JP7185415B2 - Novel polymer, curable resin composition, and use thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to novel polymers and curable resin compositions containing the same. More specifically, it relates to a novel polymer, a curable resin composition containing the same, a laminate having a cured product of the curable resin composition, a color filter, and a display device.

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

Among the above-mentioned uses, color filters are the main components that make up liquid crystal display devices, solid-state imaging devices, and the like. In addition to the pixels and the resin black matrix (BM) that separates them, it is composed of a protective film or the like that is provided to cover and protect the pixels and the resin black matrix and to smooth out the unevenness of the pixels and the resin black matrix.

Normally, when forming pixels of a color filter using a curable resin composition, each pixel is formed by (1) a coating step of applying a curable resin composition to the entire surface of the substrate, and (2) a coating step. After pattern exposure is performed on the resist film through a photomask to cure the exposed portion, the exposure step of insolubilizing the cured portion; A developing and baking process for further hardening the part is performed, and the same process is repeated for each color. Considering the application to such color filter applications, the resin to be used and the curable resin composition containing the resin have curability, solvent resistance after curing, adhesion to the substrate, and heat resistance. and various physical properties such as transparency.

So far, various proposals have been made for resins having such various physical properties.
For example, in Patent Document 1, as a polymer having excellent heat resistance, an N-substituted maleimide and/or a specific ether dimer, vinyl toluene, and a monomer having an acid group are copolymerized as monomer components. Polymers have been proposed.
However, in a resin composition containing a maleimide-derived polymer, since the maleimide-based polymer contains nitrogen atoms, the polymer is colored yellow to yellowish brown when heated, and the transparency of the cured film is insufficient. There was a problem. On the other hand, there have been proposed polymers capable of forming a coating film excellent in transparency as well as heat resistance.

For example, in Patent Document 2, as a polymer capable of forming a coating film having excellent heat resistance and transparency, a specific monomer that is an ether dimer of 2-(hydroxyalkyl) acrylic acid ester and a carboxyl group are added. A polymer obtained by copolymerizing an unsaturated monomer and an unsaturated monomer containing a hydroxyl group as monomer components has been proposed.
Further, in Patent Document 3, a tertiary carbon-containing (meta) compound that can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to substrates, heat resistance, and transparency. A curable resin composition containing a (meth)acrylate polymer having acrylate monomer units and hydroxyl group-containing monomer units, a polymerizable compound, and a photopolymerization initiator has been proposed.

Japanese Patent Application Laid-Open No. 2009-40999 JP 2012-82317 A JP 2015-42697 A

2. Description of the Related Art In recent years, optical members, electrical and electronic devices, etc. have been becoming smaller, thinner, and energy-saving. However, it is difficult to say that conventional polymers have fully met such demands, and there is still room for improvement.
Especially for color filter applications, there is a strong demand for higher brightness and higher contrast of display panels due to the higher quality of color liquid crystal display devices and the expansion of their applications. There is a demand for the development of a polymer that is more suppressed than the conventional ones and that can be applied to high coloring.

The present invention has been made in view of the above-mentioned current situation, and provides a polymer that can sufficiently suppress yellowing during heating and can be applied to high coloration, and a curable resin composition containing the polymer. intended to

In order to solve the above problems, the present inventors have made various studies on polymers that can be applied to color filters and the like. It was found that a cured product obtained by Moreover, the present inventors have 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 members for use in color filters and the like. The discovery led to the completion of the present invention.

That is, the present invention is a polymer characterized by having a vinyl monomer unit represented by the following general formula (I) and a hydroxyl group-containing monomer unit.

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

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

It is preferable that the content of the vinyl-based monomer unit represented by the general formula (I) is 10 to 60% by mass.

The polymer preferably has a (meth)acrylic acid unit content of less than 5% by mass.

The acid value of the polymer is preferably 40-160 mgKOH/g.

The present invention is also a curable resin composition comprising the above polymer and a polymerizable compound.

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

The present invention also provides a color filter comprising a cured product of the curable resin composition described above on a substrate.

A display device comprising the filter described above.

Since the polymer and the curable resin composition of the present invention have the above-described constitution, they can give cured products having excellent resistance to heat-induced coloration. Such a polymer of the present invention and a curable resin composition containing the above polymer can be suitably used for various applications such as various optical members and electrical and electronic equipment, particularly liquid crystal display devices and solid-state imaging devices. It can be suitably used for a color filter used for such purposes.

The present invention will be described in detail below.
A combination of two or more of the individual preferred embodiments of the invention described below is also a preferred embodiment of the invention.
In this 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 characterized by having a vinyl monomer unit represented by the following general formula (I) and a hydroxyl group-containing monomer unit. Since the polymer of the present invention has the constitution described above, it is possible to suppress yellowing during heating, that is, to give a cured product excellent in heat resistance to coloration.

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

The reason why the polymer of the present invention can give a cured product having excellent heat resistance is that when the polymer is heated, part of the vinyl-based monomer units represented by the general formula (I) is eliminated to form a hydroxyl group, and this hydroxyl group and the hydroxyl group of the hydroxyl group-containing monomer unit trap radicals in the reaction system to reduce the influence of the radicals.

In addition, the polymer of the present invention is excellent in curability, hardness of the cured product, solvent resistance, heat resistance, transparency, and adhesion to substrates.
The polymer can improve the curability and the properties of the cured product because, as described above, when the polymer is heated, the hydroxyl groups possessed by the polymer and the monomers constituting the polymer It is presumed that this is due to the fact that the hydroxyl group generated from the body unit and the acid group are cross-linked, and that the hydroxyl group traps radicals in the reaction system.

It is preferable that the polymer of the present invention has an acid group in the side chain portion and has a structure in which the acid group is located at a position separated from the main chain by 5 atoms or more. When the acid group is located at a distance of 5 atoms or more from the main chain, a cured product having excellent developability and excellent resistance to heat coloring can be obtained.

In the present invention, the fact that the acid group is at a position away from the main chain by 5 atoms or more means that the position of the carbon atom on the main chain of the polymer to which the side chain is bonded is 0 (zero), and from that position It refers to the state where the chain has an acid group at the position after the 5th atom. Atoms on the side chain may be non-carbon atoms or substituents. Specifically, for example, when having a structural unit of the following formula (a1), the acid group X in the formula is located 5 atoms away from the main chain, and when having a structural unit of the formula (a2), an acid Let the group X be located 7 atoms away from the main chain.

From the viewpoint of alkali solubility, the acid groups are preferably separated by 18 atoms or less, more preferably by 16 atoms or less, and even more preferably by 14 atoms or less.

Examples of the acid group include functional groups that undergo neutralization reaction with alkaline water, such as carboxyl group, phenolic hydroxyl group, carboxylic anhydride group, phosphoric acid group, and sulfonic acid group. You may have it, and you may have 2 or more types. Among them, the acid group is preferably a carboxyl group or a carboxylic anhydride group, more preferably a carboxyl group.

