JP6962778B2 - Curable resin composition and its use - Google Patents

Description

The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition capable of obtaining a cured product excellent in water unevenness suppression and heat-resistant coloring, a cured product thereof, a color filter using the cured product, and a display device.

Curable resin compositions that can be cured by heat or active energy rays include, for example, various types of curable resin compositions such as color filters, inks, printing plates, printed wiring boards, semiconductor devices, and photoresists used in liquid crystal display devices and solid-state image sensors. Various applications have been studied for various applications such as optical members and electric / electronic devices, and curable resin compositions having excellent properties required for each application have been developed. Among these applications, a color filter is a main component constituting a liquid crystal display device, a solid-state image sensor, etc., and generally has a substrate, at least three primary colors (red (R), green (G), blue (B)). In addition to the pixels and the resin black matrix (BM) that separates them, it is composed of a protective film or the like provided to cover and protect the pixels and the resin black matrix and to flatten their irregularities.

Usually, when the pixels of a color filter are formed using a curable resin composition, the curable resin composition is formed by (1) a coating step of applying the curable resin composition to the entire surface of the substrate and (2) a coating step for each color of the pixels. A pattern exposure is applied to the resist film via a photomask to cure the exposed portion, and then the cured portion is insolubilized. (3) The unexposed portion is removed with a developing solution, and then the exposed portion is exposed by firing (baking). A method is adopted in which a developing / firing (baking) processing step of further curing the portion is performed, and the same step is repeated for each color. Considering the application of such color filters to applications, the curable resin composition has various curability, solvent resistance after curing, adhesion to a substrate (base material), heat resistance, transparency, and the like. It is required to have physical properties. Further, in recent years, optical members, electric / electronic devices, and the like are becoming smaller, thinner, and energy-saving, and along with this, members such as color filters used are required to have high-quality performance.

Examples of the curable resin composition suitable for color filter applications include N-benzylmaleimide monomer unit, tertiary carbon-containing (meth) acrylate-based monomer unit, monomer unit having a hydroxyl group, and acrylic acid. A curable resin composition (see Patent Document 1) containing a (meth) acrylate-based polymer having a unit, a polymerizable compound, and a photopolymerization initiator has been proposed.

JP-A-2015-157909

However, in such a conventional curable resin composition, when developing with a developing solution after the exposure step, when the developing solution adheres to the exposed and cured portion (cured portion), the adhered portion becomes cloudy. There is a problem that unevenness of light and shade (unevenness of water) is formed in the cured portion, and the transparency and colorability of the cured product are lowered.
Further, in recent years, the curable resin composition applied to a color filter has been required to prevent discoloration such as yellowing as much as possible due to heating during production from the viewpoint of improving the brightness of the color filter. Such heat-resistant coloring properties have been studied so far, but with the increase in performance required for color filters and the like, further improvement is required.

In view of the above situation, the present invention provides a curable resin composition capable of sufficiently suppressing water unevenness, having excellent heat-resistant coloring properties, and obtaining a cured product that can be suitably used for color filter applications. The purpose is to do.

The present inventor has made various studies on curable resin compositions in order to solve the above problems, and found that N-alkylmaleimide monomer units and / or N-cycloalkylmaleimide monomer units and alicyclic hydrocarbon groups. By using a polymer having an acid group-containing monomer unit and an acid group-containing monomer unit in a specific range amount, water unevenness is sufficiently suppressed and a cured product having excellent heat-resistant coloring property can be obtained. I found that I could do it. Further, the present inventor has found that such a curable resin composition is particularly suitable as a resin composition for forming a member for use such as a color filter, and has completed the present invention.

That is, the present invention is a curable resin composition containing an acid group-containing polymer, wherein the acid group-containing polymer is an N-alkylmaleimide monomer unit and / or an N-cycloalkylmaleimide monomer unit. A curable resin composition comprising 2 to 30% by mass, an alicyclic hydrocarbon group-containing monomer unit of 10 to 40% by mass, and an acid group-containing monomer unit of 5 to 25% by mass. be.
The present invention is also a cured product, which is obtained by curing the curable resin composition.
The present invention is also a color filter characterized by having the cured product on a substrate.
The present invention is also a display device including the above color filter.

Since the curable resin composition of the present invention has the above-mentioned structure, water unevenness is suppressed and a cured product having excellent heat-resistant coloring can be obtained. Such a curable resin composition of the present invention includes optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, and electric / electronic devices used in liquid crystal display devices, solid-state image sensors, and the like. It can be suitably used for various purposes such as.

The present invention will be described in detail below.
A combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

1. 1. Curable Resin Composition The curable resin composition of the present invention contains an acid group-containing polymer, and the acid group-containing polymer is an N-alkylmaleimide monomer unit and / or an N-cycloalkylmaleimide single amount. It is characterized by having 2 to 30% by mass of a body unit, 10 to 40% by mass of an alicyclic hydrocarbon group-containing monomer unit, and 5 to 25% by mass of an acid group-containing monomer unit.
By containing the acid group-containing polymer, water unevenness is suppressed and a cured product having excellent heat-resistant coloring property can be obtained. Alternatively, it is presumed that having the N-cycloalkylmaleimide monomer unit and the alicyclic hydrocarbon group-containing monomer unit increases the hydrophobicity of the obtained cured product. Further, it is presumed that the acid group-containing polymer has an alicyclic hydrocarbon group-containing monomer unit, so that discoloration during heating is suppressed.

In addition, in this specification, "water unevenness" means that a cured product comes into contact with a water-soluble solution such as a developing solution, and after removing the water-soluble solution, discoloration occurs such that the contacted portion becomes cloudy and cured. It means that there is unevenness in light and shade on the object.
Hereinafter, each component of the curable resin composition of the present invention will be described.

<1-1. Acid group-containing polymer>
The acid group-containing polymer used in the present invention is an N-alkylmaleimide monomer unit and / or an N-cycloalkylmaleimide single amount with respect to 100% by mass of all the monomer units constituting the acid group-containing polymer. It has 2 to 30% by mass of body units, 10 to 40% by mass of alicyclic hydrocarbon group-containing monomer units, and 5 to 25% by mass of acid group-containing monomer units. Therefore, the curable resin composition containing the acid group-containing polymer is less likely to cause water unevenness, and can provide a cured product having excellent heat-resistant coloring properties.
The acid group-containing polymer has 100% by mass of all the monomer units of the acid group-containing polymer in that water unevenness is further suppressed and a cured product having more excellent heat-resistant coloring property can be obtained. On the other hand, N-alkylmaleimide monomer unit and / or N-cycloalkylmaleimide monomer unit 5 to 20% by mass, alicyclic hydrocarbon group-containing monomer unit 10 to 35% by mass, and acid group. It preferably has 10 to 25% by mass of the monomer unit contained, and 5 to 20% by mass of the N-alkylmaleimide monomer unit and / or the N-cycloalkylmaleimide monomer unit, and the alicyclic hydrocarbon group-containing unit. It is more preferable to have 10 to 33% by mass of the polymer unit and 12 to 25% by mass of the acid group-containing monomer unit.
Hereinafter, each monomer unit constituting the acid group-containing polymer will be described.

(N-alkylmaleimide monomer unit and / or N-cycloalkylmaleimide monomer unit)
The acid group-containing polymer has an N-alkylmaleimide monomer unit and / or an N-cycloalkylmaleimide monomer unit. When the acid group-containing polymer has an N-alkylmaleimide monomer unit and / or an N-cycloalkylmaleimide monomer unit, water unevenness of the obtained cured product is suppressed and heat-resistant coloring is improved. be able to. Among them, it is preferable to have an N-cycloalkylmaleimide monomer unit in that it can further suppress water unevenness and exhibit heat-resistant coloring property.

