JP6992741B2 - Resin composition for forming a high refractive index cured film - Google Patents

Description

The present invention relates to a resin composition for forming a high refractive index cured film.

Conventionally, a protective film, an insulating film, etc. required for a touch panel or the like have been formed at a required portion by pattern processing by a photolithography method using a photosensitive resin composition. However, pattern processing by the photolithography method has a problem that not only the process is complicated but also the cost is high. On the other hand, a composition capable of forming a protective film, an insulating film, or the like at a required site by a simpler method and at a lower cost has been proposed (see, for example, Patent Document 1). Further, by providing a coating film having a high refractive index to suppress light reflection, the transmittance and visibility are often improved (see, for example, Patent Document 2).

International Publication No. 2016/013543 Japanese Unexamined Patent Publication No. 2014-5437

The present invention has been made in view of the above circumstances, and provides a composition that not only can be formed at a required portion by a simple method such as a printing method but also provides a cured film having a high refractive index. The purpose.

As a result of diligent studies to achieve the above object, the present inventor has found that a composition containing a predetermined fluorene compound and a predetermined aromatic ring-containing polymer can provide a cured film having a high refractive index. , The present invention has been completed.

（式中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子又はメチル基を表し、Ｌ¹及びＬ²は、それぞれ独立に、置換基を含んでいてもよいフェニレン基又は置換基を含んでいてもよいナフタレンジイル基を表し、Ｌ³及びＬ⁴は、それぞれ独立に、炭素数１～６のアルキレン基を表し、ｍ及びｎは、０≦ｍ≦４０、０≦ｎ≦４０及び０≦ｍ＋ｎ≦４０を満たす整数を表す。）
２．更に、（ｃ）溶媒を含む１の高屈折率硬化膜形成用樹脂組成物。
３．更に、（ｄ）単官能(メタ)アクリレート化合物を含む１又は２の高屈折率硬化膜形成用樹脂組成物。
４．更に、（ｅ）多官能(メタ)アクリレート化合物を含む１～３のいずれかの高屈折率硬化膜形成用樹脂組成物。
５．（ｅ）多官能(メタ)アクリレート化合物が、１分子中に３つの(メタ)アクリロイル基を含む化合物及び４つの(メタ)アクリロイル基を含む化合物からなる群から選ばれる少なくとも１種を含む４の高屈折率硬化膜形成用樹脂組成物。
６．更に、（ｆ）イオントラップ剤を含む１～５のいずれかの高屈折率硬化膜形成用樹脂組成物。
７．（ｆ）イオントラップ剤が、ベンゾ－１Ｈ－トリアゾール化合物を含む６の高屈折率硬化膜形成用樹脂組成物。
８．更に、（ｇ）シランカップリング剤を含む１～７のいずれかの高屈折率硬化膜形成用樹脂組成物。
９．（ｇ）シランカップリング剤が、式［４］で表されるシラン化合物を含む８の高屈折率硬化膜形成用樹脂組成物。

（式中、Ｒ⁶は、メチル基又はエチル基を表し、Ｘは、加水分解性基を表し、Ｙは、反応性官能基を表し、Ｌ⁷は、単結合又は炭素数１～１０のアルキレン基を表し、ａは、０～２の整数を表す。）
１０．更に、（ｈ）ラジカル重合開始剤を含む１～９のいずれかの高屈折率硬化膜形成用樹脂組成物。
１１．スクリーン印刷法用である、１～１０のいずれかの高屈折率硬化膜形成用樹脂組成物。
１２．１～１１のいずれかの高屈折率硬化膜形成用樹脂組成物から得られる高屈折率硬化膜。
１３．金属の電極及び／又は金属の配線が形成された基材と、この基材上に前記電極及び／又は配線と接するように形成された１２の高屈折率硬化膜とを備える導電性部材。Therefore, the present invention provides the following resin composition for forming a high refractive index cured film.
1. 1. A repeating unit derived from (a) a fluorene compound represented by the formula [1] and (b) (meth) acrylic acid and / or an aliphatic (meth) acrylate compound (however, those having a silane structure in the side chain). A resin composition for forming a high refractive index cured film, which comprises an aromatic ring-containing polymer containing a repeating unit derived from an aromatic ring-containing compound containing a polymerizable double bond.

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently contain a phenylene group or a substituent which may contain a substituent. May represent a naphthalenediyl group, L ³ and L ⁴ independently represent an alkylene group having 1 to 6 carbon atoms, and m and n are 0 ≦ m ≦ 40, 0 ≦ n ≦ 40 and 0 ≦. Represents an integer that satisfies m + n ≦ 40.)
2. 2. Further, (c) the resin composition for forming a high refractive index cured film 1 containing a solvent.
3. 3. Further, (d) a resin composition for forming a high refractive index cured film of 1 or 2 containing a monofunctional (meth) acrylate compound.
4. Further, (e) a resin composition for forming a high refractive index cured film according to any one of 1 to 3, which contains a polyfunctional (meth) acrylate compound.
5. (E) A polyfunctional (meth) acrylate compound containing at least one selected from the group consisting of a compound containing three (meth) acryloyl groups and a compound containing four (meth) acryloyl groups in one molecule. A resin composition for forming a high refractive index cured film.
6. Further, (f) the resin composition for forming a high refractive index cured film according to any one of 1 to 5, which contains an ion trapping agent.
7. (F) The resin composition for forming a high refractive index cured film of 6, wherein the ion trapping agent contains a benzo-1H-triazole compound.
8. Further, the resin composition for forming a high refractive index cured film according to any one of 1 to 7, which contains (g) a silane coupling agent.
9. (G) The resin composition for forming a high refractive index cured film of 8, wherein the silane coupling agent contains a silane compound represented by the formula [4].

(In the formula, R ⁶ represents a methyl group or an ethyl group, X represents a hydrolyzable group, Y represents a reactive functional group, and L ⁷ is a single bond or an alkylene having 1 to 10 carbon atoms. Represents a group, where a represents an integer of 0 to 2.)
10. Further, the resin composition for forming a high refractive index cured film according to any one of 1 to 9, which comprises (h) a radical polymerization initiator.
11. A resin composition for forming a high refractive index cured film according to any one of 1 to 10 for a screen printing method.
A high refractive index cured film obtained from the resin composition for forming a high refractive index cured film according to any one of 12.1 to 11.
13. A conductive member comprising a base material on which a metal electrode and / or a metal wiring is formed, and 12 high-refractive index cured films formed on the base material so as to be in contact with the electrode and / or the wiring.

The cured film obtained by using the composition of the present invention can be easily formed by a simple method such as a printing method, has a high refractive index, and is excellent in light transmission. Therefore, the composition of the present invention can form a cured film such as a protective film, a flattening film, an insulating film, etc. in various displays such as an organic electroluminescence (EL) element, and a protective film, an insulating film, etc. in a touch panel. By providing a cured film having a high refractive index, it is possible to suppress the reflection of light and improve the transmittance and visibility.

The resin composition for forming a high refractive index cured film of the present invention comprises (a) a fluorene compound represented by the formula [1] described later, and (b) (meth) acrylic acid and / or an aliphatic (meth) acrylate compound. Includes repeating units derived from (except those having a silane structure in the side chain), and aromatic ring-containing polymers containing repeating units derived from aromatic ring-containing compounds containing polymerizable double bonds.

[(A) Fluorene compound]
The fluorene compound of the component (a) is represented by the following formula [1].

In the formula [1], R ¹ and R ² independently represent a hydrogen atom or a methyl group, respectively. L ¹ and L ² each independently represent a phenylene group which may contain a substituent or a naphthalenediyl group which may contain a substituent. L ³ and L ⁴ each independently represent an alkylene group having 1 to 6 carbon atoms.