As the structure having an acid group in the side chain portion and having the acid group at a position separated from the main chain by 5 atoms or more, the vinyl-based monomer unit represented by the general formula (I) is preferable. The vinyl-based monomer unit represented by the general formula (I) is described below.

<Vinyl Monomer Unit (A) Represented by Formula (I)>
The polymer of the present invention preferably has a vinyl-based monomer unit (hereinafter also referred to as "monomer unit (A)") represented by the general formula (I).

In general formula (I) above, R ¹ represents a hydrogen atom or a methyl group. Among these, R ¹ is preferably a hydrogen atom from the viewpoint of further improving pattern properties and developability.

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. , alkylene groups are 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 and dodecylene group; an arylene group such as phenylene group, tolylene group and naphthylene group; A group substituted with a functional group such as a hydroxy group or an alkoxy group; Among them, R ² is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

^R3 represents a divalent organic group. The divalent organic group preferably includes a divalent chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. a divalent chain or branched saturated hydrocarbon group or unsaturated hydrocarbon group. The organic group may have a substituent.

Examples of ^R3 include alkylene groups such as a methylene group, ethylene group, propylene group, trimethylene group, butylene group, ethylethylene group, hexylene group, octylene group and dodecylene group; vinylene group, propenylene group and isopropenylene group. , butenylene group, pentenylene group, alkenylene group such as hexenylene group; cycloalkylene group such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, norbornylene group, adamantylene group; phenylene group, tolylene group, naphthylene arylene groups such as groups, fluorene _groups ; alkyl ether groups such as ethyl ether groups and propyl ether groups; be done.
Among them, R ³ is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 5 carbon atoms, and 1 carbon atom, from the viewpoint of further excellent heat-resistant coloring resistance. ∼4 alkylene groups are particularly preferred.

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

As the monomer that provides the above-mentioned monomer unit (A), preferably, mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate, and other unsaturated groups and carboxyl groups Unsaturated monocarboxylic acids having a chain-extended chain and the like can be mentioned. A polymer having the monomer unit (A) can be obtained by polymerizing a monomer component containing such a compound.
The polymer may have only one of the above-described monomer units (A), or may have two or more of them.

The content of the monomer unit (A) in the polymer of the present invention is preferably 10 to 60 with respect to 100% by mass of the total monomer units of the polymer in terms of further excellent heat coloring resistance. % by mass, more preferably 20 to 50% by mass.

<Hydroxyl group-containing monomer unit (B)>
The polymer of the present invention further has a hydroxyl group-containing monomer unit (hereinafter also referred to as "monomer unit (B)"). By having a hydroxyl group-containing monomer unit together with the monomer unit (A), it is possible to give a cured product excellent in heat resistance to coloration. Moreover, by having a hydroxyl group-containing monomer unit, the curability of the polymer of the present invention is further improved, and a cured product having more excellent properties can be obtained.

The hydroxyl group-containing monomer that provides the hydroxyl group-containing monomer unit is not particularly limited as long as it is a compound having a hydroxyl group and a polymerizable double bond in the molecule. Examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 2,3-hydroxypropyl (meth)acrylate are preferred, and 2-hydroxyethyl (meth)acrylate is more preferred.
A polymer having the monomer unit (B) can be obtained by polymerizing a monomer component containing such a hydroxyl group-containing monomer.
The polymer may contain only one of the above-described hydroxyl group-containing monomer units, or may contain two or more of them.

The content of the monomer unit (B) in the polymer of the present invention is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, with respect to 100% by mass of the total monomer units of the polymer. %.

<Monomer Unit (C) Having Ring Structure in Main Chain>
The polymer of the present invention is preferably a ring structure-containing polymer having a ring structure in its main chain. By further including a ring structure in the main chain, the heat resistance of the polymer can be improved.
Examples of the ring structure include imide ring, tetrahydropyran ring, tetrahydrofuran ring, and lactone ring. In order to have these ring structures, the polymer of the present invention preferably has a monomer unit having a ring structure in its main chain (hereinafter also referred to as "monomer unit (C)").

Examples of the monomer that provides 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 monomer having a ring structure in the main chain through cyclopolymerization. Examples thereof include monomers that form polymers. Among them, from the viewpoint of good heat resistance, hardness, colorant dispersibility, etc., N-substituted maleimide-based monomers, dialkyl-2,2'-(oxydimethylene) diacrylate-based monomers, and α- At least one monomer selected from the group consisting of (unsaturated alkoxyalkyl) acrylate monomers is preferable, and from the viewpoint of further excellent heat coloring resistance, N-substituted maleimide monomers and dialkyl- At least one monomer selected from the group consisting of 2,2'-(oxydimethylene) diacrylate monomers is more preferred, and dialkyl-2,2'-(oxydimethylene) diacrylate monomers Amers are more preferred.

Examples of the N-substituted maleimide-based monomers include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide and the like can be mentioned, and one or more of these can be used. Among them, from the viewpoint of transparency, N-phenylmaleimide, N-benzylmaleimide, or N-cyclohexylmaleimide is preferred, and N-benzylmaleimide or N-cyclohexylmaleimide is more preferred.

Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide. , o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide and other halogen-substituted benzylmaleimides;

