is, a monomer unit represented by the above general formula (I) (hereinafter also referred to as “monomer unit (A ′)” And COO ^* R ⁴ (R ⁴ is a monovalent organic group) having a hydroxyl group-containing monomer unit (hereinafter also described as “monomer unit (C ′)”) and And a carbon atom bonded to O ^* is a tertiary carbon atom.) A vinyl monomer unit containing a group (hereinafter also referred to as "vinyl monomer unit (B ')"). The polymer which does not have) is also one of the present invention. Such a second polymer of the present invention is also excellent in heat-resistant colorability.

As the monomer unit (A '), the monomer unit (C') and the vinyl monomer unit (B ') in the polymer of the second invention, each of the above-mentioned "1. polymers" And the same as the monomer unit (A), the monomer unit (C) and the vinyl monomer unit (B) described in the above.

The polymer of the second invention preferably further has a monomer unit having a ring structure in the main chain (hereinafter, also described as “monomer unit (D ′)”). As a monomer unit (D ') in the polymer of 2nd this invention, the thing similar to the monomer unit (D) described in the above-mentioned "1. polymer" can be mentioned.

The polymer of the second invention may further have other polymerizable monomer units (hereinafter, also described as “monomer units (E ′)”) as necessary. As said monomer unit (E '), the thing similar to the other polymerizable monomer unit (E) described in the above-mentioned "1. polymer" can be mentioned.

The polymer according to the second aspect of the present invention comprises 10 to 60% by mass of monomer units (A ′) and 100% by mass of all monomer units of the above-mentioned polymer, and monomer units (C ′) 1 It is preferable to have 30 to 30% by mass, 10 to 60% by mass of monomer unit (A '), 1 to 30% by mass of monomer unit (C'), and 2 to 60 monomer units (D ') It is more preferable to have mass%, and 20 to 50 mass% of monomer units (A ′), 5 to 20 mass% of monomer units (C ′), and 5 to 50 mass of monomer units (D ′) % Is further preferable, and 20 to 50% by mass of monomer unit (A '), 5 to 20% by mass of monomer unit (C'), and 5 to 40% by mass of monomer unit (D ') It is particularly preferred to have

When the polymer of the second invention further has a monomer unit (E ′), the polymer is a monomer unit (A ′) relative to 100% by mass of all the monomer units of the polymer. ) 10 to 60 mass%, 1 to 30 mass% of monomer unit (C ′), 2 to 60 mass% of monomer unit (D ′), and 1 to 60 mass% of monomer unit (E ′) It is preferable to have 20 to 50% by mass of monomer unit (A '), 5 to 20% by mass of monomer unit (C'), 5 to 50% by mass of monomer unit (D '), and a single amount. It is more preferable to have 1 to 50% by mass of a body unit (E '), 20 to 50% by mass of a monomer unit (A'), 5 to 20% by mass of a monomer unit (C '), and a monomer unit It is more preferable to have 5 to 40% by mass of (D ′) and 1 to 30% by mass of monomer unit (E ′).

The properties such as the acid value and weight average molecular weight of the polymer of the second invention are the same as those described in the above-mentioned "1. polymer". The manufacturing method of the said polymer is the same as the manufacturing method described in the above-mentioned "1. polymer" except the point which does not use the monomer which gives the said vinyl-type monomer unit (B '). The curable resin composition containing the said polymer, the laminated body using these, those applications are the same as that of what is described about the above-mentioned "1. polymer".

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. In addition, "part" shall mean "mass part" and "%" shall mean "mass%" unless there is particular notice. The analysis of the polymer in each synthesis example was performed as follows.

<Weight average molecular weight>
It measured by the gel permeation chromatography method using tetrahydrofuran as an eluting solvent, TSK-gel SuperHZM-M (made by Tosoh Corp.) by HLC-8220GPC (made by Tosoh Corp.), and it computed in standard polystyrene conversion.

<Solid content>
The copolymer solution was accurately weighed about 1 g in an aluminum cup, and about 2 g of acetone was added thereto for dissolution, and then allowed to stand at ambient temperature for about 2 hours for natural drying. Then, after drying with a vacuum dryer (made by EYELA company) at 140 degreeC of vacuum for 1.5 hours, it stood to cool in a desiccator and the mass of the aluminum cup was measured. The solid content (mass%) of the polymer solution was calculated from the mass loss.

<Acid number>
1.5 to 2 g of the copolymer solution is precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an aqueous solution of potassium hydroxide of 0.1 N is used as a titration solution to make an automatic titrator The commercial solution: COM-1700) was used to measure the acid value of the copolymer solution, and the acid value per 1 g of polymer was determined from the acid value and the solid content of the solution.