Examples of the phenylene group which may contain the substituent include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2-methylbenzene-1,4-diyl group and 2 -Aminobenzene-1,4-diyl group, 2,4-dibromobenzene-1,3-diyl group, 2,6-dibromobenzene-1,4-diyl group and the like can be mentioned.

Examples of the naphthalene diyl group that may contain the substituent include a 1,2-naphthalenedyl group, a 1,4-naphthalenedyl group, a 1,5-naphthalenedyl group, and a 1,8-naphthalenedyl group, 2,3. -Naphthalene diyl group, 2,6-naphthalene diyl group and the like can be mentioned.

Of these, 1,4-phenylene groups and the like are preferable as L ¹ and L ² .

Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 1,1-dimethylethylene group, a pentamethylene group, and a 1-methyltetramethylene group. , 2-Methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylethylene group, 2,2-dimethyltrimethylethylene group, 1-ethyltrimethylene group, hexamethylene group, 1-methylpenta Methylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1-ethyltetramethylene group 1,1,2-trimethyltrimethylene group, 1,2,2-trimethyltrimethylethylene group, 1-ethyl-1-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group and the like can be mentioned. Of these, L ³ and L ⁴ are preferably an alkylene group having 2 to 4 carbon atoms, and specifically, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, 1 , 1-Dimethylethylene group and the like are preferable.

In the formula [1], m and n represent integers satisfying 0 ≦ m ≦ 40, 0 ≦ n ≦ 40 and 0 ≦ m + n ≦ 40. m and n are preferably integers satisfying 0 ≦ m ≦ 30, 0 ≦ n ≦ 30 and 0 ≦ m + n ≦ 30, and satisfy 0 ≦ m ≦ 20, 0 ≦ n ≦ 20 and 2 ≦ m + n ≦ 20. It is more preferably an integer, and even more preferably an integer satisfying 0 ≦ m ≦ 10, 0 ≦ n ≦ 10 and 2 ≦ m + n ≦ 10, 0 ≦ m ≦ 5, 0 ≦ n ≦ 5 and 2 ≦. It is more preferable that the integer satisfies m + n ≦ 10.

Specific examples of the compound represented by the formula [1] include 9,9-bis (4-((meth) acryloyloxy) phenyl) -9H-fluorene and 9,9-bis (4- (2- (2-)-bis). (Meta) acryloyloxyethoxy) phenyl) -9H-fluorene, 9,9-bis (4- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl) -9H-fluorene, Ogsol® EA -0200, EA-0300, EA-F5003, EA-F5503, EA-F5510, EA-F5710, GA-5000 (all manufactured by Osaka Gas Chemical Co., Ltd.), NK Ester A-BPEF (Shin Nakamura Chemical Industry Co., Ltd.) ), Etc., but not limited to these.

In the composition of the present invention, the content of the fluorene compound of the component (a) is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer of the component (b). 10 to 100 parts by mass is even more preferable. When the content of the fluorene compound (a) is in the above range, a cured film having a high refractive index and sufficient hardness can be obtained.

[(B) Aromatic ring-containing polymer]
The aromatic ring-containing polymer of the component (b) is a repeating unit derived from (meth) acrylic acid and / or an aliphatic (meth) acrylate compound (excluding those having a silane structure in the side chain), and polymerizable. Contains repeating units derived from aromatic ring-containing compounds containing double bonds.

Examples of the aliphatic (meth) acrylate compound include those represented by the formula [2].

In formula [2], R ³ represents a hydrogen atom or a methyl group. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, which may be substituted with a hydroxy group, an epoxy group, a (meth) acryloyl group or an isocyanato group.

The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or sec-. A linear or branched group having 1 to 20 carbon atoms such as a butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group and an n-decyl group. Alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group. , Bicyclononyl group, bicyclodecyl group and the like, cyclic alkyl groups having 3 to 20 carbon atoms and the like can be mentioned.

Examples of the aliphatic (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and 2,2,2 (meth) acrylate. -Trifluoroethyl, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, (meth) acrylic Examples thereof include 4-hydroxybutyl acid. Among them, from the viewpoint of light transmission of the obtained cured film, the aliphatic (meth) acrylate compound preferably contains one selected from methyl (meth) acrylate and ethyl (meth) acrylate, and more preferably. , Contains methyl (meth) acrylate.

The aromatic ring-containing compound containing the polymerizable double bond is not particularly limited as long as it can be copolymerized with (meth) acrylic acid or an aliphatic (meth) acrylate compound. Examples of such an aromatic ring-containing compound include those represented by the following formula [3].

In formula [3], R ⁵ represents a hydrogen atom or a methyl group. L ⁵ represents a single bond or —C (= O) —OL ⁶ −, and L ⁶ represents an alkylene group having 1 to 6 carbon atoms which may contain a single bond or an ether bond. Ar represents an aromatic ring-containing group having 6 to 20 carbon atoms, and a part or all of the hydrogen atom of the aromatic ring-containing group is a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group or the like. It may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms.

Examples of the alkylene group include those similar to those described above. L ⁶ includes a single bond, a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, an ethyleneoxyethylene group, and a 3,6-dioxaoctane-1,8-diyl group (-CH ₂ CH ₂ ). OCH ₂ CH ₂ OCH ₂ CH _2- ), (methylethylene) oxy (methylethylene) groups and the like are preferable.

Examples of the aromatic ring-containing group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-antryl group, a 1-phenanthryl group, a 2-phenanthryl group, and 3-. Aryl groups such as phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 9H-carbazole-9-yl group; phenoxy group, 1-naphthyloxy group, 2-Phenyloxy group, 1-Anthryloxy group, 2-Anthryloxy group, 9-Anthryloxy group, 1-Phenyltriloxy group, 2-Phenyltriloxy group, 3-Phenyltriloxy group , 4-Phenantriloxy group, 9-Phenantriloxy group, 2-Biphenylyloxy group, 3-Biphenylyloxy group, 4-Biphenylyloxy group and other aryloxy groups; 2-Phenyloxyphenyl group, 3 -Phenyloxyphenyl group, 4-phenoxyphenyl group, 2-naphthyloxyphenyl group, 3-naphthyloxyphenyl group, 4-naphthyloxyphenyl group, 2- (2-biphenylyloxy) phenyl group, 2- (3-bipheni) Lyloxy) phenyl group, 2- (4-biphenylyloxy) phenyl group, 3- (2-biphenylyloxy) phenyl group, 3- (3-biphenylyloxy) phenyl group, 3- (4-biphenylyloxy) ) Phenyl group, 4- (2-biphenylyloxy) phenyl group, 4- (3-biphenylyloxy) phenyl group, 4- (4-biphenylyloxy) phenyl group and other aryloxyaryl groups; 2-phenoxyethoxy Aryloxyalkoxy groups such as a group, a 2-naphthyloxyethoxy group, a 2- (2-biphenylyloxy) ethoxy group, a 2- (3-biphenylyloxy) ethoxy group, and a 2- (4-biphenylyloxy) ethoxy group. And so on.

Among these, the aromatic ring-containing group includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 9H-carbazole-9-yl group, and a phenoxy group. , 1-naphthyloxy group, 2-naphthyloxy group, 2-biphenylyloxy group, 3-biphenylyloxy group, 4-biphenylyloxy group, 2-phenoxyphenyl group, 3-phenoxyphenyl group, 4-phenoxyphenyl Groups are preferred.

Examples of the aromatic ring-containing compound represented by the formula [3] include an aromatic ring-containing vinyl compound and an aromatic ring-containing (meth) acrylate compound.

Examples of the aromatic ring-containing vinyl compound include styrenes such as styrene, α-methylstyrene, chlorostyrene, bromostyrene, and 4-tert-butylstyrene; 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylanthracene, and 9-. Examples thereof include aromatic vinyl compounds such as vinyl anthracene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl and N-vinylcarbazole.