Examples of the dialkyl-2,2′-(oxydimethylene) diacrylate monomers 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'-[oxybis(methylene)]bis-2- propenoate, di(stearyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(lauryl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(2- ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate and the like. Among these, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate is 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 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- allyloxymethyl acrylate Butyl, n-amyl α-allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate, α-allyloxy s-hexyl methyl acrylate, n-heptyl α-allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate , 2-ethylhexyl α-allyloxymethyl acrylate, capryl α-allyloxymethyl acrylate, nonyl α-allyloxymethyl acrylate, decyl α-allyloxymethyl acrylate, undecyl α-allyloxymethyl acrylate, α- Lauryl allyloxymethyl acrylate, α-Allyloxymethyl tridecyl acrylate, α-Allyloxymethyl myristyl acrylate, α-Allyloxymethyl pentadecyl acrylate, α-Allyloxymethyl acrylate cetyl, α-Allyloxymethyl acrylic acid Heptadecyl, stearyl α-allyloxymethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, ceryl α-allyloxymethyl acrylate, melisyl α-allyloxymethyl acrylate, etc. (α-allyloxymethyl) acrylate-based monomers; α-allyloxymethyl methoxyethyl acrylate, α-allyloxymethyl methoxyethoxyethyl acrylate, α-allyloxymethyl acrylate methoxyethoxyethoxyethyl, α-allyloxy 3-Methoxybutyl methyl acrylate, ethoxyethyl α-allyloxymethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, phenoxyethoxy α-allyloxymethyl acrylate Alkoxyalkyl-(α-allyloxymethyl) acrylate-based monomers such as ethyl; -fluoroethyl allyloxymethyl acrylate, difluoroethyl α-allyloxymethyl acrylate, chloroethyl α-allyloxymethyl acrylate, dichloroethyl α-allyloxymethyl acrylate, bromoethyl α-allyloxymethyl acrylate, α-allyl Dibromoethyl oxymethyl acrylate, vinyl α-allyloxymethyl acrylate, allyl α-allyloxymethyl acrylate, methallyl α-allyloxymethyl acrylate, crotyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid Propargyl, α-Allyloxymethyl cyclopentyl acrylate, α-Allyloxymethyl cyclohexyl acrylate, α-Allyloxymethyl 4-methylcyclohexyl acrylate, α-Allyloxymethyl acrylate 4-t-butylcyclohexyl, α-Allyloxy tricyclodecanyl methyl acrylate, isobornyl α-allyloxymethyl acrylate, adamantyl α-allyloxymethyl acrylate, dicyclopentadienyl α-allyloxymethyl acrylate, phenyl α-allyloxymethyl acrylate, α- methylphenyl allyloxymethyl acrylate, dimethylphenyl α-allyloxymethyl acrylate, trimethylphenyl α-allyloxymethyl acrylate, 4-t-butylphenyl α-allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate , α-allyloxymethyl diphenylmethyl acrylate, α-allyloxymethyl acrylate diphenylethyl acrylate, α-allyloxymethyl acrylate triphenylmethyl acrylate, α-allyloxymethyl acrylate cinnamyl, α-allyloxymethyl acrylate naphthyl, anthranyl α-allyloxymethyl acrylate; and the like. Among them, alkyl-(α-allyloxymethyl)acrylate monomers are preferred. As the alkyl-(α-allyloxymethyl) acrylate-based monomer, methyl α-allyloxymethyl acrylate (methyl-(α-allyl Oxymethyl)acrylate) is particularly preferred.
The α-(unsaturated alkoxyalkyl) acrylate-based monomer can be produced, for example, by the production method disclosed in WO 2010/114077 pamphlet.

The polymer may have only one type of monomer unit derived from these monomers as the monomer unit having a ring structure in the main chain, or may have two or more types. good too.

The content of the monomer unit (C) in the polymer is preferably 2 to 60% by mass, more preferably 5 to 50% by mass, based on 100% by mass of the total monomer units of the polymer. More preferably, it is 5 to 40% by mass.

<Other polymerizable monomer unit (D)>
In addition to the above-described monomer units (A), (B), and (C), the polymer of the present invention may optionally contain other polymerizable monomer units (hereinafter referred to as "monomer units (D) ) may be included.
Examples of the other polymerizable monomer units include acid group-containing monomers other than the vinyl-based monomer represented by the general formula (I), (meth)acrylic acid ester-based monomers, aromatic Examples include 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 that gives the monomer unit (A) described above.

Examples of the acid group include functional groups that undergo neutralization reaction with alkaline water, such as carboxyl group, phenolic hydroxyl group, carboxylic anhydride group, phosphoric acid group, and sulfonic acid group. You may have it, and you may have 2 or more types. Among them, a carboxyl group and a carboxylic anhydride group are preferred, and a carboxyl group is more preferred.
Examples of the polymerizable double bond include a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group, and the like.

Specific examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid, Unsaturated polycarboxylic acids such as citraconic acid and mesaconic acid; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; phosphoric acid group-containing unsaturated compounds such as Light Ester P-1M (manufactured by Kyoeisha Chemical); etc. Among these, carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) are preferably used from the viewpoint of versatility, availability, and the like. Unsaturated monocarboxylic acids are more preferable, and (meth)acrylic acid (that is, acrylic acid and/or methacrylic acid) is even more preferable from the viewpoints of reactivity, suppression of water unevenness, heat-resistant coloring, and the like.

Examples of the (meth)acrylic ester-based monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, (meth) ) n-butyl acrylate, s-butyl (meth)acrylate, n-amyl (meth)acrylate, s-amyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylic acid 2- Ethylhexyl, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid 2 -methoxyethyl, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, 1,4-dioxaspiro[4,5]deca-2- ylmethacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl -1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane etc.

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

Examples of other copolymerizable monomers include one or more of the following compounds.
(Meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam and the like; Macromonomers having a (meth)acryloyl group at one end of the combined 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 Class; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2- vinyl ethers such as hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine and N-vinylacetamide; (meth) unsaturated isocyanates such as isocyanatoethyl acrylate and allyl isocyanate; and the like.
The polymer may contain only one of the above-described monomer units (D), or may contain two or more of them.

When the polymer has the above-described monomer unit (D) other than the acid group-containing monomer unit, the content of the monomer unit (D) is the total amount of monomers in the polymer. It is preferably 1 to 80% by mass, more preferably 2 to 75% by mass, and even more preferably 3 to 70% by mass, based on 100% by mass of units.

The content of the acid group-containing monomer units in the polymer is preferably less than 5% by mass based on 100% by mass of the total monomer units in the polymer. When the content of the acid group-containing monomer unit is less than 5% by mass, a cured product having even more excellent heat-resistant color resistance can be obtained. The content of the acid group-containing monomer unit is more preferably less than 3% by mass, more preferably less than 1% by mass based on 100% by mass of the total monomer units in the polymer.

It is preferable that the polymer does not have a tertiary carbon-containing (meth)acrylate-based monomer unit in terms of further excellent heat-resistant coloring resistance.
With the tertiary carbon-containing (meth)acrylate monomer unit, when the polymer is heated, the tertiary carbon atom is eliminated to form an acid group, and the amount of the acid group increases. It is presumed that the cured product of the polymer tends to discolor (yellowing).

The tertiary carbon-containing (meth)acrylate monomer unit is a monomer unit derived from a tertiary carbon-containing (meth)acrylate monomer.
The tertiary carbon-containing (meth)acrylate-based monomer is a compound having one polymerizable carbon-carbon double bond in the molecule, that is, a (meth)acryloyl group (CH ₂ ═C(R ⁴ ) in the molecule. -C(=O)-) is preferably a compound having one group, for example, the following general formula (b):
_CH2 =C( ^R4 )-C(=O)-OA (b)
(Wherein, R ⁴ 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 a compound represented by is preferred.

In the general formula (b) above, the monovalent organic group represented by A can be represented, for example, by —C(R ⁵ )(R ⁶ )(R ⁷ ). In this case, R ⁵ , R ⁶ and R ⁷ are the same or different and are preferably a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group, It may be an unsaturated hydrocarbon group, may have a cyclic structure, or may have a substituent. Also, R ⁵ , R ⁶ and R ⁷ may be linked to each other at the terminal sites to form a cyclic structure.

The number of carbon atoms in the organic group represented by A above is the oxygen atom adjacent to the (meth)acryloyl group (CH ₂ =C( ^R )-C(=O)-) and the third It is preferably 12 or less, more preferably 9 or less, in that the new compound generated by breaking the O—C bond between the group carbon atoms is likely to volatilize. Moreover, the organic group represented by A may have a branched structure.

