JP7160554B2 - RESIN COMPOSITION FOR OPTICAL MATERIAL AND USES THEREOF - Google Patents

Description

The present invention relates to a resin composition for optical materials. More specifically, the present invention relates to a resin composition for optical materials that can give a cured product with a low dielectric constant, and uses thereof.

Curable resin compositions that can be cured by heat or active energy rays are used in various applications such as color filters, inks, printed wiring boards, insulating films, and spacers used in liquid crystal display devices, solid-state imaging devices, touch panel display devices, and the like. Various studies have been made on its application to constituent members of display devices, etc., and curable resin compositions having excellent properties required for each application have been developed. For example, a capacitive touch panel display device generally has a structure in which a transparent conductive film such as ITO is formed on a substrate, and a protective film or an insulating film is formed to protect the transparent conductive film. Constituent members such as protective films and insulating films are generally required to have high adhesion to transparent conductive films and high surface hardness. Further, for example, color filters are required to have various physical properties such as curability of a curable resin composition, solvent resistance after curing, adhesion to substrates, heat resistance and transparency.

Various proposals have been made for such curable resin compositions.
For example, in Patent Document 1, polybasic acid anhydride is added to at least part of the hydroxyl groups of a polymer obtained by radically polymerizing an N-substituted maleimide component and a hydroxyl group-containing monomer as essential components. A photosensitive resin composition containing a modified polymer having a carboxyl group obtained by reacting a substance is described.
Further, for example, Patent Document 2 discloses an optical material containing a (meth)acrylic polymer having a repeating unit having an ethylenically unsaturated group bonded to a side chain via an amide bond, a polymerizable compound, and a polymerization initiator. A resin composition for use is described.

JP 2005-141011 A Japanese Patent Application Laid-Open No. 2009-169300

In recent years, optical members, electric and electronic devices, etc. have been becoming smaller, thinner, and energy-saving. In particular, in recent years, as the definition of display devices has increased, there has been a demand for improved electrical characteristics such as a lower dielectric constant. For example, in a liquid crystal display device, a color filter is placed on the liquid crystal via an ITO (transparent conductive) film, and if the dielectric constant of the color filter is high, there is a problem that the voltage holding ratio of the liquid crystal cannot be kept high. . However, it cannot be said that cured products obtained from conventional curable resin compositions have a sufficiently low dielectric constant, and there is room for improvement.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition for optical materials which is excellent in electrical properties and capable of giving a cured product having a low dielectric constant. Another object of the present invention is to provide a laminate having a cured product of such a resin composition for optical materials.

In order to solve the above-mentioned problems, the present inventors conducted various studies on resin compositions for optical materials, and found that a resin composition containing an alkali-soluble resin made of a polymer having a specific structural unit can be sufficiently obtained. It has been found that a cured product having a low dielectric constant and excellent electrical properties can be obtained. Moreover, the present inventors have found that a resin composition containing such an alkali-soluble resin is suitable for use as an optical material, and have completed the present invention.

That is, the present invention provides a resin composition containing an alkali-soluble resin and a polymerization initiator, wherein the alkali-soluble resin is a polymer having a structural unit represented by the following general formula (1). It is a resin composition for optical materials characterized by the following.

(wherein R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms; X ¹ and X ³ are the same or different and are a single bond or a represents a divalent organic group of 1 to 20. X ² represents a divalent hydrocarbon group having 1 or more carbon atoms.)

The present invention also provides a resin composition containing an alkali-soluble resin and a coloring material, wherein the alkali-soluble resin is a polymer having a structural unit represented by the general formula (1). It is a resin composition for optical materials.

The resin composition for optical materials is preferably a negative photosensitive resin composition.

The structural unit represented by the general formula (1) is preferably formed by reaction between an acid group and an oxazoline group-containing compound.

The oxazoline group-containing compound is preferably 2-isopropenyl-2-oxazoline.

The double bond equivalent weight of the alkali-soluble resin is preferably 200 to 2000 g/equivalent.

The resin composition for optical materials preferably further contains a polymerizable compound.

The present invention also provides a laminate comprising a substrate and a cured product of the above resin composition for optical materials.

The resin composition for optical materials of the present invention can give a cured product having a low dielectric constant and excellent electrical properties. Such a resin composition for optical materials of the present invention can be used for color filters, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, etc., which are used in liquid crystal display devices, solid-state imaging devices, and the like. It can be suitably used for various applications such as optical members, electrical and electronic equipment, and the like.

The present invention will be described in detail below.
A combination of two or more of the individual preferred embodiments of the invention described below is also a preferred embodiment of the invention.
Moreover, in this specification, "(meth)acrylate" means "acrylate and/or methacrylate."

1. Resin Composition for Optical Materials The resin composition for optical materials of the present invention is a resin composition containing an alkali-soluble resin and a polymerization initiator or a coloring material, wherein the alkali-soluble resin is represented by the following general formula (1): It is characterized by being a polymer having a structural unit represented by
The resin composition for optical materials of the present invention can give a cured product having a low dielectric constant and excellent electrical properties by containing an alkali-soluble resin having a specific structural unit.

(wherein R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms; X ¹ and X ³ are the same or different and are a single bond or a represents a divalent organic group of 1 to 20. X ² represents a divalent hydrocarbon group having 1 or more carbon atoms.)

A first aspect of the present invention is a resin composition comprising an alkali-soluble resin and a polymerization initiator, wherein the alkali-soluble resin is a polymer having a structural unit represented by the general formula (1). It is a resin composition for materials. In this specification, the resin composition for optical materials of the first invention is also referred to as "resin composition for optical materials (A)".

A second aspect of the present invention is a resin composition containing an alkali-soluble resin and a coloring material, wherein the alkali-soluble resin is an optical material which is a polymer having a structural unit represented by the general formula (1). It is a resin composition for In this specification, the resin composition for optical materials of the second aspect of the present invention is also referred to as "resin composition for optical materials (B)".
In the present specification, the resin composition for optical materials (A) and the resin composition for optical materials (B) are collectively referred to as "the resin composition for optical materials of the present invention".

In the present invention, the term "optical material" refers to a material to which photolithography is applied, which is used as a constituent member of an apparatus in the field of optics, electrical machinery and electronics.・Color filters, black matrixes, photo spacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulation used in quantum dot/micro LED display devices, solid-state imaging devices, touch panel display devices, etc. It is used as a constituent material for membranes, etc.

<Alkali-soluble resin>
The resin composition for optical materials of the present invention contains an alkali-soluble resin.
The alkali-soluble resin used in the present invention is a polymer having a structural unit represented by the general formula (1). By having the structural unit represented by the above general formula (1), a cured product with a low dielectric constant can be obtained. Possibly.

As a conventional method for preparing an alkali-soluble resin having a polymerizable double bond in the side chain, after preparing a base polymer having an acid group, the acid group is reacted with a compound having an epoxy group and a polymerizable double bond. A method of introducing a polymerizable double bond through an addition reaction by cleaving the epoxy group is exemplified. However, the addition reaction with an epoxy group forms a hydroxyl group, resulting in a polymer with a relatively high dielectric constant. In addition, since there is a functional group with strong coordinating property such as a hydroxyl group, when a resin composition containing a colorant such as a pigment is formed, the colorant may aggregate and the dispersibility of the colorant may be lowered. rice field. In the present invention, since a highly polar group such as a hydroxyl group is not generated when a double bond is introduced into an alkali-soluble resin, a sufficiently low dielectric constant can be achieved. In addition, when the alkali-soluble resin is used together with a coloring material, it is possible to suppress the deterioration of the dispersibility of the coloring material.