<Heat resistant colorability>
An antioxidant Irganox 1010 (manufactured by BASF) was added to the copolymer solution to a concentration of 0.5% by mass to prepare a resin composition solution. Using a spin coater (1H-D7, manufactured by Mikasa Co., Ltd.), this resin composition solution is coated with 5 cm square glass substrate (soda so that the coating amount is 0.4 to 1.2 mg / cm ^{2 in} terms of solid content) It apply | coated uniformly on lime glass AS-2K (made by Toshin Riko). Under the present circumstances, about each resin composition, the rotation speed of a spin coater was changed, the application amount (solid content conversion) was changed, and the application board of 2 sheets from which an application amount differs was produced. In order to ensure that the coating amount of one of the two sheets is a value larger than 0.6 mg / cm ² , the coating amount of the other sheet is always a value smaller than 0.6 mg / cm ² .
These coated plates were dried at 100 ° C. for 3 minutes to obtain a laminate in which a coating film was formed on a glass substrate. After removing the resin adhering to the end of the glass substrate, the resulting laminate was subjected to heat treatment at 250 ° C. for 3 hours using a perfect oven thermostat (manufactured by Espec Corp.) and then cooled to room temperature. . After cooling, the coated film surface of the laminate was measured using a colorimetric color difference meter ZE6000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) to obtain the b ^* value after heat treatment. An approximate straight line (calibration curve) of the coated amount (x) and the b ^* value (y) is determined from the measured values of the two coated films prepared as described above for each coated film, and the coated amount is 0.6 mg / cm The b ^* value at ² was adopted as a result of the heat-resistant colorability of each coating.

Synthesis Example 1
Preparation of copolymer solution 1 (MD / t-BMA / HEMA / MMA / HOA-MS copolymer solution) As a reaction vessel, a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping bath introduction port A separable flask equipped with the above is prepared, while 10.0 parts of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as "MD") as a monomer dropping tank, methacrylic acid 29.5 parts of t-butyl (hereinafter referred to as "t-BMA"), 15.0 parts of hydroxyethyl methacrylate (hereinafter referred to as "HEMA"), 1.0 part of methyl methacrylate (hereinafter referred to as "MMA") Succinic acid mono (2-acryloyloxyethyl) (hereinafter referred to as “HOA-MS”) 44.5 parts, t-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation “Perbutyl O”) A mixture of 2 parts of "PBO" and 33 parts of propylene glycol monomethyl ether acetate (hereinafter "PGMEA") is thoroughly stirred and mixed to prepare a chain transfer agent dropping tank, n-dodecyl mercaptan (n-). A well-stirred mixture of 1.6 parts of DM) and 7.7 parts of PGMEA was prepared.

The reaction vessel was charged with 141 parts of PGMEA, purged with nitrogen, and heated with an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. 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 2.5 hours 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 copolymer solution 1. Various physical properties are shown in Table 1.

(Composition example 2)
Preparation of copolymer solution 2 (MD / t-BMA / HEMA / MMA / HOA-MS copolymer solution) Charged amount of monomers: 10.0 parts MD, 32.5 parts t-BMA, A monomer dropping tank and a chain transfer agent dropping tank are prepared in the same manner as in Synthesis Example 1 except that 15.0 parts of HEMA, 24.3 parts of MMA and 18.2 parts of HOA-MS are prepared, and the same operation is performed to obtain a copolymer solution. I got two. Various physical properties are shown in Table 1.

(Composition example 3)
Preparation of copolymer solution 3 (MD / t-BMA / HEMA / MMA / HO-MS copolymer solution) 10.0 parts of MD, 26.5 parts of t-BMA, and so forth. Similar to Synthesis Example 1, except that 15.0 parts of HEMA, 1.0 part of MMA, and 47.5 parts of mono (2-methacryloyloxyethyl) succinate (hereinafter referred to as “HO-MS”) were used, and chain transfer was performed with the monomer dropping tank The agent dropping tank was prepared, and the same operation was performed to obtain a copolymer solution 3. Various physical properties are shown in Table 1.

(Composition example 4)
Preparation of copolymer solution 4 (BzMI / t-BMA / HEMA / MMA / HOA-MS copolymer solution) Separa equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube and a dropping tank inlet In a bull flask, 164 parts of PGMEA was charged and purged with nitrogen, and then heated to 90 ° C. 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 PBO2. A well-stirred mixture of 2 parts was prepared, and as a chain transfer agent dropping tank, a well-stirred mixture of 2.6 parts of n-DM and 17.4 parts of PGMEA was prepared. 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 performed over 3 hours while maintaining the temperature at 90 ° C. After completion of the dropwise addition, the temperature was maintained at 90 ° C. for 30 minutes, and the temperature was raised to 115 ° C., and aging was performed for 90 minutes to obtain a copolymer solution 4. Various physical properties are shown in Table 1.