Here, in the tertiary carbon-containing (meth)acrylate-based monomer, at least one of the tertiary carbon atoms bonded to the oxygen atoms adjacent to the (meth)acryloyl group is bonded to a hydrogen atom. preferably. For example, the tertiary carbon-containing (meth)acrylate-based monomer is a compound represented by the general formula (b), and A is represented by -C(R ⁵ )(R ⁶ )(R ⁷ ) is a group, it is preferred that at least one of R ⁵ , R ⁶ and R ⁷ contains a carbon atom having one or more hydrogen atoms, and the carbon atom is bonded to a tertiary carbon atom.

R ⁵ , R ⁶ and R ⁷ are preferably the same or different and are preferably saturated hydrocarbon groups having 1 to 15 carbon atoms. A saturated hydrocarbon group having 1 to 10 carbon atoms is more preferred, a saturated hydrocarbon group having 1 to 5 carbon atoms is more preferred, and a saturated hydrocarbon group having 1 to 3 carbon atoms is particularly preferred.

Examples of the tertiary carbon-containing (meth)acrylate monomer that provides the tertiary carbon-containing (meth)acrylate monomer unit include t-butyl (meth)acrylate, t-amyl (meth)acrylate, and the like. It is preferably mentioned.

In the polymer, the content of the tertiary carbon-containing (meth)acrylate monomer unit is preferably 1% by mass or less, and 0.5% by mass or less based on 100% by mass of the total monomer units. More preferably, 0% by mass is even more preferable.

The acid value of the polymer is preferably 40 to 160 mgKOH/g, more preferably 50 to 150 mgKOH/g, even more preferably 60 to 140 mgKOH/g.
The above acid value is a value obtained by measuring by a 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 80,000, and even more preferably 4,000 to 50,000.
The weight-average molecular weight of the polymer is a value obtained by measuring by gel permeation chromatography (GPC) according to the method described in Examples.

The polymer is prepared by coating a resin composition containing the polymer on a glass substrate to form a coating film, drying the laminate at 100°C for 3 minutes, and then drying the laminate at 250°C for 3 minutes. When heat-treated for a long time, it is preferable that the b ^* value of the coating film side surface of the laminate obtained according to JIS Z 8729 is 1.0 or less. The above b ^* value is expressed as chromaticity representing saturation based on the L ^* a ^* b ^* color system standardized by CIE and adopted by JIS Z 8729 in Japan.
More preferably, the b ^* value is 0.4 or less.

The b ^* value is measured using a laminate obtained by coating a resin composition containing the polymer on a glass substrate to form a coating film.
Specifically, the above resin composition is applied onto a glass substrate in a coating amount (in terms of solid content) of 0.4 to 1.2 mg/cm ² , and dried at 100° C. for 3 minutes. A laminate is obtained in which a coating film of the resin composition is formed on a glass substrate. Then, the obtained laminate is further heat-treated at 250° C. for 3 hours, cooled to room temperature, and the b ^* value of the coating film side surface is measured using a color difference meter. The resin composition is measured using at least two laminates, and an approximate straight line between the coating amount (x) and the b ^* value (y) is prepared as a calibration curve from these results. Using the above calibration curve, the b ^* value in the case of a coating amount of 0.6 mg/cm ² is obtained, and this value is defined as the above b ^* value in the present invention.

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

<Method for producing polymer>
The method for producing the polymer of the present invention is not particularly limited as long as it is a method capable of obtaining a polymer having at least the above-described monomer units (A) and monomer units (B). Monomer components containing monomers giving the monomer units (A) and (B) described above, and, if necessary, monomers giving the above-mentioned monomer units (C) and (D), A method of polymerizing by a known method can be mentioned.

The method for polymerizing the above monomer component is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization and emulsion polymerization can be used. Among them, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy. In addition, as the polymerization mechanism of the monomer component, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used. is preferred.

The amount of the monomer component to be blended during polymerization is not particularly limited as long as a polymer having excellent heat resistance to coloration is obtained, and may be appropriately designed. A monomer that provides (10 to 60% by mass) and a monomer that provides the monomer unit (B) (1 to 30% by mass) are preferable, and a monomer that provides the monomer unit (A) ( 10 to 60% by mass), a monomer that gives the monomer unit (B) (1 to 30% by mass), and a monomer that gives the monomer unit (C) (2 to 60% by mass) More preferably, a monomer that provides the monomer unit (A) (10 to 60% by mass), a monomer that provides the monomer unit (B) (1 to 30% by mass), the monomer unit Further preferred are monomers that give (C) (2 to 60% by mass) and (meth)acrylic acid (less than 5% by mass).

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

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

Examples of the solvent include the same solvents as those described in JP-A-2015-157909, and one or more of them can be used. Among these solvents, propylene glycol monomethyl ether and propylene are preferred because of the solubility of the resulting polymer, the smoothness of the surface when forming a coating film, the low impact on the human body and the environment, and the ease of industrial availability. Glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and ethyl lactate are more preferably used.

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

When the above monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy. can be selected as appropriate. A reducing agent such as a transition metal salt or amines may be used together with the polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy- 2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis ( 2-methylpropionate), hydrogen peroxide, persulfate, and other peroxides and azo compounds that are usually used as polymerization initiators. These may be used individually by 1 type, or may be used in combination of 2 or more type.

The amount of the polymerization initiator to be used is not particularly limited, and may be appropriately set according to the type and amount of the monomer to be used, the polymerization conditions such as polymerization temperature and polymerization concentration, the molecular weight of the target polymer, and the like. However, for example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the monomer component.

A chain transfer agent may also be used in the above polymerization, if desired. 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 an increase in molecular weight distribution and gelation.

Examples of the chain transfer agent include those similar to the solvents described in JP-A-2015-157909, and one or more of them can be used. Among them, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkylmercaptans, mercaptoalcohols, aromatic mercaptans, mercapto Examples include compounds having a mercapto group such as isocyanurates, more preferably alkylmercaptans, mercaptocarboxylic acids and mercaptocarboxylic acid esters, and still more preferably n-dodecylmercaptan and mercaptopropionic acid.

The amount of the chain transfer agent to be used is not particularly limited, and may be appropriately set depending on the type and amount of the monomer to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and the molecular weight of the target polymer. good. For example, in order to obtain a polymer having a weight-average molecular weight of several thousand to several ten thousands, 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 monomer component. .

Regarding the conditions for the above polymerization, the polymerization temperature may be appropriately set according to the type and amount of the monomers used, the type and amount of the polymerization initiator, etc. For example, 50 to 150 ° C. 120°C is more preferred. In addition, the polymerization time can be set as appropriate, but is preferably 1 to 5 hours, more preferably 2 to 4 hours, for example.