Examples of the N-alkylmaleimide monomer unit include a polymer structural unit derived from the N-alkylmaleimide monomer.
Examples of the N-alkylmaleimide monomer include maleimide monomers having a chain alkyl group having 1 to 20 carbon atoms, and specific examples thereof include N-methylmaleimide and N-ethylmaleimide. , Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, Nt-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn- Examples thereof include heptylmaleimide, Nn-octylmaleimide, N-dodecylmaleimide, N-laurylmaleimide, and 2-ethylhexylmaleimide.

Examples of the N-cycloalkylmaleimide monomer unit include a polymer structural unit derived from the N-cycloalkylmaleimide monomer.
Examples of the N-cycloalkylmaleimide monomer include maleimide monomers having a cycloalkyl group having 5 to 10 carbon atoms, and specific examples thereof include N-cyclohexylmaleimide and N-cyclopentylmaleimide. , N-dicyclopentanylmaleimide, N-dicyclopentenylmaleimide, N-tricyclodecanylmaleimide and the like. Of these, N-cyclohexylmaleimide is preferable because it can further suppress water unevenness and exhibit heat-resistant coloring.
The acid group-containing polymer may have only one of the above-mentioned N-alkylmaleimide monomer units and / or N-cycloalkylmaleimide monomer units, or two types. It may have the above.

The content ratio of N-alkylmaleimide monomer unit to N-cycloalkylmaleimide monomer unit (N-alkylmaleimide monomer unit / N-cycloalkylmaleimide monomer unit) is 0/100 to mass ratio. It is preferably 50/50, more preferably 0/100 to 30/70, and even more preferably 0/100 to 10/90.

(Alicyclic hydrocarbon group-containing monomer unit)
The acid group-containing polymer has an alicyclic hydrocarbon group-containing monomer unit. When the acid group-containing polymer contains the alicyclic hydrocarbon group-containing monomer unit, the curable resin composition of the present invention can suppress water unevenness and provide a cured product having excellent heat-resistant coloring properties. Can be done.

Examples of the alicyclic hydrocarbon group-containing monomer unit include a polymer structural unit derived from a monomer having an alicyclic hydrocarbon group and having a polymerizable double bond.
Examples of the alicyclic hydrocarbon group preferably include an alicyclic hydrocarbon group having 3 to 12 carbon atoms and more preferably 7 to 10 carbon atoms, and specifically, cyclopropyl, cyclopentyl and cyclohexyl. , Cyclooctyl, cyclododecyl, cycloheptyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and other monocyclic hydrocarbon groups; dicyclopentanyl, dicyclopentenyl, tricyclodecanyl, adamantyl, isobornyl and other polycyclic hydrocarbons Hydrocarbon groups can be mentioned. Among them, the alicyclic hydrocarbon group is preferably a polycyclic hydrocarbon group, and is preferably a polycyclic hydrocarbon group, because it can further suppress water unevenness and exhibit heat-resistant coloring property. It is more preferably dicyclopentenyl or isobornyl, and particularly preferably dicyclopentanyl.

Examples of the polymerizable double bond include a (meth) acryloyl group, a vinyl group, an allyl group, and a metharyl group. The monomer having a polymerizable double bond is preferably a (meth) acrylate-based monomer. That is, the alicyclic hydrocarbon group-containing monomer is preferably an alicyclic hydrocarbon group-containing (meth) acrylate-based monomer.
In addition, in this specification, "(meth) acrylate" means "acrylate and / or methacrylate".

Specific examples of the alicyclic hydrocarbon group-containing monomer include cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and (3). , 4-Epoxycyclohexyl) methyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol- Tricyclodecanedi (meth) acrylate, pentacyclopentadecanedimethanol rudi (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, norbornan dimethanol di (meth) acrylate, p-menthan-1,8-diol di (meth) Acrylate, p-menthan-2,8-diol di (meth) acrylate, p-menthan-3,8-diol di (meth) acrylate, bicyclo [2.2.2] -octane-1-methyl-4-isopropyl-5 , 6-Dimethylol di (meth) acrylate and the like.

Among them, as the alicyclic hydrocarbon group-containing monomer, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate are more preferable, and dicyclopentanyl (meth). Acrylate is more preferred, and dicyclopentanyl methacrylate is particularly preferred.
The acid group-containing polymer may have only one kind of the above-mentioned ones or two or more kinds as the alicyclic hydrocarbon group-containing monomer unit.

(Acid group-containing monomer unit)
The acid group-containing polymer has an acid group-containing monomer unit. Since the acid group-containing polymer has an acid group-containing monomer unit, the curable resin composition of the present invention improves the surface hardness of the cured product at the time of curing, and makes the cured product adherent to the substrate and alkali-soluble. It can give an excellent cured product. Further, when the curable resin composition of the present invention is used for a color filter application, a cured film (cured product) having excellent developability can be formed.
Examples of the acid group-containing monomer unit include a polymer structural unit derived from the acid group-containing monomer. Examples of the acid group-containing monomer include compounds having a polymerizable double bond with an acid group in the molecule.

Examples of the acid group include functional groups that neutralize with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, and only one of these is present. It may be used, or it may have two or more types. Of these, a carboxyl group and a carboxylic acid anhydride group are preferable, and a carboxyl group is more preferable.
Examples of the polymerizable double bond include a (meth) acryloyl group, a vinyl group, an allyl group, and a metharyl group.

Examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, silicic acid, and vinyl benzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Unsaturated polyvalent carboxylic acids such as monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl) and other unsaturated groups in which the chain is extended between the unsaturated group and the carboxyl group. Examples thereof include carboxylic acids; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and unsaturated compounds containing a phosphoric acid group such as light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.). Among these, it is preferable to use carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) 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 more preferable in terms of reactivity, suppression of water unevenness, heat-resistant coloring and the like.
The acid group-containing polymer may have only one of the above-mentioned acid group-containing monomer units, or may have two or more of the above-mentioned acid group-containing polymers.

(Vinyl-based monomer unit containing ^{-COO *} R ^{1 group)}
The acid group-containing polymer has the above-mentioned monomer unit as a structural unit, and further, -COO ^* R ¹ (R ¹ is a monovalent organic group and is a carbon bonded to ^{O *.} The atom preferably has a vinyl-based monomer unit (hereinafter, also referred to as “vinyl-based monomer unit (A)”) containing a group (which is a tertiary carbon atom). When the acid group-containing polymer further has the vinyl-based monomer unit (A) and the hydroxyl group-containing monomer unit described later, the curability of the curable resin composition, the hardness of the cured product, and the solvent resistance It is possible to improve properties, heat resistance, transparency, adhesion to a substrate, and the like. Further, when the curable resin composition of the present invention contains a coloring material, the concentration of the coloring material in the obtained cured product can be increased. Therefore, it is possible to realize further thinning, and it is possible to further improve the color purification and the high shading rate of the black matrix.

When the acid group-containing polymer has the vinyl-based monomer unit (A) and the hydroxyl group-containing monomer unit described later, the curability of the curable resin composition and the characteristics of the cured product described above are improved. When a coating film is formed using the cured resin composition and heated, the tertiary carbon in the vinyl-based monomer unit (A) is desorbed to generate an acid group, which can be combined with the acid group. , It is presumed that this is due to cross-linking with the hydroxyl group of the hydroxyl group-containing monomer unit. Further, the reason why the colorant concentration in the cured product can be increased is that, as described above, the cross-linking reaction proceeds due to the desorption of the tertiary carbon, while the desorbed components volatilize and the amount of resin in the cured product is relative. It is presumed that this is due to the decrease.

In the vinyl-based monomer unit (A), ^{R 1} of -COO ^* R ¹ represents a monovalent organic group, the carbon atom bonded to ^{O *} is a tertiary carbon atom. The tertiary carbon atom means a carbon atom having three other carbon atoms bonded to the carbon atom.
The monovalent organic group preferably includes a monovalent chain, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 90 carbon atoms. The organic group may have a substituent.
The carbon number of R ¹ is more preferably 1 to 46 carbon atoms, further preferably 1 to 20 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
R ¹ is preferably a monovalent organic group similar to A in the general formula (a) described later.