In addition, as another method for introducing side chain double bonds, after preparing a base polymer having acid groups or hydroxyl groups, the acid groups or hydroxyl groups are reacted with a compound having an isocyanate group and a polymerizable double bond for an addition reaction. A method of introducing a polymerizable double bond can be mentioned. However, this technique generates urethane bonds, which are highly polar groups, and as a result increases the dielectric constant, which is not preferable. In particular, the site generated by the reaction between the acid group and the isocyanate group is unstable and the reverse reaction is likely to proceed, generating foreign matter and increasing the dielectric constant, so there is room for improvement.

In addition, as another method for introducing side chain double bonds, after preparing a base polymer having an isocyanate group, the isocyanate group is subjected to an addition reaction in which a compound having an acid group or a hydroxyl group and a polymerizable double bond is reacted. A method of introducing a polymerizable double bond can be mentioned. However, this method is also not preferable because it increases the dielectric constant from the viewpoint of generation of urethane bonds, which are highly polar groups, and generation of foreign matter. In addition, since acid groups and isocyanate groups react with each other, it is difficult to introduce acid groups into the base polymer, which is not preferable from the viewpoint of processability. In addition, even if an acid group is introduced by deprotection, the dielectric constant is further increased by a foreign substance or a catalyst due to the leaving group, so there is room for improvement.

The structural unit represented by the general formula (1) (hereinafter also referred to as “structural unit (A)”) will be described.
In general formula (1) above, R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms.
The organic group having 1 to 20 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples of hydrocarbon groups having 1 to 20 carbon atoms include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. is mentioned.

Some hydrogen atoms constituting the hydrocarbon group may be substituted. Examples of substituents include a hydroxy group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkyl group; an alkoxy group;
The alkyl group for the substituent is preferably an alkyl group having 1 to 15 carbon atoms, more preferably a methyl group, an ethyl group or an n-propyl group, and still more preferably a methyl group or an ethyl group.
The alkoxy group of the substituent is preferably a substituent in which an alkyl group having 1 to 15 carbon atoms is bonded to an oxygen atom, more preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like, still more preferably , methoxy group, and ethoxy group.

The aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, pentyl group, isopentyl group and neopentyl group. , hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2 -dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, octyl group, methylheptyl group, dimethylhexyl group, 2- ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, nonyl group, methyloctyl group, 3,7-dimethyloctyl group, dimethylheptyl group, 3-ethylheptyl group, 4-ethylheptyl group, trimethylhexyl group, 3,3-diethylpentyl group, decyl group, undecyl group, dodecyl group, hydroxyethyl group and chain-like substituted or unsubstituted alkyl groups such as.

Examples of the alicyclic hydrocarbon group include substituted or unsubstituted cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and cyclododecyl group.

Examples of the aromatic hydrocarbon group include substituted or unsubstituted aromatic hydrocarbon groups such as phenyl group, naphthyl group, biphenylyl group, methoxyphenyl group, trichlorophenyl group, ethylphenyl group, tolyl group, xylyl group, and benzyl group. A hydrogen group is mentioned.

Among them, from the viewpoint of heat resistance, the hydrocarbon group having 1 to 20 carbon atoms is preferably a hydrocarbon group having 1 to 15 carbon atoms, and an aliphatic hydrocarbon group having 1 to 10 carbon atoms. is more preferred, methyl group, ethyl group and n-propyl group are more preferred, and methyl group and ethyl group are particularly preferred.
More preferably, R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or a methyl group.

In the general formula (1), X ¹ and X ³ are the same or different and represent a single bond or a divalent organic group having 1 to 20 carbon atoms.

Examples of the divalent organic group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms and an arylene group, which may be partially substituted. The substituent is not particularly limited, and examples thereof include halogen atoms such as fluorine, chlorine and iodine atoms. In addition, when the divalent organic group has a ring structure, examples of substituents include alkyl groups such as methyl and ethyl groups in addition to halogen atoms.

The alkylene group may have a linear structure, or may have a branched structure or an alicyclic structure. Specifically, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, t-butylene group, pentylene group, neopentylene group, hexamethylene group, heptylene group, octylene group, 2-ethylhethylene xylene group, nonylene group, decylene group, undecylene group, dodecylene group and the like.

Specific examples of the arylene group include a phenylene group, a tolylene group, a naphthylene group, a diethylnaphthylene group and the like.

Further, examples of the divalent organic group include the following groups in addition to the above-described alkylene group and arylene group:
—O—, —SO ₂ —, —CO—, —COO—, —C ₆ H ₅ O—, —(C _n H _2n )O— (n represents an integer of 1 to 10), —NH— .

Among them, the divalent organic group is preferably an alkylene group having 1 to 10 carbon atoms, —COO—, —C ₆ H ₅ O—, —SO ₂ —, or —NH—, and preferably has 1 carbon atom. -5 alkylene groups, -COO-, -C ₆ H ₅ O-, and -NH- are more preferred, and -COO- and -C ₆ H ₅ O- are even more preferred.

Among them, X ¹ is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, -COO- or -C ₆ H ₅ O-, and a single bond, -COO- or -C ₆ H ₅ O- is more preferable.

X ³ is preferably a single bond or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a single bond or An alkylene group having 1 to 6 carbon atoms is more preferred, and a single bond is particularly preferred.

In the general formula (1), X2 represents a ^divalent hydrocarbon group having 1 or more carbon atoms.
The number of carbon atoms in the divalent hydrocarbon group in X ² is preferably 1-20, more preferably 1-15, even more preferably 1-10.
Examples of the divalent hydrocarbon group include the above-described alkylene group or arylene group, more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably an alkylene group having 1 to 2 carbon atoms.

As the structural unit (A) represented by the general formula (1), the following are preferred.

(wherein R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or a methyl group; X ¹ represents a single bond or a divalent organic group having 1 to 20 carbon atoms; X ² represents a divalent hydrocarbon group having 1 or more carbon atoms ^, and X3 represents a single bond.)
The divalent organic group having 1 to 20 carbon atoms and the divalent hydrocarbon group having 1 or more carbon atoms are as described above.

As the structural unit (A) represented by the general formula (1), the following are more preferable.

(In the formula, ^R2 represents a hydrogen atom or a methyl group.)

The said alkali-soluble resin may have 1 type as said structural unit (A), and may have 2 or more types.

The method for forming the structural unit (A) is not particularly limited as long as the structure described above can be obtained, but it is preferably formed by reaction between an acid group and an oxazoline group-containing compound.
Examples of the acid group include a carboxyl group, a phenolic hydroxyl group, a carboxylic anhydride group, a phosphoric acid group, and a sulfonic acid group. Among them, a carboxyl group is preferable from the viewpoint of a low dielectric constant.

As the oxazoline group-containing compound, a compound having an oxazoline group and a polymerizable double bond (carbon-carbon double bond) is preferable.
Examples of the polymerizable double bond include those having a carbon-carbon double bond such as a (meth)acryloyl group, vinyl group, allyl group, and methallyl group, among which the vinyl group is preferred.

Examples of the oxazoline group-containing compound include 2-isopropenyl-2-oxazoline, 2-propenyl-2-oxazoline and the like, and 2-isopropenyl-2-oxazoline is preferred from the viewpoint of synthetic stability. be done.