2. Curable Resin Composition The polymer of the present invention can be made into a curable resin composition by further combining with a polymerizable compound. Since the curable resin composition contains the polymer described above, it is possible to give a cured product having excellent heat resistance to coloration. Further, by further including a polymerizable compound, in addition to heat coloring resistance, the curability of the resin composition, adhesion to the substrate, surface hardness, heat resistance, solvent resistance, etc. are even more excellent. can give
Thus, a curable resin composition containing the above polymer and a polymerizable compound is also one aspect 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 and the blending of other components. 5 to 80% by mass is preferable, 7 to 70% by mass is more preferable, and 10 to 60% by mass is even more preferable with respect to the total amount of 100% by mass.
The term "total solid content" means the total amount of components forming the cured product (excluding the solvent and the like that volatilize during the formation of the cured product).

<Polymerizable compound>
As the polymerizable compound, free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), polymerizable unsaturated bonds (also referred to as polymerizable unsaturated groups ) is a low-molecular-weight compound. Examples thereof include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.

Examples of the monofunctional compounds include N-substituted maleimide-based monomers; (meth)acrylic acid esters; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids; Unsaturated monocarboxylic acids with chain extension between groups; Unsaturated acid anhydrides; Aromatic vinyls; Conjugated dienes; Vinyl esters; Vinyl ethers; is mentioned. A monomer having an active methylene group or an active methine group can also be used.

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

trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 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-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide Pentaerythritol tetra(meth)acrylate with ethylene oxide, dipentaerythritol hexa(meth)acrylate with ethylene oxide, trimethylolpropane tri(meth)acrylate with propylene oxide, ditrimethylolpropane tetra(meth)acrylate with propylene oxide, pentaerythritol tetra(meth)acrylate with propylene oxide (Meth)acrylates, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate Trifunctional or higher polyfunctional (meth)acrylate compounds such as (meth)acrylates and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate;

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, ditri Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide polyfunctional vinyl ethers such as adduct dipentaerythritol hexavinyl ether;

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

ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether;

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

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

As the polyfunctional polymerizable compound, among others, polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, (meth)acryloyl group-containing isocyanates, from the viewpoint of reactivity, economy, availability, etc. A compound having a (meth)acryloyl group, such as a nurate compound, is preferred, and more preferred than a polyfunctional (meth)acrylate compound. By containing 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. As the polyfunctional polymerizable compound, it is more preferable to use a trifunctional or higher polyfunctional (meth)acrylate compound.
The polymerizable compounds may be used singly or in combination of two or more.

In the curable resin composition of the present invention, the content of the polymerizable compound is not particularly limited as long as the effect of the present invention is exhibited, and may be set as appropriate. From the point of being able to have a high viscosity, the total solid content of the curable resin composition of the present invention is preferably 2 to 80% by mass, more preferably 5 to 70% by mass, and still more preferably 10% by mass. ~60% by mass.

<Photoinitiator>
The curable resin composition of the present invention preferably further contains a photopolymerization initiator. By including a photopolymerization initiator, it is possible to improve the curability of the curable resin composition and improve the performance of the obtained cured product.
The photopolymerization initiator used in the present invention is preferably a radically polymerizable photopolymerization initiator. A radically polymerizable photopolymerization initiator is one that generates polymerization initiation radicals upon irradiation with active energy rays such as electromagnetic waves and electron beams.

The photopolymerization initiator is not particularly limited, and examples thereof include alkylphenone-based compounds, benzophenone-based compounds, benzoin-based compounds, thioxanthone-based compounds, halomethylated triazine-based compounds, halomethylated oxadiazole-based compounds, and biimidazole-based compounds. , oxime ester-based compounds, titanocene-based compounds, benzoic acid ester-based compounds, acridine-based compounds, and other known photopolymerization initiators can be used.
Among them, as a photopolymerization initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE907", manufactured by BASF), 2-benzyl-2- Alkylphenone compounds such as dimethylamino-1-(4-morpholinophenyl)-butanone-1 (“IRGACURE369”, manufactured by BASF) are preferred.
The photopolymerization initiators may be used singly or in combination of two or more.

The content of the photopolymerization initiator is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately designed. For example, the total solid content of the curable resin composition of the present invention is 100 It is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and still more preferably 1 to 20% by mass.

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

Photosensitizers and photoradical polymerization accelerators that may be used in combination with the photopolymerization initiator include, for example, xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, dye compounds such as pyrromethene dyes; 4-dimethylamino dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; and mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole.

When using the above-mentioned photosensitizer and 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 of curability, the influence of decomposed products, and economic efficiency. It 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 optionally contain other components in addition to the polymer, polymerizable compound, and photopolymerization initiator described above. Other components include, for example, solvents; coloring materials (also referred to as coloring agents); dispersing agents; antioxidants; Coupling agents such as titanium; thermosetting resins such as fillers, epoxy resins, phenolic resins and polyvinylphenol; curing aids such as polyfunctional thiol compounds; plasticizers; antifoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; These may be used individually by 1 type, and may be used in combination of 2 or more type. For example, when the curable resin composition is used for color filters, the curable resin composition preferably contains a colorant.

(solvent)
As the solvent, those commonly used in curable resin compositions can be used, and may be appropriately selected depending on the purpose and application, and is not particularly limited. can be used. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

Among the coloring materials, pigments are preferred from the standpoint of durability, and dyes are preferred from the standpoint of improving the luminance of panels and the like. These can be appropriately selected according to the properties required. In the curable resin composition of the present invention, pigments are preferred because they can further improve the solvent resistance and heat-resistant coloring resistance of the cured product. Pigments similar to those described in JP-A-2015-157909 can be used.

Examples of the dye include organic dyes described in JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599. 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 singly 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. 80 mass %, more preferably 5 to 70 mass %, still more preferably 10 to 60 mass %.

(dispersant)
When the curable resin composition of the present invention contains the coloring material, it preferably further contains a dispersant.
The dispersant has a site for interaction with the colorant and a site for interaction with the dispersion medium (for example, solvent or binder resin), and has the function of stabilizing the dispersion of the colorant in the dispersion medium. They are generally classified into resin-type dispersants (eg, polymer dispersants), surfactants (eg, low-molecular-weight dispersants), and pigment derivatives. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the resin-type dispersant include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , long-chain polyaminoamide phosphates, hydrogen group-containing polycarboxylic acid esters, amides and salts thereof formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/polypropylene oxide adducts, etc. mentioned. Commercially available products of the resin-type dispersant include those described in JP-A-2015-157909.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazoline;

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

The content of the dispersant may be appropriately set according to the purpose and application. It is preferably 0.01 to 60% by mass with respect to 100% by mass of the total solid content of the resin composition. More preferably 0.1 to 50% by mass, still more preferably 0.3 to 40% by mass.