Examples of the vinyl-based monomer include a monomer having a polymerizable carbon-carbon double bond in the molecule, and among them, a (meth) acrylate-based monomer is preferable. That is, the vinyl-based monomer unit (A) is preferably a tertiary carbon-containing (meth) acrylate-based monomer unit.

Further, the tertiary carbon-containing (meth) acrylate-based monomer preferably has a structure in which an oxygen atom adjacent to the (meth) acryloyl group is bonded to a tertiary carbon atom.

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 ^{2)) in the molecule.} ) -C (= O)-) is preferable, and for example, the following general formula (a):
CH ₂ = C (R ² ) -C (= O) -OA (a)
(In the formula, R ² 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 preferable.

In the above general formula (a), the monovalent organic group represented by A can be represented by, for example, −C (R ³ ) (R ⁴ ) (R ⁵ ). In this case, R ^{3, R 4,} and R ⁵ are the same or different, is 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, it may have a cyclic structure, or it may have a substituent. Further, R ³ , R ⁴ and R ⁵ may be connected to each other at the terminal sites to form an annular structure.

The carbon number of the organic group represented by A is _{the oxygen atom adjacent to the (meth) acryloyl group (CH 2} = C (R ² ) -C (= O)-) and the third carbon atom in A adjacent thereto. It is preferably 12 or less, and more preferably 9 or less, in that a new compound formed by cleaving the OC bond with the class carbon atom is easily volatilized. Further, 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 adjacent carbon atoms of the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth) acryloyl group is bonded to the hydrogen atom. It is preferable to do so. For example, the tertiary carbon-containing (meth) acrylate-based monomer is a compound represented by the above general formula (a), and A is represented by −C (R ³ ) (R ⁴ ) (R ⁵ ). In the case of a group, it is preferable that ^{at least one of R 3} , R ⁴ and R ⁵ 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, heating cleaves the OC bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto to generate (meth) acrylic acid at the same time. , A double bond (C = C) is formed between the tertiary carbon atom and the carbon atom adjacent thereto, and a new compound is produced more stably.

The new compound produced as described above is preferably volatile. In this case, the film thickness of the cured product (cured film) is reduced due to the volatilization of the new compound from the cured product, and at the same time, for example, the curable resin composition further contains a coloring material. In some cases, the colorant concentration increases after heating. Therefore, it is possible to realize further thinning, and it is possible to further improve the color purification and the high shading rate of the black matrix. Considering this point, ^{it is preferable that R 3} , R ⁴ and R ⁵ are the same or different saturated hydrocarbon groups having 1 to 15 carbon atoms. A saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable, a saturated hydrocarbon group having 1 to 5 carbon atoms is more preferable, and a saturated hydrocarbon group having 1 to 3 carbon atoms is particularly preferable.

The (meth) acrylate-based monomer having a tertiary carbon atom is preferably t-butyl (meth) acrylate or t-amyl (meth) acrylate.
The acid group-containing polymer may have only one of the above-mentioned vinyl-based monomer units (A), or may have two or more of the above-mentioned vinyl-based monomer units (A).

The content of the vinyl-based monomer unit (A) in the acid group-containing polymer is preferably 20 to 60% by mass, based on 100% by mass of all the monomer units of the acid group-containing polymer. It is preferably 25 to 50% by mass, more preferably 25 to 40% by mass.

(Hydroxy group-containing monomer unit)
The acid group-containing polymer preferably further contains a hydroxyl group-containing monomer unit. When the acid group-containing polymer further contains a hydroxyl group-containing monomer unit together with the vinyl-based monomer unit (A), the curability of the curable resin composition of the present invention, the hardness of the cured product, and the solvent resistance It is possible to improve properties, heat resistance, transparency, adhesion to a substrate, and the like. In addition, the cured product can be thinned and the colorant density can be increased.

The hydroxyl group-containing monomer is not particularly limited as long as it is a compound having a polymerizable double bond with a hydroxyl group in the molecule, and for example, 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 Hydroxyalkyl (meth) acrylates such as −hydroxypropyl are preferred, and 2-hydroxyethyl (meth) acrylate is more preferred.
The acid group-containing polymer may have only one of the above-mentioned hydroxyl group-containing monomer units, or may have two or more of the above-mentioned hydroxyl group-containing monomer units.

The content of the hydroxyl group-containing monomer unit in the acid group-containing polymer is preferably 10 to 40% by mass, more preferably 10 with respect to 100% by mass of all the monomer units of the acid group-containing polymer. It is ~ 35% by mass, more preferably 10 to 30% by mass.

As described above, the acid group-containing polymer has an N-alkylmaleimide monomer unit and / or an N-cycloalkylmaleimide monomer unit of 2 to 30% by mass, and an alicyclic hydrocarbon group-containing monomer unit. It has 10 to 40% by mass and 5 to 25% by mass of an acid group-containing monomer unit, but further contains 20 to 60% by mass of the vinyl-based monomer unit (A) and the hydroxyl group. Having 10 to 40% by mass of monomer units is also one of the preferred embodiments.

The acid group-containing polymer may contain other polymerizable monomer units in addition to the above-mentioned monomer units.
Examples of the other polymerizable monomer unit include a single amount derived from a (meth) acrylic acid ester-based monomer, an aromatic hydrocarbon group-containing monomer, another copolymerizable monomer, and the like. The body unit can be mentioned.

Examples of the (meth) acrylic acid ester-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth). ) N-butyl acrylate, s-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-amyl (meth) acrylate Ethylhexyl, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2 acrylate (meth) acrylate -Methoxyethyl, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 1,4-dioxaspiro [4,5] deca-2- Ilmethacrylic 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 And so on.

Examples of the aromatic hydrocarbon group-containing monomer include aromatic vinyl-based monomers such as styrene, vinyltoluene, α-methylstyrene, and methoxystyrene; and N- such as N-phenylmaleimide and N-benzylmaleimide. Aromatically substituted maleimides and the like can be mentioned.

Examples of the other copolymerizable monomer include one or more of the following compounds.
(Meta) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; weights of polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam, etc. Macromonomers having a (meth) acryloyl group at one end of the coalesced molecular chain; conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. Kind: 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; 2,2'-[oxybis (methylene)] bisacrylic acid, dialkyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dialkyl -2,2'-[Oxybis (methylene)] Dialkyl-2,2'-(oxydimethylene) diacrylate-based monomers such as bis-2-propenoate; α-allyloxymethylacrylate, α-allyl Methyl oxymethylacrylate, ethyl α-allyloxymethylacrylate, n-propyl α-allyloxymethylacrylate, i-propyl α-allyloxymethylacrylate, n-butyl α-allyloxymethylacrylate, α- Allyloxymethylacrylate s-butyl, α-allyloxymethylacrylate t-butyl, α-allyloxymethylacrylate n-amyl, α-allyloxymethylacrylate s-amyl, α-allyloxymethylacrylate t Examples thereof include α- (unsaturated alkoxyalkyl) acrylate-based monomers such as −Amil and neopentyl α-allyloxymethylacrylate.

The content of the aromatic hydrocarbon group-containing monomer unit of the acid group-containing polymer is 5% by mass or less with respect to 100% by mass of all the monomer units of the acid group-containing polymer. preferable. When the content of the aromatic hydrocarbon group-containing monomer unit is 5% by mass or less, the heat-resistant coloring property is further excellent. The content of the aromatic hydrocarbon group-containing monomer unit is more preferably 3% by mass or less, still more preferably 0% by mass.
Examples of the aromatic hydrocarbon group-containing monomer unit include a monomer unit derived from the above-mentioned aromatic hydrocarbon group-containing monomer.