When 2-isopropenyl-2-oxazoline is reacted with an acid group, the oxazoline group is cleaved and added by forming an amide ester bond with the acid group. In such an addition reaction, hydroxyl groups, which are the main cause of increasing the dielectric constant, are not generated. Therefore, a cured product with a low dielectric constant can be obtained without increasing the dielectric constant of the alkali-soluble resin. Further, since hydroxyl groups with strong coordinating properties are not generated, aggregation of the coloring material can be suppressed when the alkali-soluble resin and the coloring material are used together.

The content of the structural unit (A) in the alkali-soluble resin is preferably 1 to 80% by mass with respect to 100% by mass of all structural units in the alkali-soluble resin.
The content of the structural unit (A) is more preferably 5% by mass or more, still more preferably 10% by mass or more, and 70% by mass relative to 100% by mass of all structural units in the alkali-soluble resin. % or less, and even more preferably 60 mass % or less.

(Structural Unit (B) Derived from Acid Group-Containing Monomer)
The alkali-soluble resin in the present invention preferably further has a structural unit derived from an acid group-containing monomer (hereinafter also referred to as "structural unit (B)").
By having an acid group, the alkali-soluble resin exhibits alkali-solubility and can exhibit developability and the like.

The structural unit derived from the acid group-containing monomer can be introduced by polymerizing a monomer component containing the acid group-containing monomer.
Examples of the acid group-containing monomer include monomers having an acid group and a polymerizable double bond.
Examples of the acid group include functional groups capable of neutralizing reaction with alkaline water, such as carboxyl group, phenolic hydroxyl group, carboxylic acid anhydride group, phosphoric acid group, and sulfonic acid group. Among them, a carboxyl group or a carboxylic anhydride group is preferred, a carboxyl group is more preferred, and a (meth)acrylic acid group is even more preferred.

Examples of the polymerizable double bond include a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group, and the like. The alkali-soluble resin of the present invention may have one or more of these. Among them, a (meth)acryloyl group is preferable in terms of reactivity.

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

The alkali-soluble resin may have only one type or two or more types as the structural unit (B).

The content of the structural unit (B) in the alkali-soluble resin is preferably 1 to 30% by mass, more preferably 3% by mass or more, and still more preferably 100% by mass of all structural units in the alkali-soluble resin. is 5% by mass or more, more preferably 25% by mass or less, and still more preferably 20% by mass or less.

(Structural unit (C) having a ring structure in the main chain)
The alkali-soluble resin is preferably a polymer having a ring structure in its main chain. That is, the alkali-soluble resin preferably has a structural unit (hereinafter also referred to as "structural unit (C)") having a ring structure in its main chain. When the alkali-soluble resin is a polymer having a ring structure in its main chain, it is possible to give a cured product excellent in heat resistance and dispersion stability.
The ring structure includes an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, a lactone ring and the like.

In order for the alkali-soluble resin to have a cyclic structure in the main chain, it is preferable to polymerize a monomer component containing a monomer capable of forming a cyclic structure in the main chain.
Examples of monomers capable of forming a ring structure on the main chain include N-substituted maleimide-based monomers, dialkyl-2,2′-(oxydimethylene) diacrylate-based monomers, α-(unsaturated alkoxy Alkyl) acrylate monomers are preferred. Among them, the N-substituted maleimide monomer is more preferable because it can give a cured product having excellent heat resistance.

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

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

Examples of the dialkyl-2,2′-(oxydimethylene) diacrylate monomer include 2,2′-[oxybis(methylene)]bisacrylic acid, dialkyl-2,2′-[oxybis(methylene) )]bis-2-propenoate, dialkyl-2,2′-[oxybis(methylene)]bis-2-propenoate, and the like, in which at least one of the ester sites contains a tertiary carbon. Among these, it is preferable to use, for example, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate from the viewpoint of transparency, dispersibility, industrial availability, and the like.

Examples of the α-(unsaturated alkoxyalkyl) acrylate monomers include α-allyloxymethyl acrylic acid; methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyloxymethyl n-propyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, n-amyl α-allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic s-hexyl acid, n-heptyl α-allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, α -2-ethylhexyl allyloxymethyl acrylate, capryl α-allyloxymethyl acrylate, nonyl α-allyloxymethyl acrylate, decyl α-allyloxymethyl acrylate, undecyl α-allyloxymethyl acrylate, α-allyloxy lauryl methyl acrylate, α-allyloxymethyl tridecyl acrylate, α-allyloxymethyl myristyl acrylate, α-allyloxymethyl pentadecyl acrylate, α-allyloxymethyl acrylate cetyl, α-allyloxymethyl heptadecyl acrylate, Alkyl-(α such as stearyl α-allyloxymethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, ceryl α-allyloxymethyl acrylate, melisyl α-allyloxymethyl acrylate, etc. -allyloxymethyl) acrylate-based monomers and the like. Among them, alkyl-(α-allyloxymethyl)acrylate monomers are preferred.

As the alkyl-(α-allyloxymethyl)acrylate-based monomer, for example, methyl-(α-allyloxymethyl)acrylate is preferable from the viewpoint of transparency, dispersibility, industrial availability, and the like. mentioned.
The α-(unsaturated alkoxyalkyl) acrylate can be produced, for example, by the production method disclosed in WO 2010/114077 pamphlet.

The said alkali-soluble resin may have 1 type as said structural unit (C), and may have 2 or more types.

The content of the structural unit (C) in the alkali-soluble resin is preferably 1 to 60% by mass, more preferably 2% by mass or more, and still more preferably 100% by mass of all structural units in the alkali-soluble resin. is 3% by mass or more, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

(Structural unit (D) having a ring structure in the side chain)
The alkali-soluble resin of the present invention also preferably has a ring structure in its side chain. That is, the alkali-soluble resin preferably further has a structural unit having a ring structure in its side chain (hereinafter also referred to as "structural unit (D)").

Examples of the ring structure include an aromatic ring structure such as benzene, or an alicyclic structure such as a cyclohexane skeleton, an adamantane skeleton, and a norbornene skeleton.

In order for the alkali-soluble resin to have a ring structure in the side chain, it is preferable to polymerize a monomer component containing a monomer having an aromatic hydrocarbon group or an alicyclic hydrocarbon group and a polymerizable double bond.

Examples of the aromatic hydrocarbon group include aryl groups such as benzyl, tolyl, naphthyl and biphenyl.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms. Specific examples of the alicyclic hydrocarbon group include monocyclic hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, cycloheptyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; Examples include polycyclic hydrocarbon groups such as pentanyl, dicyclopentenyl, tricyclodecanyl, adamantyl, and isobornyl.

Examples of the polymerizable double bond include a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group, and the like. Among them, a (meth)acryloyl group is preferred in terms of reactivity.

Specific examples of monomers that provide the structural unit (D) include cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (3 , 4-epoxycyclohexyl)methyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylol- Alicyclic hydrocarbon group-containing monomers such as tricyclodecane di(meth)acrylate, pentacyclopentadecanedimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, norbornanedimethanol di(meth)acrylate; Aromatic hydrocarbon group-containing monomers such as benzyl (meth)acrylate, styrene, vinyltoluene, α-methylstyrene, methoxystyrene, and 1 mol ethoxylated phenylphenol acrylate can be mentioned. Among these, alicyclic hydrocarbon group-containing monomers are preferred, and cyclohexyl (meth)acrylate is more preferred, in terms of low dielectric constant.