Examples of the aromatic ring-containing (meth) acrylate compound include phenyl (meth) acrylate, benzyl (meth) acrylate, 1-phenylethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, and (meth) acrylic. Acid 1-naphthyl, (meth) acrylic acid 1-naphthylmethyl, (meth) acrylic acid 2-naphthyl, (meth) acrylic acid 2-naphthylmethyl, (meth) acrylic acid 9-anthril, (meth) acrylic acid 9- Anthrylmethyl, 9-phenanthrylmethyl (meth) acrylate, 1-phenoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-phenoxybenzyl (meth) acrylate, (meth) acrylic Acid 3-phenoxybenzyl, (meth) acrylate 4-phenoxybenzyl, (meth) acrylate 2- (2-biphenylyloxy) ethyl, (meth) acrylate 2- (3-biphenylyloxy) ethyl, (meth) ) 2- (4-Biphenylyloxy) ethyl acrylate and the like can be mentioned.

Among these, the aromatic ring-containing compound represented by the formula [3] includes styrene, 2-phenoxybenzyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, and 4-phenoxybenzyl (meth) acrylate. , (Meta) acrylate 2- (2-biphenylyloxy) ethyl, (meth) acrylate 2- (3-biphenylyloxy) ethyl, (meth) acrylate 2- (4-biphenylyloxy) ethyl, etc. Styrene, 3-phenoxybenzyl (meth) acrylate, 2- (2-biphenylyloxy) ethyl (meth) acrylate and the like are more preferred.

The aromatic ring-containing compound may be used alone or in combination of two or more.

The aromatic ring-containing polymer of the component (b) may contain other repeating units other than the repeating unit as long as the effect of the present invention is not impaired. Monomers that provide other repeating units typically include vinyl compounds, maleimides, acrylonitrile, and maleic anhydride.

Examples of the vinyl compound include methyl vinyl ether, 2-hydroxyethyl vinyl ether, propyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether and the like.

Examples of maleimides include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

In the aromatic ring-containing polymer of the component (b), the repeating unit derived from the aromatic ring-containing compound containing a polymerizable double bond is used to increase the refractive index of the obtained cured film, and thus (meth) acrylic acid and / or (. Meta) With respect to 1 mol of the repeating unit derived from the acrylate compound, it is preferably contained in an amount of 0.3 to 20 mol, more preferably 0.5 to 10 mol, and even more preferably 1 to 5 mol. .. The aromatic ring-containing polymer of the component (b) contains a repeating unit derived from a (meth) acrylic acid and / or a (meth) acrylate compound and a repeating unit derived from an aromatic ring-containing compound containing a polymerizable double bond. The amount is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, still more preferably 100 mol%.

The aromatic ring-containing polymer of the component (b) can be synthesized by polymerizing the above-mentioned monomer giving a repeating unit. As the polymerization method, radical polymerization, anionic polymerization, cationic polymerization and the like can be adopted, but radical polymerization is preferable because a polymer having the weight average molecular weight (Mw) required in the present invention can be relatively easily produced.

Examples of the initiator include peroxides such as benzoyl peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; azobisisobutyronitrile and azobis (2). -Methylbutyronitrile), azobisisobutyronitrile, azo compounds such as 2,2'-azobis (isobutyric acid) dimethyl and the like can be mentioned. The amount of such an initiator used varies depending on the type and amount of the monomer and the reaction temperature, and therefore cannot be unconditionally specified, but is usually about 0.005 to 0.05 mol per 1 mol of the monomer. The reaction temperature at the time of polymerization may be appropriately set from 0 ° C. to the boiling point of the solvent used, but is usually about 20 to 100 ° C. The reaction time is about 0.1 to 30 hours.

The polymerization is preferably carried out in a solvent, and the solvent used for the polymerization reaction can be a solvent generally used in this type of reaction. Specifically, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2- Pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1- Alcohols such as hexanol, benzyl alcohol, cyclohexanol; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentylmethyl ether, tetrahydrofuran, 1,4-dioxane; halogenation of chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc. Hydrocarbons; Ether alcohols such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; alkylene glycol diacetates such as ethylene glycol diacetate and propylene glycol diacetate; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, Diethylene glycol monopropyl ether acetate, Diethylene glycol monoisopropyl ether acetate, Diethylene glycol monobutyl ether acetate, Diethylene glycol monoisobutyl ether acetate, Diethylene glycol monohexyl ether acetate, Dipropylene glycol monomethyl ether acetate, Dipropylene glycol monoethyl ether acetate, Dipropylene glycol mono Dialkylene glycol monoalkyl ether acetates such as propyl ether acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol monoisobutyl ether acetate, dipropylene glycol monohexyl ether acetate; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate and cellosolve acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, Cyclopentane, Methylcyclope Aliphatic or aromatic hydrocarbons such as amine, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, anisole; acetals such as methylal and diethylacetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropane, Nitro compounds such as nitrobenzene; amines such as dimethylamine, monoethanolamine and pyridine; amides such as N-methyl-2-pyrrolidone, N, N-dimethylformamide; sulfoxides such as dimethylsulfoxide; nitriles such as acetonitrile And so on. From these, the solvent to be used is appropriately selected in consideration of the type and amount of the monomer and the initiator, the reaction temperature and the like.

The weight average molecular weight (Mw) of the aromatic ring-containing polymer of the component (b) is preferably 5,000 to 500,000 from the viewpoint of ensuring the solubility of the polymer and preparing a composition that gives a suitable cured film. be. In particular, in consideration of suppressing an excessive increase in the viscosity of the composition, the upper limit of Mw of the polymer is preferably 200,000, more preferably 150,000, still more preferably 100,000, still more preferably. Is 80,000, and the lower limit thereof is preferably 10,000, more preferably 15,000, still more preferably 30,000, and further, considering suppressing an excessive decrease in the viscosity of the composition. It is preferably 40,000. In the present invention, Mw is a polystyrene-equivalent measured value by gel permeation chromatography (GPC).

The aromatic ring-containing polymer may be any of a random copolymer, an alternating copolymer, and a block copolymer.

[(C) Solvent]
The composition of the present invention may contain (c) a solvent. The solvent (c) can dissolve the above-mentioned components (a) and (b), and will be described later (d) a monofunctional (meth) acrylate compound, (e) a polyfunctional (meth) acrylate compound, and (f) an ion trap. When the agent, (g) a silane coupling agent, (h) a radical polymerization initiator, a polymerization inhibitor, other additives and the like are contained, there is no particular limitation as long as they can also be dissolved.