The acid group-containing polymer also ^{has a vinyl-based monomer unit having a -COOR 6} (R ⁶ is an alkyl group having 1 to 3 carbon atoms) group (hereinafter, "vinyl-based monomer unit (B)". ) ”) Is preferably 5% by mass or less with respect to 100% by mass of all the monomer units of the acid group-containing polymer. When the content of the vinyl-based monomer unit (B) is 5% by mass or less, the hydrophobicity of the cured product becomes higher, and the suppression of water unevenness is further excellent. The content of the vinyl-based monomer unit (B) is more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 0% by mass.

Examples of the vinyl-based monomer unit (B) include a monomer unit derived from methyl (meth) acrylate, ethyl (meth) acrylate, or propyl (meth) acrylate, and (meth) is preferable. It is a monomer unit derived from methyl acrylate.

(Method for producing acid group-containing polymer)
As a method for producing the acid group-containing polymer, at least the above-mentioned N-alkylmaleimide monomer unit and / or N-cycloalkylmaleimide monomer unit, alicyclic hydrocarbon group-containing monomer unit, and the above-mentioned alicyclic hydrocarbon group-containing monomer unit, and The method is not particularly limited as long as it can obtain an acid group-containing polymer having an acid group-containing monomer unit, for example, the above-mentioned N-alkylmaleimide monomer and / or N-cycloalkylmaleimide single amount. Examples thereof include a method of polymerizing a body, an alicyclic hydrocarbon group-containing monomer, an acid group-containing monomer, and a monomer component containing the above-mentioned other monomer, if necessary, by a known method. Be done.

The method for polymerizing the above-mentioned monomer components is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Of these, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy. Further, 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, but the radical polymerization mechanism has an industrial advantage. The polymerization method based on this is preferable.

The blending amount of the monomer component at the time of polymerization includes the N-alkylmaleimide monomer unit and / or the N-cycloalkylmaleimide monomer (2 to 30% by mass) and the alicyclic hydrocarbon group. It is preferable to contain the monomer (10 to 40% by mass) and the acid group-containing monomer (5 to 25% by mass), and the N-alkylmaleimide monomer unit and / or the N-cycloalkylmaleimide. Monomer (2 to 30% by mass), alicyclic hydrocarbon group-containing monomer (10 to 40% by mass), acid group-containing monomer (5 to 25% by mass), vinyl-based single amount It is more preferable to contain the body (A) (20 to 60% by mass) and the above-mentioned hydroxyl group-containing monomer (10 to 40% by mass).

The polymerization initiation method in the above polymerization reaction may be any method as long as the energy required for the polymerization initiation can be supplied 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. Further, when a polymerization initiator is used in combination, the energy required for the initiation of polymerization can be significantly reduced, and the reaction control becomes easy, which is preferable. The molecular weight of the polymer obtained by polymerizing the above-mentioned 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-mentioned monomer component is polymerized by the solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inactive in the polymerization reaction, and the polymerization mechanism, the type and amount of the monomer used, and the like. It may be appropriately set according to the polymerization conditions such as the polymerization temperature and the polymerization concentration. When a solvent is used as a diluent or the like in the later preparation of the curable resin composition, it is efficient and preferable to use the solvent containing the solvent for 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 available because of the solubility of the obtained polymer, the surface smoothness when forming a coating film, the small impact on the human body and the environment, and the ease of industrial availability. It is more preferable to use glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and 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 that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying heat energy, and depends on the polymerization conditions such as the polymerization temperature, the solvent, and the type of the monomer to be polymerized. Then, it may be selected as appropriate. Further, a reducing agent such as a transition metal salt or amines may be used in combination 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, and t-butylperoxy-. 2-Ethylhexanoate, t-amylperoxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-) Dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), hydrogen peroxide, persulfate and the like, peroxides and azo compounds usually used as polymerization initiators can be mentioned. These may be used alone or in combination of two or more.

The amount of the above-mentioned polymerization initiator used is not particularly limited, and may be appropriately set according to the type and amount of the monomer used, the polymerization conditions such as the polymerization temperature and the 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, and 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, a chain transfer agent may also be used if necessary. Preferably, the polymerization initiator and the chain transfer agent are used in combination. When a chain transfer agent is used during polymerization, it tends to be possible to suppress an increase in molecular weight distribution and gelation.

Examples of the chain transfer agent include the same solvents as those described in JP-A-2015-157909, and one or more of them can be used. Among them, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, and mercapto are preferable in terms of availability, cross-linking prevention ability, small degree of decrease in polymerization rate, and the like. Examples include compounds having a mercapto group such as isocyanurates, more preferably alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, and even more preferably n-dodecyl mercaptan, mercaptopropionic acid.

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

Regarding the above-mentioned polymerization conditions, 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, and the like. For example, 50 to 130 ° C. is preferable, and 60 to 60 to 130 ° C. 120 ° C. is more preferable.

The acid value of the acid group-containing polymer is preferably 50 to 200 mgKOH / g, more preferably 60 to 180 mgKOH / g, and even more preferably 70 to 170 mgKOH / g.
The acid value is a value obtained by measuring by a neutralization titration method using a KOH solution.

The weight average molecular weight of the acid group-containing polymer is not particularly limited, but is preferably 2000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000.
The weight average molecular weight of the acid group-containing polymer is a value obtained by measuring by the method described in Examples by gel permeation chromatography (GPC).

In the curable resin composition of the present invention, the content of the acid group-containing polymer is not particularly limited and may be appropriately set according to the application, blending of other components, etc., but for example, the curable resin composition. 10 to 70% by mass is preferable, 20 to 60% by mass is more preferable, and 20 to 50% by mass is further preferable with respect to 100% by mass of the total solid content.
The "total solid content" means the total amount of the components forming the cured product (excluding the solvent that volatilizes during the formation of the cured product).

<1-2. Polymerizable compounds>
The curable resin composition of the present invention preferably further contains a polymerizable compound. By further containing the polymerizable compound, the curable resin composition has excellent curability, and after curing, it not only suppresses water unevenness and heat-resistant coloring, but also has high surface hardness and high adhesion to the substrate. A cured product having excellent solvent resistance and heat resistance can be obtained.
The polymerizable compound is also referred to as a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.) and electron beams. ) Is a low molecular weight compound. For example, a monofunctional compound having one polymerizable unsaturated group in the molecule and a polyfunctional compound having two or more polymerizable unsaturated groups can be mentioned.

Examples of the monofunctional polymerizable monomer include N-substituted maleimide-based monomers; (meth) acrylic acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids; Unsaturated monocarboxylic acids with chain extensions between saturated and carboxyl groups; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated Enzymes; etc. Further, a monomer having an active methylene group or an active methine group can also be used.

Examples of the polyfunctional polymerizable monomer 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, and bisphenol F alkylene oxide di (meth) acrylate;

Trimethylol propanetri (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, trypentaerythritol hepta (meth) acrylate, trypentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylol propanetetra (meth) acrylate, ethylene oxide Addition of pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylol propanetri (meth) acrylate, propylene oxide-added ditrimethylol propanetetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate with propylene Oxide, Trimethylol Propantri (Meta) Acrylate with ε-Caprolactone, Ditrimethylol Propanetetra (Meta) Acrylate with ε-Caprolactone, Pentaerythritol Tetra with ε-Caprolactone Trifunctional or higher functional (meth) acrylate compounds such as (meth) acrylate and dipentaerythritol hexa (meth) acrylate with ε-caprolactone;

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, trimetyl propanetrivinyl ether, ditri Methylolpropan tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylol propanetrivinyl ether, ethylene oxide-added ditrimethylol propanetetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide Polyfunctional vinyl ethers such as added dipentaerythritol hexavinyl ether;

2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4 (meth) acrylate -Vinyloxybutyl, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, ( Vinyl ether group-containing (meth) acrylics such as p-vinyloxymethylphenylmethyl (meth) acrylic acid, 2- (vinyloxyethoxy) ethyl (meth) acrylic acid, and 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylic acid. Acrylic acids;

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 Falkylene oxide diallyl ether, trimethyl propantriallyl ether, Ditrimethylol propanetetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylol propanetriallyl ether, ethylene oxide-added ditrimethylol propanetetraallyl 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 reacting the polyfunctional isocyanate of (meth) 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; etc. These polymerizable compounds may be used alone or in combination of two or more.