The said alkali-soluble resin may have only 1 type as said structural unit (D), and may have 2 or more types.

The content of the structural unit (D) in the alkali-soluble resin is preferably 1 to 90% by mass, more preferably 5% by mass or more, and further It is preferably 10% by mass or more, more preferably 85% by mass or less, and still more preferably 80% by mass or less.

(Other structural units (E))
The alkali-soluble resin may further have other structural units as necessary.
Examples of the other structural units include structural units derived from (meth)acrylic acid ester-based monomers, hydroxyl group-containing monomers, other copolymerizable monomers, and the like.

Examples of the (meth)acrylic ester-based monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, (meth) ) n-butyl acrylate, t-butyl (meth)acrylate, s-butyl (meth)acrylate, n-amyl (meth)acrylate, t-amyl (meth)acrylate, s- (meth)acrylate Amyl, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) ) Lauryl acrylate, stearyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-(meth)acrylate dimethylaminoethyl, 1,4-dioxaspiro[4,5]dec-2-ylmethacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3- Dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (Meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane and the like.

Examples of the hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. , 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and 2,3-hydroxypropyl (meth)acrylate.

Examples of other copolymerizable monomers include one or more of the following compounds.
(Meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam and the like; Macromonomers having a (meth)acryloyl group at one end of the combined molecular chain; Conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Class; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2- vinyl ethers such as hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine and N-vinylacetamide; (meth) unsaturated isocyanates such as isocyanatoethyl acrylate and allyl isocyanate; and the like.

The said alkali-soluble resin may have only 1 type as said structural unit (E), and may have 2 or more types.

The content of the structural unit (E) is preferably 0 to 90% by mass, more preferably 0.3 to 85% by mass, and still more preferably 100% by mass of the total structural units of the alkali-soluble resin. 0.5 to 80% by mass.

The acid value of the alkali-soluble resin is preferably 20-200 mgKOH/g. Alkali solubility is expressed more suitably as an acid value is the above-mentioned range. Also, the dispersion stability is improved. The acid group is more preferably 25 to 180 mgKOH/g, even more preferably 30 to 150 mgKOH/g.
In the present specification, the acid value can be determined by the method described in Examples below.

The double bond equivalent weight of the alkali-soluble resin is preferably 200 to 2000 g/equivalent. When the double bond equivalent is within the above range, the dielectric constant becomes lower. In addition, it is excellent in developability, sensitivity to light, and the like. The double bond equivalent is preferably 250 g/equivalent or more, more preferably 300 g/equivalent or more, still more preferably 330 g/equivalent or more from the viewpoint of suppressing pattern line thickening, and is also preferably from the viewpoint of maintaining photosensitivity. is 1900 g/equivalent or less, more preferably 1800 g/equivalent or less, and still more preferably 1700 g/equivalent or less.

As used herein, the double bond equivalent is a measure of the amount of double bonds contained in a molecule, and means the molecular weight per double bond of a polymer. For compounds with the same molecular weight, the larger the double bond equivalent, the smaller the amount of double bond introduced.
The double bond equivalent can be calculated from the charged amount of raw materials, and can be obtained by dividing the mass (g) of the polymer solid content by the double bond amount (mol) of the polymer. It can also be measured by titration, elemental analysis, various analyzes such as NMR and IR, and differential scanning calorimetry.

The weight average molecular weight of the alkali-soluble resin is preferably 3,000 to 50,000. Developability is excellent as the weight average molecular weight is within the above range. The weight average molecular weight is more preferably 4,000 to 40,000, even more preferably 5,000 to 35,000.
In the present specification, the weight average molecular weight can be determined by gel permeation chromatography (GPC) by the method described in Examples below.

(Method for producing alkali-soluble resin)
As a method for producing the alkali-soluble resin, for example, a compound (X) for forming the structural unit (A) is added to a base polymer obtained by polymerizing a monomer component containing at least an acid group-containing monomer. A method of reacting can be mentioned.
The acid group of the base polymer reacts with the compound (X) for forming the structural unit (A) to form a polymer having the structural unit (A).
The monomer component that gives the base polymer contains at least an acid group-containing monomer.
As the acid group-containing monomer, the same monomer as the acid group-containing monomer that gives the structural unit (B) described above is preferably exemplified.

The compound (X) for forming the structural unit (A) is a compound having a polymerizable double bond (carbon-carbon double bond) and a group capable of reacting with an acid group. Although it is not particularly limited as long as it can form the unit (A), the above-mentioned oxazoline group-containing compounds are preferred, and 2-isopropenyl-2-oxazoline is more preferred.

Examples of monomer components that provide the base polymer include the acid group-containing monomer, the monomer (c) that provides the structural unit (C), and the monomer (d) that provides the structural unit (D). are contained, the content ratio of these monomers is 3 to 80% by mass of the acid group-containing monomer and the monomer (c ) 1 to 50% by mass, and 3 to 90% by mass of the monomer (d), 5 to 75% by mass of the acid group-containing monomer, and 5 to 40% by mass of the monomer (c) %, and 5 to 85% by mass of the monomer (d).

Further, as the monomer components that provide the base polymer, the acid group-containing monomer, the monomer (c), the monomer (d), and the monomer (e) that provides the structural unit (E) ), the content ratio of these monomers is 3 to 80% by mass of the acid group-containing monomer and the monomer ( c) 1 to 50% by mass, preferably 3 to 90% by mass of the monomer (d), and 0.5 to 90% by mass of the monomer (e), and the acid group-containing monomer 5 ~75% by mass, 5 to 40% by mass of the monomer (c), 5 to 85% by mass of the monomer (d), and 1 to 85% by mass of the monomer (e) preferable.

In the above method, the method of polymerizing the monomer component is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used, and may be appropriately selected according to the purpose and application. . Among them, the solution polymerization is industrially advantageous, and the structure adjustment such as the molecular weight is easy, so it is suitable. In addition, as the polymerization mechanism of the monomer component, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used. is also advantageous, so it is preferable.
Preferred forms of the polymerization reaction are as described in [0062] to [0072] of JP-A-2016-29151.

The polymerization initiation method in the above polymerization reaction may be performed by supplying energy necessary for polymerization initiation from an active energy source such as heat, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays), and electron beams to the monomer components. Combined use of an initiator is preferable because the energy required for polymerization initiation can be greatly reduced and the reaction can be easily controlled. Further, the molecular weight of the polymer obtained by polymerizing the above monomer components can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.

The compound (X) for forming the structural unit (A) is added to some of the acid groups contained in the base polymer. The reaction method is not particularly limited, and a known method may be employed as appropriate. For example, the reaction temperature is preferably 90 to 150°C. In addition, as a basic catalyst, known catalysts such as amine compounds such as triethylamine and dimethylbenzylamine; ammonium salts such as tetraethylammonium chloride; phosphonium salts such as tetraphenylphosphonium bromide; and amide compounds such as dimethylformamide; is also preferred. As the acidic catalyst, it is also preferable to use known catalysts such as phosphoric acid and p-toluenesulfonic acid.