Specific examples of the solvent include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), and 1,2-butanediol. 2,3-Butanediol, 1,3-Butanediol, 1,4-Butanediol, 1,5-Pentanediol, 2-Methyl-2,4-Pentanediol (hexylene glycol), 1,3-octylene Glycols such as glycol, 3,6-octylene glycol;
Triols such as glycerin;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, propylene glycol Alkylene glycol mono such as propylene glycol monoalkyl ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether and propylene glycol monohexyl ether. Alkyl ethers;
Ethylene glycol monoaryl ethers such as ethylene glycol monophenyl ether, alkylene glycol monoaryl ethers such as propylene glycol monoaryl ethers such as propylene glycol monophenyl ether;
Ethylene glycol monoaralkyl ethers such as ethylene glycol monobenzyl ether, alkylene glycol monoaralkyl ethers such as propylene glycol monoaralkyl ethers such as propylene glycol monobenzyl ether;
Ethylene glycol alkoxyalkyl ethers such as ethylene glycol butoxyethyl ether, alkylene glycol alkoxyalkyl ethers such as propylene glycol alkoxyalkyl ethers such as propylene glycol butoxyethyl ether;
Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol diisopropyl Alkylene glycol dialkyl ethers such as propylene glycol dialkyl ethers such as ether and propylene glycol dibutyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Alkylene glycol monoalkyl ether acetates such as propylene glycol monoalkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate;
Ethylene glycol monoacetates such as ethylene glycol monoacetate, alkylene glycol monoacetates such as propylene glycol monoacetate such as propylene glycol monoacetate;
Ethylene glycol diacetates such as ethylene glycol diacetate, alkylene glycol diacetates such as propylene glycol diacetate such as propylene glycol diacetate;
Diethylene glycol monomethyl ethers, diethylene glycol monomethyl ethers, diethylene glycol monoisopropyl ethers, diethylene glycol monobutyl ethers, diethylene glycol monoisobutyl ethers, diethylene glycol monoalkyl ethers, dipropylene glycol monomethyl ethers, dipropylene glycol monomethyl ethers, diethylene glycol monomethyl ethers, diethylene glycol monomethyl ethers, diethylene glycol monomethyl ethers, diethylene glycol monomethyl ethers, diethylene glycol monomethyl ethers Dialkylene glycols such as dipropylene glycol monoalkyl ethers such as ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monohexyl ether, etc. Monoalkyl ethers;
Dialkylene glycol monoaralkyl ethers such as diethylene glycol monobenzyl ether;
Diethylene glycol monoaryl ethers such as diethylene glycol monophenyl ether, dialkylene glycol monoaryl ethers such as dipropylene glycol monoaryl ethers such as dipropylene glycol monophenyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol diisopropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol diisopropyl ether, Dialkylene glycol dialkyl ethers such as dipropylene glycol dialkyl ethers such as dipropylene glycol dibutyl ether;
Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoisopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoisobutyl ether acetate, diethylene glycol monoalkyl ether acetates such as diethylene glycol monohexyl ether acetate, dipropylene Glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol monoisobutyl ether acetate, dipropylene glycol monohexyl ether Dipropylene glycol monoalkyl ether acetates such as acetate Dialkylene glycol monoalkyl ether acetates such as acetate;
Triethylene glycol monoalkyl ethers such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, and trialkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether. Ethers;
Triethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether and triethylene glycol diethyl ether, trialkylene glycol dialkyl ethers such as tripropylene glycol dialkyl ethers such as tripropylene glycol dimethyl ether and tripropylene glycol diethyl ether;
1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetradecanol Linear fatty alcohols such as, cyclohexanol, cyclic aliphatic alcohols such as 2-methylcyclohexanol, and other fatty alcohols;
Phenols such as phenol;
Aromatic alcohols such as benzyl alcohol;
Heterocyclic alcohols such as furfuryl alcohol;
Hydrogenated heterocyclic-containing alcohols such as tetrahydrofurfuryl alcohol;
Dialkyl ethers such as diisopropyl ether, di-n-butyl ether and di-n-hexyl ether;
Methyl phenyl ether, ethyl phenyl ether, n-butyl phenyl ether, benzyl (3-methyl butyl) ether, (2-methyl phenyl) methyl ether, (3-methyl phenyl) methyl ether, (4-methyl phenyl) methyl ether, etc. Alkyl aryl ethers;
Alkylaralkyl ethers such as ethylbenzyl ether;
Cyclic alkyl monoethers such as 2-methylfuran, tetrahydrofuran, tetrahydropyran;
Cyclic alkyl diethers such as 1,4-dioxane;
Cyclic alkyl triethers such as trioxane;
Diepoxy alkyl ethers such as diglycidyl ether;
Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, (3-methylbutyl) acetate, n-hexyl acetate, (2-ethylbutyl) ) Acetates, linear or branched alkyl acetates such as (2-ethylhexyl) acetate, alkyl acetates such as cyclic alkyl acetates such as cyclohexyl acetate and 2-methylcyclohexyl acetate; ethylpropionate, n-propylpro Pionate, isopropylpropionate, n-butylpropionate, isobutylpropionate, sec-butylpropionate, tert-butylpropionate, n-pentylpropionate, (3-methylbutyl) propionate, n- Linear or branched alkyl propionates such as hexylpropionate, (2-ethylbutyl) propionate, (2-ethylhexyl) propionate, cyclic alkylpropionates such as cyclohexylpropionate, 2-methylcyclohexylpropionate. Alkylpropionates such as nates; ethyl butylate, n-propylbutyrate, isopropylbutyrate, n-butylbutyrate, isobutylbutyrate, sec-butylbutyrate, tert-butylbutyrate, n-pentylbuty Linear or branched alkyl butyrate, such as rate, (3-methylbutyl) butylate, n-hexylbutyrate, (2-ethylbutyl) butylate, (2-ethylhexyl) butylate, cyclohexylbutyrate, 2-methylcyclohexylbutyrate. Alkyl Butylates such as Cyclic Alkyl Butylates such as Rates; Ethyl Lactate, n-propyl Lactate, Isopropyl Lactate, n-Butyl Lactate, Isobutyl Lactate, sec-Butyl Lactate, tert-Butyl Lactate, n-Pentyl Lactate, ( Linear or branched alkyl lactates such as 3-methylbutyl) lactate, n-hexyl lactate, (2-ethylbutyl) lactate, (2-ethylhexyl) lactate, cyclic alkyl lactates such as cyclohexyl lactate, 2-methylcyclohexyl lactate. Alkyl lactates such as alkyl esters such as;
Aralkyl acetates such as benzyl acetate, aralkyl propionates such as benzyl propionate, aralkyl butyrates such as benzyl butyrate, aralkyl alkyl esters such as aralkyl lactates such as benzyl lactate;
Dialkyl ketones such as diethyl ketone, diisobutyl ketone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-propyl ketone, methyl n-hexyl ketone, ethyl n-butyl ketone, di-n-propyl ketone, etc. Kind;
Cyclic alkenyl ketones such as isophorone;
Cyclic alkyl ketones such as cyclohexanone;
Hydroxydialkyl ketones such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol);
Heterocyclic aldehydes such as furfural;
Linear or branched alkanes such as heptane, octane, 2,2,3-trimethylhexane, decane, dodecane;
Alkylbenzenes such as toluene, xylene, o-xylene, m-xylene, p-xylene, mesitylene, tetralin, cyclohexylbenzene;
Cyclic alkanes such as cyclohexane, methylcyclohexane, and ethylcyclohexane may be mentioned, but are not limited thereto. These solvents can be used alone or in admixture of two or more.

The composition of the present invention preferably has a temperature of 150 ° C. or higher, more preferably 180 ° C. or higher, still more preferably 200 ° C. or higher, from the viewpoint of obtaining a suitable film with good reproducibility when the composition is applied by a printing method. Contains a solvent having a standard boiling point. By including a solvent having such a boiling point, a suitable liquid film state can be realized with good reproducibility.

For these reasons, when the printing method is adopted as the coating method, the composition of the present invention is a solvent having a characteristic of satisfactorily dissolving the aromatic ring-containing polymer of the component (b), specifically, glycols. , At least 1 selected from alkylene glycol diacetates, dialkylene glycol monoalkyl ethers, dialkylene glycol monoaralkyl ethers, dialkylene glycol monoaryl ethers, alkylene glycol monoalkyl ether acetates and alkylene glycol monoaralkyl ethers. It is preferable to include seeds.

Specific examples of such a solvent include propylene glycol diacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. Diethylene glycol monohexyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, etc. However, but not limited to these.

The solvent of the component (c) is preferably in an amount such that the solid content concentration in the composition of the present invention is 1 to 95% by mass, more preferably 5 to 90% by mass. An amount such that the solid content concentration is 10 to 85% by mass is even more preferable. Here, the solid content means a composition obtained by removing the solvent from all the components of the present invention.