Among the above-mentioned 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 functional number of the polyfunctional polymerizable compound is preferably 3 or more, and more preferably 4 or more. The functional number is preferably 10 or less, more preferably 8 or less.
The molecular weight of the polymerizable compound is not particularly limited, but is preferably 2000 or less from the viewpoint of handling.

Among the above-mentioned polyfunctional polymerizable compounds, a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate compound, and a (meth) acryloyl group-containing isocia are used from the viewpoints of reactivity, economy, availability, and the like. A compound having a (meth) acryloyl group, such as a nurate compound, is preferable, and a polyfunctional (meth) acrylate compound is preferable. By containing the compound having a (meth) acryloyl group, the curable resin composition becomes more excellent in photosensitivity and curability, and a cured product having even higher hardness and high transparency can be obtained. As the polyfunctional polymerizable compound, it is more preferable to use a trifunctional or higher functional (meth) acrylate compound.

In the curable resin composition of the present invention, the content of the polymerizable compound is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately set, but the curable resin composition is suitable. The curable resin composition of the present invention has a solid content of preferably 10 to 70% by mass, more preferably 10 to 60% by mass, still more preferably 10 to 100% by mass, from the viewpoint of being able to have a high viscosity. ~ 55% by mass.

<1-3. Photopolymerization initiator>
The curable resin composition of the present invention preferably further contains a photopolymerization initiator. By including the photopolymerization initiator, the curability of the curable resin composition can be improved, and the performance of the obtained cured product can be improved.
The photopolymerization initiator in the present invention preferably includes a radically polymerizable photopolymerization initiator. The radically polymerizable photoinitiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam.

The photopolymerization initiator is not particularly limited, and for example, an alkylphenone-based compound, a benzophenone-based compound, a benzoin-based compound, a thioxanthone-based compound, a halomethylated triazine-based compound, a halomethylated oxadiazole-based compound, and a biimidazole-based compound. , Oxym ester compounds, titanosen compounds, benzoic acid ester compounds, aclysin compounds and other known photopolymerization initiators can be used.
Among them, as the photopolymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl-2- Alkylphenone-based compounds such as dimethylamino-1- (4-morpholinophenyl) -butanone-1 ("IRGACURE369", manufactured by BASF) are preferable.
The above-mentioned photopolymerization initiator may be used alone 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 2 to 30% by mass, more preferably 5 to 20% by mass, and further preferably 5 to 18% by mass with respect to the mass%.

Further, if necessary, one or more photosensitizers, photoradical polymerization accelerators and the like may be used in combination. Sensitivity and curability are further improved by using a photosensitizer and / or a photoradical polymerization accelerator in combination with the photopolymerization initiator. The photosensitizer and the photoradical polymerization accelerator are not particularly limited, and may be appropriately selected from known ones generally used in the curable resin composition.

Examples of the photosensitizer and photoradical polymerization accelerator that may be used in combination with the above photopolymerization initiator include dye-based compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin dyes, and pyromethene dyes; 4-dimethylamino. Dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole can be mentioned.

When the above photosensitizer and photo-radical polymerization accelerator are used, the content thereof is 100% by mass of the total solid content of the curable resin composition from the viewpoint of the balance between curability, influence of decomposition products and economic efficiency. It is preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, and further preferably 0.05 to 10% by mass.

<1-4. Other ingredients>
The curable resin composition of the present invention may contain other components, if necessary, in addition to the (meth) acrylate-based polymer, the polymerizable compound, and the photopolymerization initiator described above. Other components include, for example, a solvent; a coloring material (also referred to as a colorant); a dispersant; an antioxidant; a heat resistance improver; a leveling agent; a developing aid; an inorganic fine particle such as silica fine particles; a silane type, an aluminum type, Coupling agents such as titanium; thermosetting resins such as fillers, epoxy resins, phenol resins, polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; ultraviolet absorbers; matting agents; Antifoaming agents; antistatic agents; slip agents; surface modifiers; rocking agents; rocking aids; quinonediazide compounds; polyhydric phenol compounds; cationically polymerizable compounds; acid generators; and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type. For example, when the curable resin composition is used for a color filter application, the curable resin composition preferably contains a coloring material.

(solvent)
As the solvent, a solvent usually used in a curable resin composition can be used, and it may be appropriately selected depending on the purpose and application, and is not particularly limited, but is described in, for example, JP-A-2015-157909. A similar one can be used. These may be used individually by 1 type, or 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 should be contained in an amount of 10 to 90% by mass in the total amount of 100% by mass of the curable resin composition. Is preferable. More preferably, it is 20 to 80% by mass.

(Color material)
Examples of the coloring material include pigments and dyes. As the coloring material, either a pigment or a dye may be used, or a pigment and a 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 the desired color characteristics by appropriately combining color materials such as blue and purple and green and yellow. When 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 appropriately selected according to the required characteristics. In the curable resin composition of the present invention, pigments are preferable in that the solvent resistance and heat-resistant coloring property of the cured product can be further improved. As the pigment, the same pigment as that described in JP-A-2015-157909 can be used.

As the dye, for example, the organic dyes described in JP-A-2010-9033, JP-A-2010-21198, JP-A-2009-51896, and JP-A-2008-50599 can be used. can. Of these, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable.
These coloring materials 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 according to the purpose and application, but is preferably 0% with respect to 100% by mass of the total solid content of the curable resin composition. 1 to 20% by mass, more preferably 1 to 15% by mass, still more preferably 2 to 12% by mass.

(Dispersant)
When the curable resin composition of the present invention contains the above-mentioned coloring material, it is preferable that the curable resin composition further contains a dispersant.
The dispersant has a site of interaction with a coloring material and a site of interaction with a dispersion medium (for example, a solvent or a binder resin), and has a function of stabilizing dispersion of the color material in the dispersion medium. Yes, it is generally classified into a resin type dispersant (for example, a polymer dispersant), a surfactant (for example, a low molecular weight dispersant), and a dye derivative. These may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of the resin type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , Long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide and its salt formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, (meth) acrylic acid-styrene. Copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, polyvinylpyrrolidones, polyesters, modified polyacrylates, ethylene oxide / polypropylene oxide adducts, etc. Can be mentioned. Examples of commercially available products of the resin type dispersant include those similar to those described in JP-A-2015-157909.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, sodium alkylnaphthalinsulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, and 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. Sexual surfactants; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkyl imidazoline; and the like.

The dye derivative is a compound having a structure in which a functional group is introduced into the dye, and examples of the functional group include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, and an amide group. , Phtalimide group and the like. The maternal pigment structure includes, for example, azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrone, perylene, and diketopyrrolopyrrole. The system etc. can be mentioned.

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

(Antioxidant)
The curable resin composition of the present invention can further improve the heat-resistant coloring property of the cured product by containing an 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, a hindered phenol-based antioxidant and a phosphite ester-based antioxidant may be used. Agents are preferred. These may be used individually by 1 type, or 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 acid group-containing 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-mentioned contained components using various mixers and dispersers can be mentioned. Be done. The mixing / dispersing step is not particularly limited, and a known method may be used. In addition, other steps that are usually performed may be further included. When the curable resin composition contains a coloring material, it is preferably prepared through a process of dispersing the coloring material.

In the dispersion treatment step of the coloring material, for example, first, a coloring material (preferably an organic pigment), a dispersant, and a solvent are weighed in predetermined amounts, and the coloring material is finely dispersed using a disperser to disperse the coloring material into a liquid coloring material. A method of obtaining a dispersion liquid (also referred to as a mill base) can be mentioned. Examples of the disperser include a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, a blender and the like. The dispersion treatment step preferably includes a method of kneading and dispersing with a roll mill, a kneader, a blender or the like, and then performing a fine dispersion treatment with a media mill such as a bead mill filled with beads of 0.01 to 1 mm. .. A composition containing a (meth) acrylate-based 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. (Preferably a transparent liquid) is added and mixed to obtain a uniform dispersion solution, and a curable resin composition can be obtained.
The obtained curable resin composition is preferably filtered with a filter or the like to remove fine dust.