The amount of the compound (X) used to form the structural unit (A) is preferably set appropriately so that the acid value and double bond equivalent are within the desired ranges. It is preferably 1 to 70 parts by mass with respect to 100 parts by mass of the total amount of the monomer components. As a result, not only can the dielectric constant be sufficiently lowered, but also the curability is further enhanced and the strength of the cured product is further enhanced. More preferably 3 to 60 parts by mass, still more preferably 5 to 50 parts by mass.

Further, the amount of the compound (X) used to form the structural unit (A) is 25 to 90 mol per 100 mol % of the acid group-containing monomer in the monomer component that provides the base polymer. %, more preferably 20 to 85 mol %, even more preferably 15 to 80 mol %.

The content of the alkali-soluble resin is not particularly limited, and may be appropriately set according to the application and the blending of other components. It is preferably up to 60% by mass, more preferably 15 to 55% by mass, even more preferably 20 to 50% by mass.
The term "total solid content" means the total amount of components forming the cured product (excluding the solvent and the like that volatilize during the formation of the cured product).

<Polymerization initiator>
The resin composition for optical materials (A) of the present invention further contains a polymerization initiator.
By including a polymerization initiator, it is possible to improve the curability of the resin composition and improve the performance of the obtained cured product.

The polymerization initiator preferably includes a radically polymerizable photopolymerization initiator. A radically polymerizable photopolymerization initiator is one that generates polymerization initiation radicals upon irradiation with active energy rays such as electromagnetic waves and electron beams.

The photopolymerization initiator is not particularly limited, and examples thereof include alkylphenone-based compounds, benzophenone-based compounds, benzoin-based compounds, thioxanthone-based compounds, halomethylated triazine-based compounds, halomethylated oxadiazole-based compounds, and biimidazole-based compounds. , oxime ester-based compounds, oxime ether-based compounds, titanocene-based compounds, benzoic acid ester-based compounds, acridine-based compounds, and other known photopolymerization initiators can be used.

Among them, as the photopolymerization initiator, it is preferable to use an alkylphenone compound, an oxime ester compound, an oxime ether compound, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopro Alkylphenones such as pan-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (“IRGACURE369”, manufactured by BASF) compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime)] (“OXE01”, manufactured by BASF), ethanone, 1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) ("OXE02", manufactured by BASF), 1,2-octanedione, 1-[4- (Phenylthio)-,2-,(O-benzoyloxime)], ethanone (“OXE03”, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl ]-,1-(O-Acetyloxime) (“OXE04”, manufactured by BASF)) and other oxime esters are more preferably used.
The photopolymerization initiators may be used singly or in combination of two or more.

The content of the polymerization initiator is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately designed. On the other hand, it is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and still more preferably 1 to 20% by mass.

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

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

When the photosensitizer and the photoradical polymerization accelerator are used, the content thereof should be 100 mass of the total solid content of the resin composition for optical materials, from the viewpoint of the balance between curability, influence of decomposed products, and economic efficiency. %, preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, and still more preferably 0.05 to 10% by mass.

<Color material>
The resin composition for optical materials (B) of the present invention further contains a colorant.
Examples of the coloring material include pigments and dyes. As the coloring material, either a pigment or a dye may be used, or a combination of the pigment and the dye may be used. For example, when forming red, blue, and green pixels of a color filter, it is preferable to use a known technique that achieves desired color characteristics by appropriately combining color materials such as blue and purple, green and yellow, and the like. Also, when forming a black matrix or a black column spacer, it is preferable to use a black coloring material.

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

Examples of the dye include organic dyes described in JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599. can. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable.

These colorants may be used singly or in combination of two or more.

The content of the coloring material is not particularly limited, and can be appropriately set according to the purpose and application. 80 mass %, more preferably 5 to 70 mass %, still more preferably 10 to 60 mass %.

<Polymerizable compound>
The resin compositions (A) and (B) for optical materials of the present invention preferably further contain a polymerizable compound.
By further including a polymerizable compound, it is possible to provide a cured product excellent in various physical properties such as curability of the resin composition, adhesion to substrates, mechanical strength and heat resistance.

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

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

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

trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide Pentaerythritol tetra(meth)acrylate with ethylene oxide, dipentaerythritol hexa(meth)acrylate with ethylene oxide, trimethylolpropane tri(meth)acrylate with propylene oxide, ditrimethylolpropane tetra(meth)acrylate with propylene oxide, pentaerythritol tetra(meth)acrylate with propylene oxide (Meth)acrylates, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate (Meth) acrylate, ε-caprolactone-added dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinic acid-modified, pentaerythritol triacrylate succinic acid-modified, dipentaerythritol pentaacrylate phthalic acid-modified, pentaerythritol tri Trifunctional or higher polyfunctional (meth)acrylate compounds such as modified acrylate phthalic acid;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditri Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide polyfunctional vinyl ethers such as adduct dipentaerythritol hexavinyl ether;

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

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

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

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

As the polyfunctional polymerizable compound, among others, polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, (meth)acryloyl group-containing isocyanates, from the viewpoint of reactivity, economy, availability, etc. A compound having a (meth)acryloyl group such as a nurate compound is preferable, and a polyfunctional (meth)acrylate compound is more preferable. By containing a compound having a (meth)acryloyl group, the resin composition for an optical material becomes more excellent in photosensitivity and curability, and a cured product with higher hardness and higher transparency can be obtained. As the polyfunctional polymerizable compound, it is more preferable to use a trifunctional or higher polyfunctional (meth)acrylate compound.
The polymerizable compounds may be used singly or in combination of two or more.

In the resin composition for optical materials of the present invention, the content of the polymerizable compound is not particularly limited, and can be appropriately set according to the purpose and application. From the standpoint of better properties and the like, it is preferably 3 to 90% by mass, more preferably 5 to 80% by mass, and still more preferably 10% by mass, relative to 100% by mass of the total solid content of the resin composition for optical materials. ~70% by mass.

<Other ingredients>
The resin composition for optical materials of the present invention may further contain other components as necessary. Examples of other components include solvents; dispersants; antioxidants; heat-resistant improvers; leveling agents; development aids; Fillers, epoxy resins, phenolic resins, thermosetting resins such as polyvinylphenol; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; UV absorbers; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinonediazide compounds; polyhydric phenol compounds; These may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, these can be appropriately selected from known ones and used, and the amount of use thereof is also preferably designed appropriately.

Further, the resin composition for optical materials (A) may further contain the coloring material described above, and the resin composition for optical materials (B) may further include the polymerization initiator and the photosensitizer described above. or a photoradical polymerization accelerator.

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

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

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

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

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

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

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

(Preparation of resin composition for optical material)
The method for preparing the above-mentioned resin composition for optical materials is not particularly limited, and a known method may be used. For example, a method of mixing and dispersing each of the above-described components using various mixers or dispersers may be used. mentioned. The mixing/dispersing step is not particularly limited, and may be performed by a known method. In addition, other steps that are normally performed may be further included. When the resin composition for optical materials contains a colorant, it is preferably prepared through a colorant dispersion treatment step.

As the above-described colorant dispersion treatment step, for example, first, predetermined amounts of a colorant (preferably an organic pigment), a dispersant, and a solvent are weighed, and the colorant is finely dispersed using a disperser to obtain a liquid colorant. Methods of obtaining dispersions (also referred to as "millbases") are included. Examples of the dispersing machine include paint conditioners, bead mills, roll mills, ball mills, jet mills, homogenizers, kneaders and blenders. As the dispersion treatment step, preferably, after kneading and dispersing with a roll mill, a kneader, a blender, etc., fine dispersion treatment is performed with a media mill such as a bead mill filled with beads of 0.01 to 1 mm. . A composition (preferably a transparent liquid) containing the alkali-soluble resin and the like, which has been separately stirred and mixed, is added to the obtained mill base and mixed to form a uniform dispersion solution, whereby a resin composition for optical materials can be obtained. .
The obtained resin composition for optical materials is preferably filtered using a filter or the like to remove fine dust.