The composition of the present invention further comprises a monofunctional (meth) acrylate compound, a polyfunctional (meth) acrylate compound, a radical polymerization initiator, a silane coupling agent, and a polymerization agent for the purpose of adjusting the adhesion and hardness of the cured film. It may contain a banning agent or the like.

[(D) Monofunctional (meth) acrylate compound]
The composition of the present invention may contain (d) a monofunctional (meth) acrylate compound. In the present invention, the monofunctional (meth) acrylate compound is a compound containing one (meth) acryloyl group in the molecule, and is, for example, an aliphatic exemplified as a monomer component of the aromatic ring-containing polymer of the component (b). Examples thereof include (meth) acrylate compounds and aromatic ring-containing (meth) acrylate compounds. Among these, as the (d) monofunctional (meth) acrylate compound, an aromatic ring-containing (meth) acrylate compound is preferable, and in particular, those exemplified as the aromatic ring-containing (meth) acrylate compound represented by the formula [3] are exemplified. preferable. The monofunctional (meth) acrylate compound can be used alone or in combination of two or more.

Specific examples of the preferred aromatic ring-containing (meth) acrylate compound include benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-phenoxybenzyl (meth) acrylate, and 3-phenoxy (meth) acrylate. Benzyl, 4-phenoxybenzyl (meth) acrylic acid, 2- (2-biphenylyloxy) ethyl (meth) acrylic acid, 2- (3-biphenylyloxy) ethyl (meth) acrylic acid, 2 (meth) acrylic acid -(4-Biphenylyloxy) ethyl and the like can be mentioned. Of these, benzyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, 2- (2-biphenylyloxy) ethyl (meth) acrylate are more preferred, and 3-phenoxybenzyl (meth) acrylate. Even more preferable.

The content of the monofunctional (meth) acrylate compound of the component (d) is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer of the component (b) from the viewpoint of the refractive index of the obtained cured film. , 0 to 50 parts by mass is more preferable, and 0 to 30 parts by mass is even more preferable.

[(E) Polyfunctional (meth) acrylate compound]
The composition of the present invention may contain (e) a polyfunctional (meth) acrylate compound from the viewpoint of adjusting the physical characteristics of the cured film. In the present invention, the polyfunctional (meth) acrylate compound is a compound containing at least two (meth) acryloyl groups in the molecule, and specifically, an ester of a polyhydric alcohol and (meth) acrylic acid is used. Can be mentioned. Further, the number of (meth) acryloyl groups in one molecule of the polyfunctional (meth) acrylate compound is preferably 3 to 6, but more preferably 3 or 4, from the viewpoint of particularly improving the hardness. Examples of such a polyhydric alcohol include glycerol, erythritol, pentaerythritol, trimethylolethane, trimethylolpropane, dipentaerythritol, and trimethylolpropane.

Specific examples of the polyfunctional (meth) acrylate compound include two (meth) acryloyl groups such as neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, and ethylene oxide-modified bisphenol A di (meth) acrylate. Bifunctional (meth) acrylate compound having; trifunctional (meth) having three (meth) acryloyl groups such as pentaerythritol tri (meth) acrylate, trimethylol ethanetri (meth) acrylate, and trimethylol propanthry (meth) acrylate. Acrylate compound; A tetrafunctional (meth) acrylate compound having four (meth) acryloyl groups such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropanetetra (meth) acrylate; dipentaerythritol penta (meth) acrylate and dipentaerythritol. Examples thereof include, but are not limited to, 5 to 6 functional (meth) acrylate compounds having 5 or 6 (meth) acryloyl groups such as hexa (meth) acrylate. The polyfunctional (meth) acrylate compound can be used alone or in combination of two or more.

The polyfunctional (meth) acrylate compound can be easily obtained as a commercially available product, and specific examples thereof include, for example, KAYARAD (registered trademark) NPGDA, R-551, T-1420 manufactured by Nippon Kayaku Co., Ltd. , DPHA, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, MANDA, GPO-303, TMPTA , THE-330, TPA-320, TPA-330, PET-30, RP-1040; Aronix (registered trademark) manufactured by Toa Synthetic Co., Ltd. M-211B, M-6200, M-309, M-400, M- 402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050; Viscoat 700HV, 295, 300, 360, GPT, 3PA, 400, 312 manufactured by Osaka Organic Chemical Industry Co., Ltd .; NK Ester ABE-300, A-BPE-4, A-BPE-10 manufactured by Shin Nakamura Chemical Industry Co., Ltd. , A-BPE-20, A-BPE-30, A-BPP-3, A-B1206PE, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, NPG, A -9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM -35E, A-TMMT, A-9550, A-DPH, TMPT, etc. can be mentioned.

According to a preferred embodiment of the present invention, the polyfunctional (meth) acrylate compound contained in the composition of the present invention contains at least one polyfunctional (meth) acrylate compound having 3 or 4 (meth) acryloyl groups. ..

When the polyfunctional (meth) acrylate compound of the component (e) is contained, the content thereof is preferably 10 to 300 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer of the component (b). More preferably, 50 to 150 parts by mass is even more preferable. When the content is within the above range, the effect of improving the hardness of the cured film can be obtained and cracks do not occur.

[(F) Ion trap agent]
The composition of the present invention may contain (f) an ion trapping agent. (F) The ion trap agent prevents migration due to contact with water, especially when the substrate is made of metal or when metal wiring is formed on the substrate. Has the function of

From the viewpoint of improving the migration inhibitory ability of the obtained cured film, a preferable example of the ion trapping agent is a compound having a nitrogen-based heterocycle in the structure. The nitrogen-based heterocycle has a cyclic structure of three or more members having a saturated or unsaturated bond, and has one or more nitrogen atoms in the cyclic structure.

Examples of the nitrogen-based heterocycle include those having a saturated bond, such as aziridine (ethyleneimine), azetidine (azacyclobutane), azolidine (pyrrolidin), azinan (piperidin), and azepan (hexamethyleneimine). Those having a saturated bond include azirine (1H-azirine, 2H-azirine), azeto (azacyclobutadiene), azole (1H-pyrrole, 2H-pyrrole, imidazole, pyrazole, 1,2,3-triazole, 1,2). , 4-triazole, 1H-tetrazole), pyridine, azepine (azatropylidene), imidazoline, pyrazine, triazine (1,2,3-triazole, 1,2,4-triazine, 1,3,5-triazine) and the like. Further, porphyrin, choline, phthalocyanine and the like to which a plurality of nitrogen-based heterocycles are bonded can also be mentioned.

Further, the nitrogen-based heterocycle may be fused with nitrogen-based heterocycles or an aromatic ring hydrocarbon compound (benzene ring, naphthalene ring, etc.), and may be, for example, benzotriazole, indole, isoindole, benzimidazole, quinoline. , Isoquinoline, quinoxalin, cinnoline, purine, pteridine, acridine, carbazole and the like.

Further, the nitrogen-based heterocycle may contain a heteroatom other than the nitrogen atom, for example, thiazole, isothiazole, thiazine and the like containing a sulfur atom, oxazole and isoxazole containing an oxygen atom, and the like. Frazan, morpholine, 3-pyrazolone, 5-pyrazolone, benzoxazole and the like can also be mentioned.

Further, it may be an addition compound of a nitrogen-based heterocycle in which another nitrogen-based heterocycle such as isocyanuric acid is added to these nitrogen-based heterocycles. In the present invention, these nitrogen-based heterocycles can be used alone or in combination of two or more.