2. Cured product As described above, the curable resin composition of the present invention provides a cured product in which water unevenness is suppressed and excellent heat-resistant coloring is achieved. In addition, the cured product is also excellent in basic performance such as curability, developability, adhesion to a substrate, heat resistance and transparency. A cured product obtained by curing such a curable resin composition is also one of the present inventions.

When the cured product is a cured film, the film thickness thereof is preferably 0.1 to 20 μm. When the film thickness is within the above range, it can be excellent in image forming property and surface smoothness in addition to suppressing water unevenness and heat-resistant coloring property. The film thickness is more preferably 1 to 15 μm, still more preferably 1 to 10 μm.

The method for obtaining a cured product using the curable resin composition of the present invention is not particularly limited, and a known method may be used. For example, the curable resin composition of the present invention is applied onto a substrate. Examples thereof include a method of obtaining a cured product by drying, heating, or irradiating an energy ray such as ultraviolet rays to cure the coated product.

The cured product is used for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used for liquid crystal display devices, solid-state image sensors, etc., and for electric / electronic devices, etc. It is preferably used for. Above all, it is preferable to use it as a color filter. A color filter containing the cured product as described above is also one of the present inventions. The color filter will be described below.

3. 3. Color filter The color filter of the present invention has a form in which the cured product is contained on a substrate.
In the above color filter, the cured product formed by the curable resin composition of the present invention is particularly suitable as a black matrix or a segment requiring coloring such as each pixel of red, green, blue, yellow, etc. However, it is also suitable as a segment such as a photo spacer, a protective layer, and an orientation control rib that does not necessarily require coloring.

Examples of the substrate used for the color filter include glass substrates such as white plate glass, blue plate glass, alkali-reinforced glass, and silica-coated blue plate glass; ring-opening polymers of polyester, polycarbonate, polyolefin, polysulfone, and cyclic olefin, and hydrogen thereof. 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 color material layer on the surface (for example, a color filter for LCD); and the like. Of these, a glass substrate or a sheet, film or substrate made of a heat-resistant resin is preferable from the viewpoint of heat resistance. Further, the substrate is preferably a transparent substrate.
Further, the base material may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent or the like, if necessary.

4. Manufacturing Method of Color Filter To obtain the color filter, for example, a step of arranging the curable resin composition on a substrate for each pixel color (that is, for each pixel of one color) (also referred to as an arranging step). A step of irradiating the curable resin composition arranged on the substrate with light (also referred to as a light irradiation step), a step of developing with a developing solution (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step). It is preferable to adopt a method including (referred to as) and a manufacturing method in which the same method is repeated for each color. The order of forming the pixels of each color is not particularly limited.

4-1. Placement process (preferably coating process)
It is preferable that the arrangement step is performed by coating. Examples of the method of applying the curable resin composition on the substrate include spin coating, slit coating, roll coating, cast coating and the like, and any of these methods can be preferably used.
In the arrangement step, it is also preferable to apply the curable resin composition onto the substrate and then dry the coating film. The coating film can be dried by 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 the curing component, the film thickness, the performance of the dryer, etc., but are usually carried out at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds. Suitable.

4-2. Light irradiation step As the light source of the active light used in the above light irradiation step, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, etc. A lamp light source such as a fluorescent lamp, a laser light source such as an argon ion laser, a YAG laser, an excima laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser is used. Further, examples of the exposure machine method include a proximity method, a mirror projection method, and a stepper method, and the proximity method is preferably used.
In the step of irradiating the active energy ray, the active energy ray may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed portion is cured, and the cured portion is insolubilized or hardly soluble in the developing solution.

4-3. Development step The development step is a step of forming a pattern by removing an unexposed portion by developing with a developing solution after the above-mentioned light irradiation step. This makes it possible to obtain a patterned cured film. The development process can usually be performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, and ultrasonic development.

The developing solution used in the above developing 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. .. When an alkaline aqueous solution is used as the developing solution, it is preferable to wash with water after the development.

Examples of the organic solvent suitable as the developing solution 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. Species, isopropanol, benzyl alcohol and the like.

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

Examples of the alkaline agent include inorganic substances such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, sodium secondary phosphate, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. Alkali agents; trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and other amines can be mentioned, and these can be used alone. Two or more types may be used in combination.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitanoic acid alkyl esters and monoglyceride alkyl esters; alkylbenzene sulfonates and alkylnaphthalene sulfonic acids. Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids, etc. The above may be used in combination.

4-4. Heating step The heating step is a step (also referred to as a post-curing step) in which the exposed portion (cured portion) is further cured by firing after the above-mentioned developing step. ^{For example, a step of post-exposure with a light amount of 0.5 to 5} J / cm 2 using a light source such as a high-pressure mercury lamp, a step of post-heating at a temperature of 60 to 260 ° C. for 10 seconds to 120 minutes, and the like are performed. Can be mentioned. By performing such a post-curing step, the hardness and adhesion of the patterned cured film can be further strengthened. Further, as described above, the carboxyl group generated by the desorption of the tertiary carbon-containing moiety of the structural unit of the (meth) acrylate-based polymer contained in the curable resin composition by this heating step is described above ( The cured product of the curable resin composition of the present invention obtained by reacting with the hydroxyl group of the hydroxyl group-containing monomer unit contained in the meta) acrylate-based polymer to form a crosslinked structure is further excellent in solvent resistance and curability. It becomes a thing.

The film thickness of the cured film obtained by the heating step (that is, the cured film obtained by heat-curing the curable resin composition) is preferably 0.1 to 20 μm. By using the curable resin composition of the present invention, it is possible to provide a cured film having a sufficiently reduced film thickness. Further, since the film thickness is reduced, the concentration of the coloring material per unit volume of the cured film is increased, and the brightness of the color filter can be improved. The film thickness is more preferably 1 to 15 μm, still more preferably 1 to 10 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%. It is more preferably 80% or less, still more preferably 70% or less.

In the heating step, the heating temperature is preferably 150 ° C. or higher. As a result, the portion derived from a part of the tertiary carbon-containing (meth) acrylate-based monomer is more effectively decomposed, and the above-mentioned curability and solvent resistance can be further improved. The heating temperature is more preferably 160 ° C. or higher, further preferably 170 ° C. or higher, and particularly preferably 180 ° C. or higher. The temperature is preferably 260 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 240 ° C. or lower.

The heating time in the heating step is not particularly limited, but is preferably 5 to 60 minutes, for example. Further, the heating method is not particularly limited, but for example, it can be performed by using a heating device such as a hot plate, a convection oven, or a high frequency heater.

5. Display device The present invention is also a display device configured by using the above color filter.
A display device member and a display device having a cured product obtained by curing the curable resin composition are also included in a preferred embodiment of the present invention. The cured product (cured film) formed by the curable resin composition is stable, has excellent adhesion to a substrate or 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 image sensor, a touch panel type display device, or the like is suitable.
When the cured product (cured film) is used as a display device member, the member may be a film-like single-layer or multilayer member composed of the cured film, or the single-layer or multilayer member. It may be a member in which another layer is further combined with the member of the above, or it may be a member including the cured film in the composition.

As described above, the curable resin composition of the present invention is less likely to cause water unevenness and can provide a cured product having excellent heat-resistant coloring properties. Further, the cured product obtained by using the curable resin composition of the present invention is also excellent in adhesion to a substrate, transparency and the like. Such a curable resin composition of the present invention is useful for various applications such as color filters. Further, a color filter and a display device having a cured product formed of such a curable resin composition are very useful in the fields of optics and electric / electronic fields.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".
In the following synthetic examples and the like, various physical properties were measured as follows.