(Composition example 5)
Preparation of copolymer solution 5 (CHMI / t-BMA / HEMA / MMA / HOA-MS copolymer solution) Synthesis example except using N-cyclohexyl maleimide (hereinafter referred to as "CHMI") instead of BzMI A monomer dropping tank and a chain transfer agent dropping tank were prepared with the same monomer preparation amount as that of 4, and the same operation was performed to obtain a copolymer solution 5. Various physical properties are shown in Table 1.

Synthesis Example 6
Preparation of copolymer solution 6 (MD / t-BMA / MMA / HOA-MS copolymer solution) The amount of the monomer charged was 10.0 parts MD, 44.5 t-BMA, MMA1. A monomer dropping tank and a chain transfer agent dropping tank were prepared in the same manner as in Synthesis Example 1 except that 0 parts and 44.5 parts of HOA-MS were used, and the same operation was performed to obtain a copolymer solution 6. Various physical properties are shown in Table 1.

Synthesis Example 7
Preparation of copolymer solution 7 (MD / t-BMA / HEMA / MMA / AA copolymer solution) The amount of monomers charged was 10.0 parts MD, 32.5 parts t-BMA, and 15 parts HEMA. A monomer dropping tank and a chain transfer agent dropping tank were prepared in the same manner as in Synthesis Example 1 except that 0 parts, 26.7 parts of MMA and 15.8 parts of AA were prepared, and the same operation was performed to obtain a copolymer solution 7. . Various physical properties are shown in Table 1.

Synthesis Example 8
Preparation of copolymer solution 8 (MD / t-BMA / MMA / MAA copolymer solution) The amount of the monomer charged is 10.0 parts MD, 42.7 parts t-BMA, 29.6 parts MMA A monomer dropping tank and a chain transfer agent dropping tank were prepared in the same manner as in Synthesis Example 1 except that 17.7 parts of MAA was used, and the same operation was performed to obtain a copolymer solution 8. Various physical properties are shown in Table 1.

(Examples 1 to 5, Comparative Examples 1 to 3)
The heat resistant colorability was evaluated using the obtained copolymer solutions 1-8. The results are shown in Table 1.

The description in Table 1 represents the following.
MD: dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate BzMI: N-benzylmaleimide CHMI: N-cyclohexylmaleimide t-BMA: t-butyl methacrylate HEMA: hydroxyethyl methacrylate MMA: methacrylate Acid methyl ester HOA-MS: succinic acid mono (2-acryloyloxyethyl)
HO-MS: succinic acid mono (2-methacryloyloxyethyl)
AA: acrylic acid MAA: methacrylic acid

From Table 1, polymers having HOA-MS or HO-MS monomer units, t-BMA monomer units, and HEMA monomer units (Examples 1 to 5) are It was confirmed that the heat-resistant colorability is excellent as compared with the polymers (comparative examples 1 to 3) which do not have any monomer unit.

Claims (9)

Monomer unit represented by the following general formula ^{(I), -COO * R 4} (R 4 represents a monovalent organic group, the carbon atom bonded to ^{O *} is a tertiary carbon atom. ) A polymer having a vinyl-based monomer unit containing a group and a hydroxyl group-containing monomer unit.

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or an unsaturated hydrocarbon group having 1 to 12 carbon atoms. R ³ represents a divalent organic group, X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid anhydride group or a phosphoric acid group, and m represents a group represented by the general formula (I) Represents the average number of repeating units of the monomer units, and is a number of 1 or more, n is 0 or 1.) The polymer according to claim 1, wherein the polymer is a ring structure-containing polymer having a ring structure in its main chain. The polymer according to claim 1 or 2, wherein the content of the monomer unit represented by the general formula (I) is 10 to 60% by mass. The polymer according to any one of claims 1 to 3, wherein the content of (meth) acrylic acid units is less than 5% by mass. The polymer according to any one of claims 1 to 4, which has an acid value of 40 to 160 mg KOH / g. A curable resin composition comprising the polymer according to any one of claims 1 to 5 and a polymerizable compound. A laminate comprising a cured product of the polymer according to any one of claims 1 to 5 or a cured product of the curable resin composition according to claim 6 on a substrate. A color filter comprising a cured product of the curable resin composition according to claim 6 on a substrate. A display device comprising the color filter according to claim 8.