Specific examples of compounds having a nitrogen-based heterocycle in the structure include 2,4-diamino-6-vinyl-1,3,5-triazine, 2,4-diamino-6-vinyl-1,3,5-. Triazine isocyanuric acid adduct salt, 2,4-diamino-6- (2- (meth) acryloyloxyethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (hexyloxy) phenyl]- 4,6-Diphenyl-1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-Hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- [3- (2-ethylhexyl-1-oxy)- 2-Hydroxypropyloxy] phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- [2-hydroxy-3- (dodecyloxy) propyloxy] -2-Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2, Triazine compounds such as 4-dibutoxyphenyl) -1,3,5-triazine, N'-tert-butyl-N-cyclopropyl-6- (methylthio) -1,3,5-triazine-2,4-diamine 1,2,3-benzotriazole, 1,2,3-benzotriazole sodium salt, 3-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, carboxybenzo Triazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, 2,2'-[[(methyl) -1H-benzotriazole-1-yl) methyl] imino] bisethanol, 6- (2-benzotriazoleyl) -4-tert-octyl-6'-tert-butyl-4'-methyl-2,2' -Methylenebisphenol, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole, 2-( 3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotri Azole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (3-dodecyl-) 2-Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5 Chlorobenzotriazole 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4-tert-octylphenol], 2- (3-sec-butyl-5-tert-butyl-2-hydroxyphenyl) ) Benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2-benzotriazole, 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl)- Examples thereof include benzotriazole compounds such as 4- (1,1,3,3-tetramethylbutyl) phenol and 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole. However, it is not limited to these.

Among them, the ion trap agent preferably contains a 1H-benzotriazole compound, more preferably contains 1H-benzotriazole which may be substituted with an alkyl group having 1 to 3 carbon atoms, and more preferably 5-methyl-1H-. It is even more preferred to include benzotriazole.

The compound having a nitrogen-based heterocycle in the structure can be synthesized by a known method and can also be obtained as a commercially available product. Specific examples of commercially available products include Tinuvin® 234, 326, 328, 329, 400, 405, 460, 571, 928, 1577, P, PS, UVITEX® OB, IRGAGUARD® D. 1071 (above, BASF), SB-UVA 6164, SB-UVA 6577, EVERSORB 70, EVERSORB 75 (above, manufactured by Sort Co., Ltd.), Curesol (registered trademark) VT, VT-OK, MAVT (above, Shikoku) Chemical Industry Co., Ltd.), BT-120, JCL-400, CBT-1, BT-LX, TT-LX, TT-LYX, JAST-500, JF-832 (all manufactured by Johoku Chemical Industry Co., Ltd.) , 5MBT (manufactured by Chemipro Kasei Co., Ltd.), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.), 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.

Other preferable examples of the ion trap agent include hydrazide derivatives, sulfur-containing phosphites and the like. Specific examples thereof include decamethylene dicarboxylic acid disalicyloyl hydrazide, N, N'-bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl] hydrazine, 2,2'-. Oxamidebis [ethyl 3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], bisbenzoic acid hydride hydrazide, bis isophthalate (2-phenoxypropionylhydrazide), tris [2-tert-butyl-4- (2-tert-butyl-4- (2-tert-butyl-4-) 2'-Methyl-4'-hydroxy-5'-tert-butylphenylthio) -5-methylphenyl] phosphite and the like can be mentioned. These may be used alone or in combination of two or more.

Hydrazide derivatives and sulfur-containing phosphites can be synthesized by known methods and can also be obtained as commercial products. Specific examples of commercially available products include Inhibitor OABH (manufactured by Eastman), ADEKA STAB (registered trademark) CDA-6 (manufactured by ADEKA Corporation), Irganox (registered trademark) MD 1024 (manufactured by BASF), and the like.

When the ion trapping agent of the component (f) is contained, the content thereof is preferably from the viewpoint of obtaining a thin film having excellent hardness, adhesion and the like with good reproducibility with respect to 100 parts by mass of the aromatic ring-containing polymer of the component (b). It is 20 parts by mass or less, more preferably 10 parts by mass or less, and is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and even more preferably 0.01, from the viewpoint of excellent migration suppressing ability. It is more than a mass part.

[(G) Silane coupling agent]
The composition of the present invention may contain (g) a silane coupling agent from the viewpoint of improving the adhesion of the obtained cured film to a substrate or the like, and according to a preferred embodiment, the silane coupling agent may contain a formula. It contains a silane compound represented by [4].

In formula [4], R ⁶ represents a methyl group or an ethyl group. X represents a hydrolyzable group. Y represents a reactive functional group. L ⁷ represents a single bond or an alkylene group having 1 to 10 carbon atoms. a represents an integer of 0 to 2.

Examples of the alkylene group having 1 to 10 carbon atoms represented by L ⁷ include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, a pentamethylene group and 2,2-dimethyl. Examples thereof include a trimethylene group, a hexamethylene group, an octamethylene group, and a decamethylene group. Among these, a trimethylene group is preferable.

Examples of the hydrolyzable group represented by X include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and an alkoxyalkoxy group having 2 to 4 carbon atoms. Examples of the halogen atom include a chlorine atom and a bromine atom. The alkoxy group having 1 to 3 carbon atoms is preferably linear or branched, and specifically, it is a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group. Specific examples of the alkoxyalkoxy group having 2 to 4 carbon atoms are a methoxymethoxy group, a 2-methoxyethoxy group, an ethoxymethoxy group and a 2-ethoxyethoxy group.

Examples of the reactive functional group represented by Y include an amino group, a ureido group, a (meth) acryloyloxy group, a vinyl group, an epoxy group, a mercapto group and the like. Of these, an amino group, a ureido group, and a (meth) acryloyloxy group are preferable, and an amino group or a ureido group is more preferable.

Specific examples of the silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl (methyl) (dimethoxy) silane, and 3-aminopropyl ( Methyl) (diethoxy) silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, vinyltrichlorosilane , Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl (methyl) (diethoxy) silane, 3 -Glysidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl (methyl) (dimethoxy) silane, 3-mercaptopropyl (methyl) (diethoxy) silane, 7 -Octenyltrichlorosilane, 7-octenyltrimethoxysilane, 7-octenyltriethoxysilane, 8-glycidoxyoctyltrichlorosilane, 8-glycidoxyoctyltrimethoxysilane, 8-glycidoxyoctyltriethoxysilane , 8- (meth) acryloyloxyoctyltrichlorosilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 8- (meth) acryloyloxyoctyltriethoxysilane, 8-oxylanyloctyltrichlorosilane, 8-oxylanyl Examples thereof include octyltrimethoxysilane and 8-oxylanyloctyltriethoxysilane.

Among them, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth). ) Acryloyloxypropyltriethoxysilane and the like are preferable.

The silane coupling agent can be synthesized by a known method and is also available as a commercially available product. Further, the silane coupling agent can be used alone or in combination of two or more.

When the silane coupling agent of the component (g) is contained, the content thereof is preferably 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer of the component (b). Is more preferable, and 0.05 to 1 part by mass is even more preferable. When the content is within the above range, the effect of improving the adhesion can be obtained, and the hardness does not decrease.

[(H) Radical Polymerization Initiator]
The composition of the present invention may contain (h) a radical polymerization initiator in order to promote the polymerization of the polymerizable component contained in the composition. For example, the polymer is spontaneously polymerized by the treatment at a high temperature, but when there is a situation that the high temperature curing treatment cannot be performed due to the modification of the substrate, the low temperature curing treatment or the photocuring treatment can be performed by the radical polymerization initiator.

The radical polymerization initiator may be any as long as it can release a substance that initiates radical polymerization by irradiation with light and / or heating. For example, as the photoradical polymerization initiator, benzophenone derivative, imidazole derivative, bisimidazole derivative, N-arylglycine derivative, organic azido compound, titanosen compound, aluminat complex, organic peroxide, N-alkoxypyridinium salt, thioxanthone derivative And so on. More specifically, benzophenone, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3', 4,4'-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5- Isooxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl = phenyl = ketone, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, bis (η ^5-2,4 -cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-) Examples thereof include, but are not limited to, pyrrol-1-yl) phenyl) titanium.