(1) Weight average molecular weight (Mw)
Weight average molecular weight of polymer by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh), column: TSKgel SuperHZM-M (manufactured by Tosoh) using polystyrene as a standard substance and tetrahydrofuran as an eluent. Was measured.

(2) About 1 g of the solid content polymer solution was weighed in an aluminum cup, about 3 g of acetone was added to dissolve the solution, and then the solution was naturally dried at room temperature. Then, using a vacuum dryer (manufactured by EYELA, trade name: VOS-301SD), the product was dried under vacuum at 140 ° C. for 1.5 hours, then allowed to cool in a desiccator, and the mass was measured. From the amount of mass reduction, the mass (solid content concentration, mass%) of the solid content (polymer) of the polymer solution was calculated.

(3) 3 g of an acid value polymer solution is precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1N KOH aqueous solution as a titrant. The acid value of the polymer solution was measured by a trade name: COM-555), and the acid value per 1 g of the solid content (mgKOH / g) was determined from the acid value of the solution and the solid content of the solution.

(Synthesis Example 1)
Preparation of Polymer Solution 1 508 parts of propylene glycol monomethyl ether acetate (PGMEA) was charged into a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dropping tank introduction port, substituted with nitrogen, and then stirred. It was heated to 90 ° C.
On the other hand, as the dropping tank (A), 35 parts of N-cyclohexylmaleimide (CHMI), 123 parts of t-butyl methacrylate (t-BMA), dicyclopentanyl methacrylate ("Funkryl FA-513M" manufactured by Hitachi Chemical Co., Ltd. " 68 parts (hereinafter also referred to as DCPMA), 70 parts of 2-hydroxyethyl methacrylate (HEMA), 54 parts of acrylic acid (AA) and t-amylperoxy-2-ethylhexanoate (“Luperox 575” manufactured by Alchema Yoshitomi). , 8 parts (hereinafter also referred to as L575) and 35 parts of PGMEA were prepared by stirring, and 2 parts of n-dodecyl mercaptan (n-DM) and 106 parts of PGMEA were prepared by stirring and mixing in the dropping tank (B). After the temperature of the reaction vessel reached 90 ° C., the dropping was started from the dropping tank over 3 hours while maintaining the same temperature, and polymerization was carried out. Then, after maintaining 90 ° C. for 30 minutes, 1.4 parts of L575 was added. After further holding at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and aging was carried out for 90 minutes to obtain a polymer solution 1.
When the obtained polymer solution 1 was analyzed, the weight average molecular weight was 21,500, the acid value was 122 mgKOH / g, and the resin solid content was 34.8% by mass.

(Synthesis Example 2)
Preparation of polymer solution 2 Synthesis example except that the amount of monomer charged was 25 parts for CHMI, t-BMA 73 parts, DCPMA 79 parts, HEMA 35 parts, AA 39 parts, and PGMEA 25 parts, and the amount of n-DM charged was 2 parts. The same operation as in 1 was carried out to obtain a polymer solution 2.
When the obtained polymer solution 2 was analyzed, the weight average molecular weight was 20700, the acid value was 122 mgKOH / g, and the resin solid content was 34.5% by mass.

(Synthesis Example 3)
Synthesis example except that the amount of the prepared monomer of the polymer solution 3 was 25 parts of CHMI, 66 parts of t-BMA, 80 parts of DCPMA, 30 parts of HEMA, 49 parts of AA, and 25 parts of PGMEA, and the amount of n-DM charged was 2 parts. The same operation as in 1 was carried out to obtain a polymer solution 3.
When the obtained polymer solution 3 was analyzed, the weight average molecular weight was 21,600, the acid value was 155 mgKOH / g, and the resin solid content was 34.8% by mass.

(Synthesis Example 4)
Preparation of polymer solution 4 The amount of monomer charged is 25 parts for CHMI, 88 parts for t-BMA, 49 parts for dicyclopentanyl acrylate (“Funkril FA-513AS” manufactured by Hitachi Chemical Co., Ltd., hereinafter also referred to as DCPA), HEMA50. The same operation as in Synthesis Example 1 was carried out except that the parts, AA 39 parts and PGMEA 25 parts were used and the amount of n-DM charged was 2 parts to obtain a polymer solution 4. When the obtained polymer solution 4 was analyzed, the weight average molecular weight was 22000, the acid value was 122 mgKOH / g, and the resin solid content was 34.4% by mass.

(Synthesis Example 5)
The amount of the prepared monomer of the polymer solution 5 was 35 parts of CHMI, 88 parts of t-BMA, 112 parts of DCPMA, 35 parts of HEMA, 81 parts of methacrylic acid (MAA), and 35 parts of PGMEA, and the amount of n-DM charged was 2 parts. The same operation as in Synthesis Example 1 was carried out except that 250 parts of PGMEA was added after aging to obtain a polymer solution 5. When the obtained polymer solution 5 was analyzed, the weight average molecular weight was 19,900, the acid value was 145 mgKOH / g, and the resin solid content was 29.1% by mass.

(Synthesis Example 6)
Preparation of polymer solution 6 The amount of monomer charged was 25 parts of CHMI, t-BMA 88 parts, DCPMA 30 parts, HEMA 50 parts, MAA 58 parts, PGMEA 25 parts, the amount of n-DM charged was 2 parts, and PGMEA 119 parts after aging. The same operation as in Synthesis Example 1 was carried out except that the above was added to obtain a polymer solution 6. When the obtained polymer solution 6 was analyzed, the weight average molecular weight was 19,500, the acid value was 152 mgKOH / g, and the resin solid content was 30.1% by mass.

(Synthesis Example 7)
The amount of the prepared monomer of the polymer solution 7 was 25 parts of N-benzylmaleimide (BzMI), 88 parts of t-BMA, 49 parts of methyl methacrylate (MMA), 50 parts of HEMA, 39 parts of AA, and 25 parts of PGMEA. The same operation as in Synthesis Example 1 was carried out except that the amount of DM charged was 2 parts, to obtain a polymer solution 7. When the obtained polymer solution 7 was analyzed, the weight average molecular weight was 19,500, the acid value was 120 mgKOH / g, and the resin solid content was 34.5% by mass.

(Synthesis Example 8)
Preparation of polymer solution 8 Synthesis example except that the amount of monomer charged was 25 parts for CHMI, 88 parts for t-BMA, 49 parts for MMA, 50 parts for HEMA, 39 parts for AA, and 25 parts for PGMEA, and the amount of n-DM charged was 2 parts. The same operation as in 1 was carried out to obtain a polymer solution 8. When the obtained polymer solution 8 was analyzed, the weight average molecular weight was 21100, the acid value was 121 mgKOH / g, and the resin solid content was 35.0% by mass.

(Synthesis Example 9)
Preparation of polymer solution 9 The amount of monomer charged was 25 parts of BzMI, 88 parts of t-BMA, 30 parts of DCPMA, 50 parts of HEMA, 58 parts of MAA, 25 parts of PGMEA, the amount of n-DM charged was 2 parts, and 119 parts of PGMEA after aging. The same operation as in Synthesis Example 1 was carried out except that the above was added to obtain a polymer solution 9. When the obtained polymer solution 9 was analyzed, the weight average molecular weight was 20100, the acid value was 151 mgKOH / g, and the resin solid content was 30.1% by mass.

Using the obtained polymer solutions 1 to 9, a curable resin composition was prepared by the following method, and the heat resistance coloring property and water unevenness were evaluated.

(Example 1)
In terms of solid content, 60 parts of polymer solution 1, 30 parts of dipentaerythritol hexaacrylate as radically polymerizable compound, 9.8 parts of Irgacure 907 (manufactured by BASF) as radically polymerizable photopolymerization initiator, antioxidant 0.2 part of Irganox 1010 (manufactured by BASF) was added as an agent, and a diluting solvent (PGMEA) was further added so as to have a solid content concentration of 20% by mass, and the mixture was stirred to obtain a curable resin composition (1-1). Obtained.