(Antioxidant)
By containing an antioxidant, the curable resin composition of the present invention can further improve the heat-resistant coloring resistance of the cured product.
The antioxidant that can be used in the present invention is not particularly limited, and a known antioxidant may be appropriately selected and used. agents are preferred. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

<Preparation of 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-described ingredients using various mixers and dispersers may be mentioned. be done. The mixing/dispersing step is not particularly limited, and may be performed by a known method. In addition, other steps that are normally performed may be further included. When the curable resin composition contains a colorant, it is preferably prepared through a colorant dispersion treatment step.

As the above-described colorant dispersion treatment step, for example, first, predetermined amounts of a colorant (preferably an organic pigment), a dispersant, and a solvent are weighed, and the colorant is finely dispersed using a disperser to obtain a liquid colorant. Methods of obtaining dispersions (also called millbases) can be mentioned. Examples of the dispersing machine include paint conditioners, bead mills, roll mills, ball mills, jet mills, homogenizers, kneaders and blenders. As the dispersion treatment step, preferably, after kneading and dispersing with a roll mill, a kneader, a blender, etc., fine dispersion treatment is performed with a media mill such as a bead mill filled with beads of 0.01 to 1 mm. . A composition containing a (meth)acrylate polymer, a polymerizable monomer, a photopolymerization initiator, and, if necessary, a solvent, a leveling agent, etc., which have been separately stirred and mixed in the obtained mill base. A curable resin composition can be obtained by adding (preferably a transparent liquid) and mixing to form a uniform dispersion solution.
The obtained curable resin composition is preferably filtered using a filter or the like to remove fine dust.

3. Laminate The polymer and curable resin composition of the present invention, as described above, provide a cured product with excellent heat-resistant color resistance. In addition, the cured product is excellent in performance such as surface hardness, adhesion to substrates, heat resistance and transparency. A laminate having a cured product of such a polymer or a cured product of the curable resin composition is also one aspect of the present invention.

When the cured product is a cured film, the film thickness is preferably 0.1 to 20 μm. When the film thickness is within the above range, excellent heat resistance to coloration can be exhibited. In addition, various performances such as surface hardness, adhesion to substrates, 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.

The method for obtaining the laminate is not particularly limited, and a known method may be used. For example, the above-described polymer or the above-described curable resin composition is applied on a substrate, and the applied product is dried. , 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 according to the purpose and application. Examples thereof include substrates made of various materials such as a glass plate and a plastic plate.

For example, the laminate is used for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used in liquid crystal display devices and solid-state imaging devices, and applications such as electrical and electronic equipment. is preferably used for Among them, it is preferable to use the curable resin composition of the present invention for a color filter. Thus, a color filter having a cured product of the curable resin composition is also one aspect of the present invention. The color filters are described below.

3-1. Color Filter The color filter of the present invention comprises a substrate and a cured product of the curable resin composition described above.
In the color filter, the cured product formed from 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. , photospacers, protective layers, alignment control ribs, and other segments that do not necessarily require coloring.

Examples of the substrate used in the color filter include glass substrates such as white plate glass, soda plate glass, alkali-strengthened glass, silica-coated soda plate glass; Sheets, films or substrates made of thermoplastic resins such as additives; Sheets, films or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Metal substrates such as aluminum plates, copper plates, nickel plates and stainless steel plates a ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member composed of various materials such as a glass substrate having a coloring material layer on its surface (for example, a color filter for LCD); Among them, a glass substrate and a sheet, film or substrate made of a heat-resistant resin are preferable from the viewpoint of heat resistance. Also, the substrate is preferably a transparent substrate.
If necessary, the base material may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a silane coupling agent, or the like.

<Manufacturing method of color filter>
In order to obtain the color filter, for example, for each pixel color (that is, for each pixel of one color), a step of disposing the curable resin composition on a substrate (also referred to as a disposing step), and disposing on the substrate A step of irradiating the cured resin composition with light (also referred to as a light irradiation step), a step of developing with a developer (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step). It is preferable to employ a manufacturing method that employs a technique and repeats the same technique for each color. Note that the order in which the pixels of each color are formed is not particularly limited.

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

(Light irradiation step)
In the light irradiation step, the light source of actinic rays used includes, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an extra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a fluorescent lamp, and the like. lamp light sources, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. As for the system of the exposure machine, there are a proximity system, a mirror projection system, and a stepper system, and the proximity system is preferably used.
In addition, in the step of irradiating the active energy beam, depending on the application, the active energy beam may be irradiated through a predetermined mask pattern. In this case, the exposed portion is cured, and the cured portion becomes insoluble or slightly soluble in the developer.

(Development process)
The developing step is a step of developing with a developing solution after the above-described light irradiation step to remove the unexposed portion to form a pattern. Thereby, a patterned cured film can be obtained. Development can be carried out at a development temperature of generally 10 to 50° C. by methods such as immersion development, spray development, brush development and ultrasonic development.

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

Examples of organic solvents suitable for the developer include ether-based solvents and alcohol-based solvents. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkylphenyl ethers, aralkylphenyl ethers, diaromatic ethers , isopropanol, benzyl alcohol, and the like.

The alkaline aqueous solution may contain surfactants, organic solvents, buffers, dyes, pigments, etc., if necessary, in addition to the alkaline agent. Examples of the organic solvent in this case include organic solvents suitable for the developer described above.

Examples of the alkali agent include inorganic compounds such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, sodium tertiary phosphate, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. alkaline agents; amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., and these may be used alone. , may be used in combination of two or more.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; Anionic surfactants such as salts, alkylsulfates, alkylsulfonates, and sulfosuccinate salts; amphoteric surfactants such as alkylbetaines and amino acids; The above may be used in combination.

(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 developing step described above. For example, using a light source such as a high-pressure mercury lamp, a step of post-exposure with a light amount of, for example, 0.5 to 5 J/cm ² , a step of post-heating, for example, at a temperature of 60 to 260° C. for 10 seconds to 120 minutes, etc. mentioned. By performing such a post-curing step, it is possible to further increase the hardness and adhesion of the patterned cured film.

The thickness of the cured film obtained by the heating step (that is, the cured film obtained by thermally curing the curable resin composition) is preferably 0.1 to 20 μm. By using the curable resin composition of the present invention, a cured film having a sufficiently reduced film thickness can be obtained. In addition, since the film thickness is reduced, the density of the coloring material per unit volume of the cured film increases, and the brightness 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.
The film thickness of the coating film (that is, the cured film) obtained by the heating step is preferably 90% or less, assuming that the film thickness of the coating film before heating is 100%. More preferably 80% or less, still more preferably 70% or less.

In the heating step, the heating temperature is preferably 150° C. or higher. The heating temperature is more preferably 160° C. or higher, still more preferably 170° C. or higher, and particularly preferably 180° C. or higher. Also, the temperature is preferably 270° C. or lower, more preferably 260° C. or lower, and still more preferably 250° C. or lower.