Commercially available products can also be used as the photoradical polymerization initiator, and examples thereof include IRGACURE (registered trademark) 651, 184, 369, and 784 manufactured by BASF. In addition, commercially available products other than the above can also be used. Specifically, BASF's IRGACURE 500, 907, 379, 819, 127, 754, 250, 1800, 1870, OXE01, TPO, DAROCUR (registered trademark) 1173; Lambson. Speedcure (registered trademark) MBB, PBZ, ITX, CTX, EDB; Lamberti Esacure (registered trademark) ONE, KIP150, KTO46; KAYACURE (registered trademark) DETX-S, CTX, BMS manufactured by Nippon Kayaku Co., Ltd. , DMBI, etc.

Examples of the thermal radical polymerization initiator include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, and dicumyl peroxide. Peroxides such as lauroyl peroxide, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate (tert-butyl2-ethylhexaneperoxoate); 2,2'-azo Bisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) , Dimethyl 2,2'-azobis isobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobuty Lonitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), etc. Azo-based compounds; examples thereof include, but are not limited to, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

Examples of commercially available thermal radical polymerization initiators include Parloyl® IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, Perbutyl® ND, NHP, manufactured by Nichiyu Co., Ltd. MA, PV, 355, A, C, D, E, L, I, O, P, Z, Perhexyl® ND, PV, D, I, O, Z, Per Octa® ND, Niper (Registered Trademark) Registered Trademarks PMB, BMT, BW, Pertetra® A, Perhexa® MC, TMH, HC, 250, 25B, C, 25Z, 22, V, Perocta® O, Park Mill (Registered Trademarks) ) ND, D, Permenta (registered trademark) H, Novmer (registered trademark) BC; Wako Pure Chemical Industries, Ltd. V-70, V-65, V-59, V-40, V-30, VA-044 , VA-046B, VA-061, V-50, VA-057, VA-086, VF-096, VAm-110, V-601, V-501; BASF IRGACURE 184, 369, 651, 500, 819 , 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, TPO, DAROCUR 1116, 1173; Cytec Surface Specialty's UVECRYL® P36; Lamberti's Esacure KIP150, KIP65LT, KIP100F, KT37, KT55 , KTO46, KIP75 / B, etc., but are not limited to these.

When the radical polymerization initiator of the component (h) is contained, the content thereof is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer of the component (b).

The composition of the present invention may contain a polymerization inhibitor, if necessary. Specific examples of the polymerization initiator include 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and the like. Examples thereof include 4-methoxy-1-naphthol. When the polymerization inhibitor is contained, the content thereof is preferably 1% by mass or less, more preferably 0.5% by mass or less in the total solid content.

The composition of the present invention further comprises a surfactant, a cross-linking agent, an antifoaming agent, a rheology adjuster, a pigment, a dye, a storage stabilizer, a polyvalent phenol, and the like, as long as the effect of the present invention is not impaired. It can contain a dissolution accelerator such as a polyvalent carboxylic acid.

The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant. Examples of this type of surfactant include Ftop (registered trademark) EF301, EF303, EF352 manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd .; Megafuck (registered trademark) F171, F173 manufactured by DIC Co., Ltd .; FLUORAD manufactured by 3M Co., Ltd. (Registered Trademarks) FC430, FC431; Asahi Guard (registered trademark) AG710 manufactured by Asahi Glass Co., Ltd., Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106, etc. manufactured by AGC Seimi Chemical Co., Ltd. Can be mentioned.

Examples of the cross-linking agent include a polyfunctional epoxy compound, a polyfunctional isocyanate compound, a polyfunctional thiol compound, a melamine-based cross-linking agent, and the like, and when a polyfunctional (meth) acrylate compound is contained, a trifunctional or higher functional thiol compound is preferable. The polyfunctional thiol compound can be obtained as an addition reaction product of a polyhydric alcohol with a monofunctional and / or a polyfunctional thiol compound. Specific compounds include 1,3,5-tris (2- (3-mercaptopropionyloxy) ethyl) isocyanurate, 1,3,5-tris (2- (3-mercaptobutylyloxy) ethyl) isocia. Trifunctional thiol compounds such as Nurate (Showa Denko Co., Ltd., Karenz MT (registered trademark) NR1), Trimethylol propanthris (3-mercaptopropionate); Pentaerythritol tetrakis (3-mercaptopropionate), Penta Tetrafunctional thiol compounds such as erythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd., Karenz MT PEI); Be done.

Examples of the defoaming agent include, but are not limited to, acetylene glycols, silicone fluids and emulsions, ethoxylated or propoxylated silicones, hydrocarbons, fatty acid ester derivatives, acetylated polyamides, poly (alkylene oxide) polymers and copolymers. .. When screen printing is performed, the composition of the present invention preferably contains an antifoaming agent.

The viscosity of the composition of the present invention at 25 ° C. is preferably 1 to 10,000 mPa · s, more preferably 1 to 5,000 mPa · s, still more preferably 1 to 1,000 mPa · s from the viewpoint of coatability. s. When the viscosity is in the above range, the coatability is good and the desired film thickness can be obtained.

The viscosity of the composition of the present invention at 25 ° C. is preferably 10 to 100,000 mPa · s, more preferably 500 to 100,000 mPa · s, and even more preferably 1,000 to 1,000 mPa · s from the viewpoint of printability. It is 100,000 mPa · s. When the viscosity is within the above range, the ejection property is good, no load is generated on the process, the composition does not diffuse after application, and the transferability of the composition to the substrate does not decrease. ..

When forming a cured film with a fine structure such as an insulating film to form a bridge structure at the portion of the touch panel where the X-axis electrode and the Y-axis electrode are orthogonal to each other, printing methods such as screen printing and gravure offset printing are adopted. The viscosity of the composition of the present invention at 25 ° C. is preferably 10 to 100,000 mPa · s, more preferably 5,000 to 100,000 mPa · s, and even more preferably 20,000 to 100,000 mPa · s.・ S. When the viscosity is within the above range, the ejection property is good, no load is generated on the process, the composition does not diffuse after application, and the transferability of the composition to the substrate does not decrease. .. In the present invention, the viscosity is a value measured by an E-type viscometer.

The method for preparing the composition of the present invention is not particularly limited. As an example, there is a method in which the aromatic ring-containing polymer of the component (b) is dissolved in a solvent, and other components are mixed with this solution at a predetermined ratio to obtain a uniform solution. Further, in the preparation of the composition of the present invention, the aromatic ring-containing polymer-containing solution obtained by the polymerization reaction in the solvent can be used as it is. In this case, other components may be added to the aromatic ring-containing polymer-containing solution to make a uniform solution. Further, a solvent may be further added for the purpose of adjusting the concentration.

The composition thus prepared is preferably used after being filtered using a filter or the like having a pore size of about 0.2 μm from the viewpoint of obtaining a more uniform cured film.

[Cured film]
The composition of the present invention can be applied to a substrate having electrodes and / or wiring (for example, silicon / silicon dioxide coated substrate; silicon nitride substrate; metal such as aluminum, molybdenum, chromium, copper, silver, metal nanowire such as silver nanowire, etc. Coated with conductive polymers such as silver nanoparticles, metal nanoparticles such as copper nanoparticles, poly (3,4-ethylenedioxythiophene) / poly (styrene sulfonate) (PEDOT / PSS), graphene, carbon nanotubes, etc. Substrate; Glass substrate; Quartz substrate; Indium tin oxide (ITO) substrate; ITO film substrate; Triacetyl cellulose (TAC) film, polyester film, acrylic film, resin film substrate such as cycloolefin (COP) film), etc. Apply by rotation coating, flow coating, roll coating, slit coating, rotary coating following the slit, inkjet coating, screen printing, flexo printing, gravure printing, offset printing, gravure offset printing, etc. A coating film can be formed by pre-drying (pre-baking) with a hot plate, an oven, or the like. The composition of the present invention is particularly suitable for printing methods such as inkjet coating, screen printing, flexographic printing, and gravure offset printing.