The resin composition for optical materials of the present invention can give a cured product having a low dielectric constant and excellent electrical properties. Moreover, the cured product obtained using the optical material resin composition of the present invention is excellent in adhesiveness, heat resistance, transparency, and the like. The resin composition for optical materials of the present invention can be suitably used as a negative photosensitive resin composition.
Such a resin composition for optical materials of the present invention is used for insulating films (protective films) of color filters, colored layers of color filters, black matrices, photospacers, and black column spacers used in liquid crystal display devices, solid-state imaging devices, and the like. It is suitably used for liquid crystal display panel manufacturing applications such as.

2. Laminate As described above, the resin composition for optical materials of the present invention has a low dielectric constant and gives a cured product having excellent electrical properties. In addition, the above cured product is excellent in various performances such as adhesion to substrates, heat resistance and transparency. Such a laminate having a cured product of the resin composition for optical materials on a substrate (base material) is also one aspect of the present invention.

When the cured product is a cured film, the film thickness is preferably 0.1 to 20 μm. A dielectric constant can be made sufficiently low as a film thickness is the above-mentioned range. In addition, various performances such as adhesion to substrates, heat resistance and transparency can be sufficiently exhibited. The film thickness is more preferably 0.2 to 15 μm, still more preferably 0.3 to 10 μm.

The method for obtaining the laminate is not particularly limited, and a known method may be used. For example, as described above, the resin composition for optical materials is applied onto a substrate, and the applied product is dried and heated. , or a method of obtaining a cured product by curing by irradiating active energy rays such as ultraviolet rays.
The substrate (substrate) is not particularly limited and may be appropriately selected according to the purpose and application. Examples thereof include substrates made of various materials such as a glass plate and a plastic plate.

The above-mentioned laminate is, for example, an insulating film (protective film) of a color filter used in a liquid crystal display device, a solid-state imaging device, etc., a colored layer of a color filter, a black matrix, a photospacer, a black column spacer, etc. for manufacturing a liquid crystal display panel. It is preferably used for various applications such as.

Next, as an example, a method for forming a colored layer of a color filter using the resin composition for optical materials of the present invention will be described.

A color filter is a main component that constitutes a liquid crystal display device, a solid-state imaging device, etc. Generally, a substrate, pixels of at least three primary colors (red (R), green (G), blue (B)) and In addition to the resin black matrix (BM) for partitioning, it is composed of a protective film and the like provided to cover and protect the pixels and the resin black matrix and to flatten the irregularities thereof.

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

In order to obtain the colored layer of the color filter, for example, for each pixel color (that is, for each pixel of one color), a step of disposing the above-described resin composition for optical materials on a substrate (also referred to as a disposing step); A step of irradiating the resin composition for optical materials disposed on the substrate with light (also referred to as a light irradiation step), a step of developing with a developer (also referred to as a developing step), and a step of heat treatment (heating (also referred to as a step) is preferably employed. A color filter can be manufactured by repeating the same technique for each color. Note that the order in which the pixels of each color are formed is not particularly limited.
Each step of the arrangement step, the light irradiation step, the development step, and the heating step is, for example, the same as each step in the method for manufacturing a color filter described in [0125] to [0137] of JP-A-2016-29151. method is preferred.
Moreover, when forming the colored layer of a color filter, it is preferable to use the resin composition (B) for optical materials containing a coloring material as the resin composition for optical materials to be used.

A display device equipped with a constituent member such as a color filter having a cured product formed using the resin composition for an optical material of the present invention has a low dielectric constant and excellent electrical properties, so that the liquid crystal voltage can be maintained. Excellent rate.
Moreover, the cured product (cured film) formed from the resin composition for optical materials is stable, has excellent adhesion to substrates, etc., has high hardness, exhibits high smoothness, and has high transmittance.

Examples of the display device include a liquid crystal display device, a solid-state imaging device, a touch panel display device, and the like.
Examples of constituent members of the display device include an insulating film, a colored layer of a color filter, a black matrix, a photospacer, a black column spacer, and the like.

When the cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multilayer member composed of the cured film, or the single-layer or multilayer It may be a member in which another layer is further combined with the member of (1), or a member including the cured film in its configuration.

As described above, the resin composition for optical materials of the present invention can give a cured product having a low dielectric constant and excellent electrical properties. In addition, the resin composition for optical materials of the present invention is excellent in curability and can give a cured product excellent in adhesiveness to substrates, transparency, heat resistance and the like. Such a resin composition for an optical material of the present invention is very useful for various applications in the optical field such as liquid crystal display panel production and electrical/electronic fields.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "mass part" and "%" means "mass %". Evaluation of the polymer and resin composition in each production example was performed as follows.

(1) weight average molecular weight (Mw)
Measured by GPC (HLC-8220GPC, manufactured by Tosoh Corporation) using tetrahydrofuran (THF) as an eluent, using TSKgel SuperHZM-N (manufactured by Tosoh Corporation) as a column, and calculated in terms of standard polystyrene.

(2) Solid Content About 0.3 g of the copolymer solution prepared in Production Example was weighed into an aluminum cup, and about 1 g of acetone was added to dissolve it, followed by air drying at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC Co., Ltd.), it was dried at 140° C. for 3 hours, allowed to cool in a desiccator, and the mass was measured. The solid content (acrylic resin) (% by mass) of the polymer solution was calculated from the amount of mass reduction.

(3) Acid value 1.5 g of the copolymer solution prepared in Production Example was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated with a 0.1 N KOH aqueous solution. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of polymer was obtained from the solid content concentration (mgKOH/g).

(4) A resin composition was applied to an ITO deposited glass substrate having a dielectric constant of 5 cm square by a spin coating method so as to have a thickness of 2.0 μm after drying, followed by heat treatment (90° C. for 3 minutes). Exposure was performed with a UV aligner (manufactured by TOPCON, trade name “TME-150RNS”) equipped with a 0 kW ultra-high pressure mercury lamp at an exposure amount of 100 mJ/cm ² (365 nm illuminance conversion), followed by heat treatment (230° C. for 30 minutes). did Furthermore, gold (Au) was vapor-deposited on the surface to a thickness of 40 nm to form an electrode and obtain an evaluation sample. The capacitance of this sample was measured using an impedance analyzer 4294A (manufactured by Agilent Technologies) (25° C.), and the dielectric constant was determined by calculation.
Also for the resin alone, the dielectric constant was obtained in the same manner as described above except that the exposure was not performed.
(5) Dispersion stability The obtained resin composition was allowed to stand at 40°C for 7 days under light-shielding conditions, and then the viscosity was measured. was evaluated.
Viscosity increase rate (%) = [(viscosity after standing) - (initial viscosity)] / (initial viscosity) x 100
(Evaluation criteria)
○: Viscosity increase rate is less than 10% △: Viscosity increase rate is 10% or more and less than 15% ×: Viscosity increase rate is 15% or more