The heating time in the heating step is not particularly limited, but is preferably 5 to 60 minutes, for example. Moreover, the heating method is not particularly limited, either, but for example, it can be performed using 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.
A member for a display device and a display device having a cured product formed from the curable resin composition are also included in the preferred embodiments of the present invention. The cured product (cured film) formed from the curable resin composition has excellent heat-resistant color resistance, is stable, has excellent adhesion to substrates, etc., exhibits high hardness, and exhibits high smoothness. Since it has a high transmittance, 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, or the like is suitable.
When the cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multilayer member composed of the cured film, or the single-layer or multilayer It may be a member in which another layer is further combined with the member of (1), or a member including the cured film in its configuration.

As described above, the polymer of the present invention and the curable resin composition containing the polymer can give a cured product having excellent heat-resistant color resistance. Moreover, the cured product obtained by using the polymer and the curable resin composition of the present invention is excellent in adhesiveness to substrates, transparency, heat resistance and the like. Such a polymer and a curable resin composition of the present invention are extremely useful for various applications in the optical field, electrical/electronic field, such as color filters.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited only to these examples. Unless otherwise specified, "part" means "mass part" and "%" means "mass %". Analysis of the polymer in each synthesis example was carried out as follows.

<Weight average molecular weight>
Measured by gel permeation chromatography using HLC-8220GPC (manufactured by Tosoh Corporation) using tetrahydrofuran as an eluent and TSK-gel SuperHZM-M (manufactured by Tosoh Corporation) as a column, and calculated in terms of standard polystyrene.

<Solid content>
About 1 g of the copolymer solution was precisely weighed in an aluminum cup, and about 2 g of acetone was added to dissolve it. After that, it was dried in a vacuum dryer (manufactured by EYELA) at a vacuum of 140° C. for 1.5 hours, then allowed to cool in a desiccator, and the mass of the aluminum cup was measured. The solid content (% by mass) of the polymer solution was calculated from the amount of mass reduction.

<Acid value>
Precisely weigh 1.5 to 2 g of the copolymer solution, dissolve it in a mixed solvent of 90 g of acetone and 10 g of water, use a 0.1 N potassium hydroxide aqueous solution as a titrant, and use an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd. , product: COM-1700), and the acid value per gram of polymer was determined from the acid value of the solution and the solid content.

<Heat resistant coloring>
A resin composition solution was prepared by adding an antioxidant Irganox 1010 (manufactured by BASF) to the copolymer solution so as to have a concentration of 0.5% by mass. Using a spin coater (manufactured by Mikasa Co., Ltd., MS-B-100), this resin composition solution was coated on a 5 cm square glass substrate so that the coating amount was 0.4 to 1.2 mg/cm ² in terms of solid content. (Soda lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.) was uniformly coated. At this time, for each resin composition, the rotation speed of the spin coater was changed to change the coating amount (in terms of solid content), and two coated plates with different coating amounts were produced. The amount applied to one of the two sheets was always greater than 0.6 mg/cm ² , and the amount applied to the other sheet was always less than 0.6 mg/cm ² .
By drying these coated plates at 100° C. for 3 minutes, a laminate having a coating film formed on a glass substrate was obtained. After removing the resin adhering to the edges of the glass substrate, the obtained laminate was heat-treated at 250° C. for 3 hours using a perfect oven thermostat (manufactured by Espec) and cooled to room temperature. After cooling, the coating film surface of the laminate was measured using a colorimetric color difference meter ZE6000 (manufactured by Nippon Denshoku Industries Co., Ltd.) to obtain the b* value after the heating test. For each coating film, an approximate straight line (calibration curve) of the coating amount (x) and b ^* value (y) is obtained from the measured values of the two coating films prepared as described above, and the coating amount is 0.6 mg / cm. The b ^* value for ² was taken as the result of the heat stain resistance of each coating. In addition, it can be said that the smaller the b ^* value, the smaller the yellowing after heating, and the better the heat-resistant coloring resistance.

(Synthesis example 1)
Preparation of copolymer solution 1
Preparation of copolymer solution 1 (MD/HEMA/MMA/HOA-MS copolymer solution)
A separable flask equipped with a thermometer, a stirrer, a gas inlet tube, a condenser tube and a dropping tank inlet is prepared as a reaction tank, and dimethyl-2,2'-[oxybis(methylene)] is prepared as a monomer dropping tank. Bis-2-propenoate (hereinafter referred to as "MD") 10.0 parts, 2-hydroxyethyl methacrylate (hereinafter referred to as "HEMA") 15.0 parts, methyl methacrylate (hereinafter referred to as "MMA") 30.2 parts, mono (2-acryloyloxyethyl) succinate (hereinafter referred to as "HOA-MS") 44.8 parts, t-butyl peroxy-2-ethylhexanoate ("Perbutyl 2 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) and 34 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) are mixed well with stirring, and n-dodecyl is used as a chain transfer agent dropping tank. A mixture of 1.6 parts of mercaptan (hereinafter referred to as “n-DM”) and 7.7 parts of PGMEA was thoroughly stirred and mixed.

After charging 141 parts of PGMEA into the reactor and purging with nitrogen, the temperature of the reactor was raised to 90°C by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was carried out over 2.5 hours while maintaining the temperature at 90°C. After 60 minutes from the end of the dropwise addition, the temperature of the reactor was raised to 110°C. After maintaining the temperature at 110° C. for 3 hours, the copolymer solution 1 was obtained by cooling to room temperature. Various physical properties are shown in Table 1.

(Synthesis example 2)
Preparation of copolymer solution 2 (MD/HEMA/MMA/HOA-MS copolymer solution)
Copolymer solution 2 was prepared in the same manner as in Synthesis Example 1 except that the amounts of the monomers charged were MD 10.0 parts, HEMA 15.0 parts, MMA 58.4 parts, and HOA-MS 16.6 parts. Obtained. Various physical properties are shown in Table 1.

(Synthesis Example 3)
Preparation of copolymer solution 3 (MD/CHMA/HEMA/MMA/HOA-MS/AA copolymer solution)
The amount of charged monomers was MD 10.0 parts, cyclohexyl methacrylate (hereinafter referred to as "CHMA") 20.0 parts, HEMA 15.0 parts, MMA 20.8 parts, HOA-MS 29.8 parts, acrylic acid ( Hereinafter referred to as "AA".) A copolymer solution 3 was obtained in the same manner as in Synthesis Example 1, except that 4.4 parts was used. Various physical properties are shown in Table 1.

(Synthesis Example 4)
Preparation of copolymer solution 4 (MD/t-BMA/HEMA/MMA/HOA-MS copolymer solution)
The amount of monomer charged was 10.0 parts MD, 29.5 parts t-butyl methacrylate (hereinafter referred to as “t-BMA”), 15.0 parts HEMA, 1.0 parts MMA, and 44.5 parts HOA-MS. A copolymer solution 4 was obtained in the same manner as in Synthesis Example 1 except that Various physical properties are shown in Table 1.