<Evaluation of heat-resistant coloring>
The curable resin composition (1-1) obtained above is dried on a non-alkali glass plate (5 cm × 5 cm, manufactured by Toshin Riko Co., Ltd.) using a spin coater, and the thickness of the coating film is 3 μm. Then, after drying on a hot plate at 100 ° C. for 3 minutes, ultraviolet rays were irradiated so ^{that the irradiation amount was 100 mJ / cm 2 using an ultra-high pressure mercury lamp.} After irradiation, the test piece was further dried on a hot plate at 230 ° C. for 30 minutes to prepare a test piece. The obtained test piece is heated on a hot plate at 250 ° C. for 3 hours, cooled to room temperature, and then the b ^* value of the coated surface is used using a spectrocolorimeter (“ZE-6000” manufactured by Nippon Denshoku Kogyo Co., Ltd.). Was measured. The results are shown in Table 2.

(Examples 2 to 6, Comparative Examples 1 to 3)
As shown in Table 2, the curable resin compositions (2-1) to (9-) were operated in the same manner as in Example 1 except that the polymer solutions 2 to 9 were used instead of the polymer solution 1. 1) was obtained, and the heat-resistant coloring property of the coating film was evaluated. The results are shown in Table 2.

(Example 7)
In terms of solid content, 45 parts of the polymer solution 1, 20 parts of the coloring material composition (b-1), 25 parts of dipentaerythritol hexaacrylate as a radically polymerizable compound, and Irgacure 907 as a radically polymerizable photopolymerization initiator. Add 9.8 parts (manufactured by BASF), 0.2 parts of Irganox 1010 (manufactured by BASF) as an antioxidant, and further add a diluting solvent (PGMEA) to a solid content concentration of 20% by mass, and stir. As a result, a curable resin composition (1-2) was obtained.
The coloring material composition (b-1) used here was prepared by the following method.
(Preparation of Color Material Composition (b-1))
Dispersion resin solution (resin monomer composition: BzMI / cyclohexyl methacrylate / methyl methacrylate / methacrylate = 30/30/30/10 (mass ratio), Mw: 10000, acid value: 65 mgKOH / g, in resin solution 8.3 parts by mass (solid content: 42%), 2.9 parts by mass of dispersant (manufactured by Big Chemie Japan, trade name "DISPERBYK-2001", non-volatile content 1.3 g), pigment (CI). Pigmen Blue 15: 6) 8.0 parts by mass was weighed into a 225 ml container and diluted with PGMEA so that the non-volatile content concentration (solid content concentration) was 20% by mass. To this, 64 g of zirconia beads having a diameter of 1.0 mm was added, and the mixture was shaken with a paint shaker for 3 hours to disperse the beads, and then the zirconia beads were removed by decantation to obtain a coloring material composition (b-1).

<Evaluation of water unevenness>
The curable resin composition (1-2) obtained above is dried on a non-alkali glass plate (10 cm × 10 cm, manufactured by Geomatec Co., Ltd.) using a spin coater so that the thickness of the coating film becomes 3 μm. And dried on a hot plate at 100 ° C. for 3 minutes, then irradiated with ultraviolet rays using an ultra-high pressure mercury lamp so that the irradiation amount was 100 mJ / cm ^2. After the exposure, a 0.04 mass% potassium hydroxide aqueous solution was sprayed on the coating film with a spin developer for 60 seconds to perform shower development. Next, the exposed portion was washed with pure water for 10 seconds, and then the water on the glass plate surface was removed by air blowing.
Water unevenness (unevenness of shading) of the coating film was observed using an optical microscope (magnification 100 times) and evaluated according to the following criteria. Based on the following criteria, ○ to △ were set to levels that would not cause any problems in practical use. The results are shown in Table 3.
◯: No unevenness in shading is observed on the surface of the coating film.
Δ: Slight unevenness in shading is observed on the surface of the coating film.
X: Clear shading unevenness and peeling are observed on the surface of the coating film.

(Examples 8 to 12, Comparative Examples 4 to 6)
As shown in Table 3, the curable resin compositions (2-2) to (9-) were operated in the same manner as in Example 7 except that the polymer solutions 2 to 9 were used instead of the polymer solution 1. 2) was obtained, and the water unevenness of the coating film was evaluated. The results are shown in Table 3.

In Table 1, each component is as follows. The value of the monomer composition shown in Table 1 is the mass% of each unit of the polymer with respect to 100% by mass of the total unit of the polymer.
BzMI: N-benzylmaleimide CHMI: N-cyclohexylmaleimide TBMA: t-butyl methacrylate MMA: methyl methacrylate DCPMA: dicyclopentanyl methacrylate DCPA: dicyclopentanyl acrylate HEMA: 2-hydroxyethyl methacrylate MAA: Methacrylic acid AA: Acrylic acid

According to Tables 2 and 3, as the monomer unit, 10% by mass of N-cyclohexylmaleimide, 12 to 32% by mass of dicyclopentanyl methacrylate or dicyclopentanyl acrylate, and 15 by mass of methacrylic acid or acrylate. The curable resin composition (Examples 1 to 12) containing a polymer containing 5 to 23% by mass contains N-cyclohexylmaleimide as a monomer unit and dicyclobenzenyl methacrylate or dicyclopenta acrylate. Compared with the curable resin composition (Comparative Examples 1 to 6) containing a polymer having both or only one of Nyl, the obtained cured product sufficiently suppresses water unevenness and is heat resistant. It was found that the colorability was also very excellent.
As described above, the curable resin composition of the present invention has very little discoloration in heat treatment at a high temperature of 250 ° C., has extremely excellent heat-resistant coloring property, and can sufficiently suppress water unevenness. It is clear that there is.

Claims (10)

A curable resin composition containing an acid group-containing polymer.
The acid group-containing polymer is a fat having an N-alkylmaleimide monomer unit and / or an N-cycloalkylmaleimide monomer unit of 2 to 30% by mass and an alicyclic hydrocarbon group having 3 to 12 carbon atoms. A cyclic hydrocarbon group-containing (meth) acrylate-based monomer unit of 10 to 40% by mass, a carboxylic acid-based monomer unit of 5 to 25% by mass, and an oxygen atom adjacent to the (meth) acryloyl group is a tertiary carbon atom. Curing for a color filter, which comprises 20 to 60% by mass of a tertiary carbon-containing (meth) acrylate-based monomer unit having a structure bonded to and 10 to 40% by mass of a hydroxyalkyl (meth) acrylate unit. Sex resin composition. The curing for a color filter according to claim 1, wherein the alicyclic hydrocarbon group contained in the alicyclic hydrocarbon group-containing (meth) acrylate-based monomer unit is a polycyclic hydrocarbon group. Sex resin composition. The curable resin composition for a color filter according to claim 1 or 2 , wherein the acid group-containing polymer has a content of an aromatic hydrocarbon group-containing monomer unit of 5% by mass or less. The acid group-containing polymer has a ^{content of a vinyl-based monomer unit containing a −COOR 6} (R ⁶ is an alkyl group having 1 to 3 carbon atoms) group of 5% by mass or less. The curable resin composition for a color filter according to any one of claims 1 to 3. The curable resin composition for a color filter according to any one of claims 1 to 4 , wherein the N-cycloalkylmaleimide monomer unit is an N-cyclohexylmaleimide monomer unit. The hydroxyalkyl (meth) acrylate unit is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Claimed to be at least one selected from the group consisting of 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2,3-hydroxypropyl (meth) acrylate. Item 2. The curable resin composition for a color filter according to any one of Items 1 to 5. The curable resin composition for a color filter according to any one of claims 1 to 6 , further comprising a polymerizable compound and a photopolymerization initiator. A cured product obtained by curing the curable resin composition for a color filter according to any one of claims 1 to 7. A color filter comprising the cured product according to claim 8 on a substrate. A display device comprising the color filter according to claim 9.