Production example 1
A separable flask equipped with a cooling tube was prepared as a reactor.
On the other hand, a monomer composition containing 10.0 g of benzylmaleimide (BzMI), 26.0 g of methacrylic acid (MAA), 63.0 g of cyclohexyl methacrylate (CHMA), and 1.0 g of methyl methacrylate (MMA) was placed in the monomer dropping tank. , t-butyl peroxy-2-ethylhexanoate (trade name "Perbutyl (registered trademark) O", manufactured by NOF Corporation, hereinafter referred to as PBO) 2.0 g, propylene glycol methyl ether acetate (PGMEA) 63.0 g , and 27.0 g of propylene glycol monomethyl ether (PGME) were added and mixed with stirring. Further, 1.0 g of dodecyl mercaptan (nDM) and 19.0 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and mixed with stirring.
A reactor was charged with 36.0 g of PGMEA and 24.0 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started.
Next, 0.2 g of 2,2′-methylenebis(4-methyl-6-t-butylphenol) (trade name “Antage W400”, manufactured by Kawaguchi Chemical Industry Co., Ltd., hereinafter referred to as W400) was added to the reaction tank as a polymerization inhibitor. 0.4 g of triethylamine (TEA) was charged as a catalyst. After the temperature of the reactor was stabilized at 110° C., 12.9 g of 2-isopropenyl-2-oxazoline (IPO) was added dropwise over 3 hours. After the dropwise addition was completed, the reaction was further carried out at 110° C. for 12 hours. After that, it was cooled to room temperature to obtain a copolymer solution (A-1). Various physical properties are shown in Table 1.

Production example 2
A separable flask equipped with a cooling tube was prepared as a reactor.
On the other hand, in the monomer dropping tank, dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate (MD) 10.0 g, MAA 26.0 g, CHMA 63.0 g, MMA 1.0 g, 2.0 g of PBO, 63.0 g of PGMEA, and 27.0 g of PGME were added and mixed with stirring. Further, 1.0 g of nDM and 19.0 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 36.0 g of PGMEA and 24.0 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started.
Then, 0.2 g of W400 as a polymerization inhibitor and 0.4 g of TEA as a catalyst were charged into the reactor. After the temperature of the reactor was stabilized at 110° C., 12.9 g of IPO was added dropwise over 3 hours. After the dropwise addition was completed, the reaction was further carried out at 110° C. for 12 hours. Then, it was cooled to room temperature to obtain a copolymer solution (A-2). Various physical properties are shown in Table 1.

Production example 3
A separable flask equipped with a cooling tube was prepared as a reactor.
On the other hand, a monomer composition containing 10.0 g of methyl 2-allyloxymethyl acrylate (AMA), 26.0 g of MAA, 63.0 g of CHMA, 1.0 g of MMA, 2.0 g of PBO, 63.0 g of PGMEA, and 27 PGME was placed in the monomer dropping tank. 0 g was added and mixed with stirring. Further, 1.0 g of nDM and 19.0 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 36.0 g of PGMEA and 24.0 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started.
Then, 0.2 g of W400 as a polymerization inhibitor and 0.4 g of TEA as a catalyst were charged into the reactor. After the temperature of the reactor was stabilized at 110° C., 12.9 g of IPO was added dropwise over 3 hours. After the dropwise addition was completed, the reaction was further carried out at 110° C. for 12 hours. After that, it was cooled to room temperature to obtain a copolymer solution (A-3). Various physical properties are shown in Table 1.

Production example 4
A separable flask equipped with a cooling tube was prepared as a reactor.
On the other hand, 26.0 g of MAA, 73.0 g of CHMA, 1.0 g of MMA, and 2.0 g of PBO were put into the monomer dropping tank and mixed with stirring. Further, 1.0 g of nDM and 19.0 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 99.0 g of PGMEA and 51.0 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started.
Then, 0.2 g of W400 as a polymerization inhibitor and 0.4 g of TEA as a catalyst were charged into the reactor. After the temperature of the reactor was stabilized at 110° C., 12.9 g of IPO was added dropwise over 3 hours. After the dropwise addition was completed, the reaction was further carried out at 110° C. for 12 hours. Then, it was cooled to room temperature to obtain a copolymer solution (A-4). Various physical properties are shown in Table 1.

Production example 5
A separable flask equipped with a cooling tube was prepared as a reactor.
On the other hand, 26.0 g of MAA, 73.0 g of CHMA, 1.0 g of MMA, and 2.0 g of PBO were put into the monomer dropping tank and mixed with stirring. Further, 1.0 g of nDM and 19.0 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 103.0 g of PGMEA and 52.0 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started.
Next, 16.5 g of glycidyl methacrylate (GMA), 0.2 g of W400 as a polymerization inhibitor, and 0.4 g of TEA as a catalyst were charged into the reactor, and reacted at 110° C. for 2 hours and at 115° C. for 6 hours. . After that, it was cooled to room temperature to obtain a copolymer solution (A-5). Various physical properties are shown in Table 1.

Production example 6
A separable flask equipped with a cooling tube was prepared as a reactor.
On the other hand, 17.0 g of MAA, 63.0 g of CHMA, 20.0 g of 2-hydroxyethyl methacrylate (HEMA), and 2.0 g of PBO were charged into the monomer dropping tank and mixed with stirring. Further, 1.0 g of nDM and 19.0 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 105.0 g of PGMEA and 53.0 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started.
Next, 0.2 g of W400 as a polymerization inhibitor and 0.05 g of dibutyltin dilaurate were charged into the reaction vessel, and after the temperature of the reaction vessel was stabilized at 50° C., 2-isocyanatoethyl methacrylate (IEMA) 18. 6 g was added dropwise over 30 minutes. After the dropwise addition was completed, the reaction was continued at 50° C. for an additional 3 hours. After that, it was cooled to room temperature to obtain a copolymer solution (A-6). Various physical properties are shown in Table 1.

Example 1
8.98 g of the copolymer solution (A-1) (that is, 3.5 g of an alkali-soluble resin), DISPERBYK-2001 as a dispersant (1.3 g of nonvolatile content, acid value: 19 mg KOH / g, amine value: 29 mg KOH / g ; Byk Chemie Japan, hereinafter referred to as byk2001) 2.77 g, a pigment as a coloring material (manufactured by Clariant, trade name "C.I. Pigment Violet 23"; hereinafter referred to as PV23) 1.6 g and a dye ( MP Biomedicals, trade name "C.I. Solvent Blue 35"; hereinafter referred to as SB35) was mixed. The obtained mixture was diluted with PGMEA so that the concentration of non-volatile matter was 20% by mass to obtain millbase B1.
Dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., hereinafter referred to as DPHA) 1.8 g, the copolymer solution (A-1) 8.98 g (that is, alkali-soluble resin 3.5 g), and a photopolymerization initiator 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (manufactured by BASF Japan, trade name "IRGACURE (registered trademark) 369"; hereinafter referred to as Irg369) 1.9 g and PGMEA to obtain a clear resist B1.
Next, millbase B1 and clear resist B1 were mixed and diluted with PGMEA so that the non-volatile content concentration was 20% by mass to obtain resin composition B1.
The obtained resin composition B1 was subjected to the above evaluation (4). Table 2 shows the results.