(Synthesis Example 5)
Preparation of copolymer solution 5 (BzMI/HEMA/MMA/HOA-MS copolymer solution)
Same as Synthesis Example 1 except that the amount of the monomers charged was 10.0 parts of N-benzylmaleimide (hereinafter referred to as "BzMI"), 15.0 parts of HEMA, 29.0 parts of MMA, and 46.0 parts of HOA-MS. A copolymer solution 5 was obtained by performing the same operation. Various physical properties are shown in Table 1.

(Synthesis Example 6)
Preparation of copolymer solution 6 (CHMI/HEMA/MMA/HOA-MS copolymer solution)
Same as Synthesis Example 1 except that the amount of the monomers charged was 10.0 parts of N-cyclohexylmaleimide (hereinafter referred to as "CHMI"), 15.0 parts of HEMA, 29.0 parts of MMA, and 46.0 parts of HOA-MS. A copolymer solution 6 was obtained by performing the same operation. Various physical properties are shown in Table 1.

(Synthesis Example 7)
Preparation of copolymer solution 7 (MD/t-BMA/MMA/HOA-MS copolymer solution)
The same operation as in Synthesis Example 1 was performed except that the amounts of the monomers charged were 10.0 parts MD, 44.5 parts t-BMA, 1.0 parts MMA, and 44.5 parts HOA-MS to obtain a copolymer solution. got 7. Various physical properties are shown in Table 1.

(Synthesis Example 8)
Preparation of copolymer solution 8 (MD/t-BMA/HEMA/MMA/AA copolymer solution)
The same operation as in Synthesis Example 1 was performed except that the charged amounts of the monomers were 10.0 parts MD, 32.5 parts t-BMA, 15.0 parts HEMA, 26.7 parts MMA, and 15.8 parts AA. A polymer solution 8 was obtained. Various physical properties are shown in Table 1.

(Synthesis Example 9)
Preparation of copolymer solution 9 (MD/t-BMA/MMA/MAA copolymer solution)
Copolymer solution 9 was prepared in the same manner as in Synthesis Example 1, except that the amounts of the monomers charged were 10.0 parts MD, 42.7 parts t-BMA, 29.6 parts MMA, and 17.7 parts MAA. Obtained. Various physical properties are shown in Table 1.

(Examples 1 to 6, Comparative Examples 1 to 3)
The obtained copolymer solutions 1 to 9 were used to evaluate heat resistance to coloration. Table 1 shows the results.

Descriptions in Table 1 represent the following.
MD: dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate BzMI: N-benzylmaleimide CHMI: N-cyclohexylmaleimide t-BMA: t-butyl methacrylate CHMA: cyclohexyl methacrylate HEMA: methacrylic acid 2-hydroxyethyl MMA: methyl methacrylate HOA-MS: mono(2-acryloyloxyethyl) succinate
AA: acrylic acid MAA: methacrylic acid

From Table 1, the vinyl-based monomer unit represented by the general formula (I) and the polymer having a hydroxyl group-containing monomer unit (Examples 1 to 6) are Compared with the polymers (Comparative Examples 1 to 3) that do not have at least any monomer unit, the b ^* value was very small and the heat-resistant coloring resistance was remarkably excellent.
Further, according to Table 1, among the polymers having vinyl-based monomer units represented by the general formula (I) and hydroxyl-containing monomer units, tertiary carbon-containing (meth)acrylate-based Polymers containing no monomer units (Examples 1, 2, 3, 5 and 6) are compared with polymers containing tertiary carbon-containing (meth)acrylate monomer units (Example 4) As a result, it was recognized that the heat coloring resistance was even more excellent.
Further, according to Table 1, in the polymer containing no tertiary carbon-containing (meth)acrylate-based monomer unit, the polymer containing no acid group-containing monomer unit (Examples 1, 2, 5 and 6) was found to be much more excellent in heat-resistant coloring resistance than the polymer containing 4.4% by mass of acid group-containing monomer units (Example 3).

Claims (8)

A ring structure-containing polymer having a ring structure in the main chain,
The polymer comprises vinyl-based monomer units represented by the following general formula (I), hydroxyalkyl (meth)acrylate units, N-benzylmaleimide, N-cyclohexylmaleimide, dialkyl-2,2′-( Oxydimethylene) diacrylate-based monomers and α-(unsaturated alkoxyalkyl) ring structures in the main chain derived from at least one monomer selected from the group consisting of acrylate-based monomers and a monomer unit having
The content of the vinyl-based monomer unit represented by the general formula (I) is 10 to 60% by mass with respect to 100% by mass of the total monomer units of the polymer,
The content of the hydroxyalkyl (meth)acrylate unit is 1 to 30% by mass with respect to 100% by mass of the total monomer units of the polymer,
The polymer is characterized in that the content of (meth)acrylic acid units is less than 1 % by mass with respect to 100% by mass of the total monomer units of the polymer.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms. R ³ represents a divalent organic group, X represents a carboxyl group, a sulfonic acid group, a carboxylic acid anhydride group, or a phosphoric acid group, m represents a vinyl 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 1. ) 2. The polymer according to claim 1, which has an acid value of 40 to 160 mgKOH/g. 3. The content of the monomer unit having a ring structure in the main chain is 2 to 60% by mass with respect to 100% by mass of the total monomer units of the polymer. polymer. Claims 1 to 3, wherein the polymer excludes a polymer having a repeating unit represented by the following general formula (II) or a polymer having a repeating unit represented by the following general formula (III). The polymer according to any one of

(In formula (II), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent organic group, (C ¹ ) ⁺ is -N ⁺ R ¹⁴ R ¹⁵ - or -P ⁺ R ¹⁶ R ¹⁷ -, R ¹⁴ to R ¹⁷ each independently represent a monovalent organic group, (A 1 ⁾ - ^is CO ₂ ^- , SO ₃ ^- or PO ₄ ^- .)

(In formula (III), R ²¹ represents a hydrogen atom or a methyl group, R ²² and R ²³ each independently represent a divalent organic group, (A 2 ⁾ - ^is -OP (= ^O )(-O- ₎ ^O- , -SO2N - _SO2- ^or -C ⁽ = O ⁾ N ^- SO2- , ( C2 ₎ + ^is N ⁺ R24R25R26 ^or P ⁺ represents R ²⁷ R ²⁸ R ²⁹ and R ²⁴ to R ²⁹ each independently represent a monovalent organic group.) A curable resin composition comprising the polymer according to any one of claims 1 to 4 and a polymerizable compound. A laminate comprising a cured product of the polymer according to any one of claims 1 to 4 or a cured product of the curable resin composition according to claim 5 on a substrate. A color filter comprising a cured product of the curable resin composition according to claim 5 on a substrate. A display device comprising the color filter according to claim 7 .