(Examples 2-4)
Resin compositions B2 to B4 were prepared in the same manner as in Example 1, except that the copolymer solutions shown in Table 2 were used instead of the copolymer solution (A-1) contained in the millbase and clear resist. Obtained. In any of the experimental examples, the copolymer solution contained in the millbase contained 3.5 g of the alkali-soluble resin added to the millbase, and the copolymer solution contained in the clear resist contained 3.5 g of the alkali-soluble resin added to the clear resist. 3.5 g of resin was used.
The obtained resin compositions B2 to B4 were subjected to the above evaluation (4). Table 2 shows the results.

(Comparative Examples 1 and 2)
Resin compositions B5 and B6 were prepared in the same manner as in Example 1, except that the copolymer solution shown in Table 2 was used instead of the copolymer solution (A-1) contained in the millbase and clear resist. Obtained. In any of the experimental examples, the copolymer solution contained in the millbase contained 3.5 g of the alkali-soluble resin added to the millbase, and the copolymer solution contained in the clear resist contained 3.5 g of the alkali-soluble resin added to the clear resist. 3.5 g of resin was used.
The obtained resin compositions B5 and B6 were subjected to the above evaluation (4). Table 2 shows the results.

(Example 5)
As an alkali-soluble resin, 8.98 g of the copolymer solution (A-1) (that is, 3.5 g of resin), and as a dispersant, DISPERBYK-2000 (nonvolatile content: 1.3 g, acid value: 0 mg KOH / g, amine value: 4 mg KOH/g; manufactured by BYK-Chemie Japan, hereinafter referred to as byk2000) 3.25 g, C.I. I. Pigment Green 36 (manufactured by Heubach, hereinafter referred to as PG36) 4.8 g and C.I. I. Pigment Yellow 150 (manufactured by Lanxess, hereinafter referred to as PY150) (3.2 g) was weighed into a 225 ml mayonnaise bottle and diluted with PGMEA so that the non-volatile content concentration was 20% by mass. 64 g of zirconia beads with a diameter of 1.0 mm were added to this, and the lid was closed. This was shaken with a paint shaker for 3 hours, and after 3 hours, the pigment dispersion composition and zirconia beads were separated, 64 g of 0.5 mm zirconia beads were added, and the mixture was further shaken with a paint shaker for 3 hours. Thereafter, the pigment dispersion composition and zirconia beads were separated, 64 g of 0.3 mm zirconia beads were added, and the mixture was shaken with a paint shaker for another 3 hours to obtain mill base G1.
3.3 g of DPHA, 8.98 g of the copolymer solution (A-1) (that is, 3.5 g of alkali-soluble resin), and 2-methyl-1-[4-(methylthio)phenyl] as a photopolymerization initiator. 0.4 g of -2-morpholino-propan-1-one (manufactured by BASF Japan, trade name "IRGACURE (registered trademark) 907"; hereinafter referred to as Irg907) was mixed with PGMEA to obtain clear resist G1. .
Next, the mill base G1 and the clear resist G1 were mixed and diluted with PGMEA so that the non-volatile content concentration was 20% by mass. After removing the zirconia beads, it was filtered through a filter with a pore size of 1.0 μm to obtain a resin composition G1.
The obtained resin composition G1 was subjected to the above evaluation (5). Table 3 shows the results.

(Examples 6-8)
Resin compositions G2 to G4 were prepared in the same manner as in Example 5, except that the copolymer solution shown in Table 3 was used instead of the copolymer solution (A-1) contained in the millbase and clear resist. Obtained. In any of the experimental examples, the copolymer solution contained in the millbase contained 3.5 g of the alkali-soluble resin added to the millbase, and the copolymer solution contained in the clear resist contained 3.5 g of the alkali-soluble resin added to the clear resist. 3.5 g of resin was used.
The obtained resin compositions G2 to G4 were subjected to the above evaluation (5). Table 3 shows the results.

(Comparative Examples 3-4)
Resin compositions G5 to G6 were prepared in the same manner as in Example 5, except that the copolymer solution shown in Table 3 was used instead of the copolymer solution (A-1) contained in the millbase and clear resist. Obtained. In any of the experimental examples, the copolymer solution contained in the millbase contained 3.5 g of the alkali-soluble resin added to the millbase, and the copolymer solution contained in the clear resist contained 3.5 g of the alkali-soluble resin added to the clear resist. 3.5 g of resin was used.
The obtained resin compositions G5 and G6 were subjected to the above evaluation (5). Table 3 shows the results.

Descriptions in Table 1 represent the following.
BzMI: benzylmaleimide MD: dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate AMA: methyl 2-allyloxymethyl acrylate MAA: methacrylate CHMA: cyclohexyl methacrylate MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate IPO: 2-isopropenyl-2-oxazoline GMA: glycidyl methacrylate IEMA: 2-isocyanatoethyl methacrylate

From Tables 1 to 3, the following items were confirmed.
The copolymers (A-1) to (A-4) obtained in Production Examples 1 to 4 correspond to polymers having the structural unit (A) of the present invention. On the other hand, the copolymers (A-5) to (A-6) obtained in Production Examples 5 to 6 are the copolymers (A-1) to (A-4) in that they do not contain the structural unit (A). ).
Comparing the dielectric constant of the cured product of the resin composition when used in combination with the coloring material under such a difference, Comparative Examples 1 and 2 using the copolymers (A-5) to (A-6) On the other hand, it was found that Examples 1 to 4 using the copolymers (A-1) to (A-4) had low dielectric constants (see Table 2).

In contrast to Comparative Examples 3 and 4 using the copolymers (A-5) to (A-6), in Examples 5 to 8 using the copolymers (A-1) to (A-4), It was found that the dispersion stability of the resin composition was good (see Table 3).
Although not shown in the tables, the cured products of the resin compositions B1 to B4 obtained in Examples 1 to 4 are excellent in various physical properties such as transparency, developability, solvent resistance, and adhesion to substrates. It was something.

Claims (7)

A resin composition containing an alkali-soluble resin and a polymerization initiator,
The alkali-soluble resin is a polymer having a structural unit represented by the following general formula (1),
The structural unit represented by the general formula (1) is formed by a reaction between an acid group and an oxazoline group-containing compound ,
The resin composition is a negative photosensitive resin composition
A resin composition for an optical material characterized by:

(wherein R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or a methyl group; X ¹ represents a single bond or a divalent organic group having 1 to 20 carbon atoms; X ² represents a divalent hydrocarbon group having 1 or more carbon atoms ^, and X3 represents a single bond.) A resin composition containing an alkali-soluble resin and a coloring material,
The alkali-soluble resin is a polymer having a structural unit represented by the following general formula (1),
A resin composition for optical materials, wherein the structural unit represented by the general formula (1) is formed by a reaction between an acid group and an oxazoline group-containing compound.

(wherein R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or a methyl group; X ¹ represents a single bond or a divalent organic group having 1 to 20 carbon atoms; X ² represents a divalent hydrocarbon group having 1 or more carbon atoms ^, and X3 represents a single bond.) 3. The resin composition for optical materials according to claim 2 , wherein the resin composition for optical materials is a negative photosensitive resin composition. 4. The resin composition for optical materials according to claim 1 , wherein the oxazoline group-containing compound is 2-isopropenyl-2-oxazoline. 5. The resin composition for optical materials according to claim 1, wherein the alkali-soluble resin has a double bond equivalent of 200 to 2000 g/equivalent. 6. The resin composition for optical materials according to any one of claims 1 to 5, further comprising a polymerizable compound. A laminate comprising a cured product of the resin composition for optical materials according to claim 6 on a substrate.