Prebake is generally treated at 60-150 ° C, more preferably 80-120 ° C, for 0.5-30 minutes when using a hot plate and 0.5-90 minutes when using an oven. The method is adopted.

Then, post-baking for thermosetting is performed. Specifically, it is heated using a hot plate, an oven, or the like. Post-baking is generally performed at a temperature of 150 to 300 ° C, more preferably 200 to 250 ° C, for 1 to 30 minutes when using a hot plate, and for 1 to 90 minutes when using an oven. Be done.

When the composition of the present invention contains a thermal radical polymerization initiator, it can be cured at a low temperature. In this case, the pre-baking conditions are the same as described above, but the post-baking temperature is preferably 60 to 200 ° C, more preferably 80 to 150 ° C. Other conditions are the same as described above.

When the composition of the present invention contains a photoradical polymerization initiator, photocuring can be performed by irradiating the coating film with light such as ultraviolet rays (UV) after prebaking. The light has a wavelength in the range of 200 to 500 nm, and its exposure amount is preferably 100 to 5,000 mJ / cm ² .

After photo-curing, post-baking for thermosetting may be performed. Specifically, it is heated using a hot plate, an oven, or the like. Post-baking is generally performed at 60 to 150 ° C, more preferably 80 to 120 ° C, for 1 to 30 minutes when using a hot plate, and for 1 to 90 minutes when using an oven. Be done.

By curing the composition of the present invention under the above conditions, the steps of the substrate can be sufficiently flattened and a cured film having a high refractive index can be formed.

The cured film of the present invention can be easily formed by a simple method such as a printing method, and further has a high refractive index. Therefore, a touch panel such as a protective film, a flattening film, an insulating film, etc. in various displays such as organic EL elements. It is expected as a material for forming a cured film such as a protective film and an insulating film.

The conductive member provided with the cured film of the present invention formed in contact with the electrode and / or the wiring on the base material on which the metal electrode and / or the metal wiring is formed has corrosion of the electrode and / or the wiring. Since it is suppressed, an increase in resistance in the electrodes and wiring, peeling of the electrodes and metal from other members, and the like are suppressed, and as a result, the durability is excellent.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Comparative Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the examples, the equipment and conditions used for sample preparation and analysis of physical properties are as follows.
(1) Stirring and defoaming device: Shinky Co., Ltd. Rotating / Revolving Mixer Awatori Rentaro (registered trademark) ARE-310
(2) Spin coating device: Cee (registered trademark) 100 manufactured by Brewer Science
(3) UV exposure device: Heraeus belt conveyor type UV lamp system (H bulb)
(4) Constant temperature bath device: Small environmental tester SH-222 manufactured by ESPEC CORPORATION
(5) Gel Permeation Chromatography (GPC)
Equipment: Showa Denko Corporation Shodex (registered trademark) GPC-101
Column: Showa Denko Corporation Shodex GPC KF-803L + KF-804L
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1 mL / min Detector: RI
Calibration curve: Standard polystyrene (6) Refractive index measuring device: Metricon model 2010 / M Prism coupler Measuring temperature: 25 ° C
(7) Total light transmittance measuring device: Haze meter NDH 5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
Wavelength range: 380-780nm

The abbreviations have the following meanings.
EPPA: Ethoxylated o-phenylphenol acrylate (NK ester A-LEN-10 manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
MAA: Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
MMA: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
POBA: 3-Phenoxybenzyl acrylate (Light acrylate POB-A manufactured by Kyoeisha Chemical Co., Ltd.)
St: Styrene (manufactured by Tokyo Chemical Industry Co., Ltd.)
MAIB: 2,2'-azobis (isobutyric acid) dimethyl (manufactured by Tokyo Chemical Industry Co., Ltd.)
BPFDA: Bisphenol full orange acrylate (Ogsol EA-F5710 manufactured by Osaka Gas Chemical Co., Ltd.)
TMPTA: Trimethylolpropane triacrylate (NK ester A-TMPT manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
A771: Polysiloxane defoamer (AGITAN771 manufactured by MUNZING)
APTES: (3-aminopropyl) triethoxysilane (LS-3150 manufactured by Shin-Etsu Chemical Co., Ltd.)
MBT: 5-Methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
I184: 1-Hydroxycyclohexyl = Phenyl = Ketone (IRGACURE® 184 manufactured by BASF)
DEGEEA: Diethylene glycol monoethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)
PGDA: Propylene glycol diacetate (manufactured by Wako Pure Chemical Industries, Ltd.)

[1] Production of polymer [Production example 1] Production of aromatic ring-containing polymer 1
324.5 g of PGDA was charged as a solvent into a 1 L four-necked flask. A mixture of 61.6 g (0.62 mol) of MMA, 15.0 g (1.44 mol) of St15.0 g (1.44 mol) and 4.72 g (0.02 mol) of MAIB was added to this PGDA while stirring at 70 ° C. (internal temperature) under a nitrogen atmosphere. It was dropped over 2 hours. After the dropping, the reaction was further carried out at 70 ° C. for 20 hours to obtain a polymer solution P1 having a polymer concentration of 40% by mass. The Mw of the polymer in P1 was 65,000.

[Production Example 2] Production of an aromatic ring-containing polymer 2
315.1 g of PGDA was charged as a solvent into a 1 L four-necked flask. A mixture of 30.0 g (0.30 mol) of MMA, 177.8 g (0.70 mol) of POBA and 2.30 g (0.01 mol) of MAIB was added to this PGDA while stirring at 70 ° C. (internal temperature) under a nitrogen atmosphere. It was dropped over 2 hours. After the dropping, the reaction was further carried out at 70 ° C. for 20 hours to obtain a polymer solution P2 having a polymer concentration of 40% by mass. The Mw of the polymer in P2 was 125,000.

[Production Example 3] Production of an aromatic ring-containing polymer 3
329.5 g of PGDA was charged as a solvent into a 1 L four-necked flask. A mixture of 30.0 g (0.30 mol) of MMA, 187.4 g (0.70 mol) of EPPA and 2.30 g (0.01 mol) of MAIB was added to this PGDA while stirring at 70 ° C. (internal temperature) under a nitrogen atmosphere. It was dropped over 2 hours. After the dropping, the reaction was further carried out at 70 ° C. for 20 hours to obtain a polymer solution P3 having a polymer concentration of 40% by mass. The Mw of the polymer in P3 was 56,000.

[Production Example 4] Production of an aromatic ring-containing polymer 4
345.0 g of PGDA was charged as a solvent into a 1 L four-necked flask. A mixture of 27.5 g (0.32 mol) of MAA, 20.0 g (0.75 mol) of EPPA and 2.45 g (0.01 mol) of MAIB was added to this PGDA while stirring at 70 ° C. (internal temperature) under a nitrogen atmosphere. It was dropped over 2 hours. After the dropping, the reaction was further carried out at 70 ° C. for 20 hours to obtain a polymer solution P4 having a polymer concentration of 40% by mass. The Mw of the polymer in P4 was 70,000.

[Comparative Production Example 1] Production of Polymer without Aromatic Ring 303.5 g of DEGEEA was charged as a solvent into a 1 L four-necked flask. A mixture of 20.0 g (2.00 mol) of MMA and 2.30 g (0.01 mol) of MAIB was added dropwise to this DEGEEA over 2 hours while stirring at 70 ° C. (internal temperature) under a nitrogen atmosphere. After the dropping, the reaction was further carried out at 70 ° C. for 20 hours to obtain a polymer solution P5 having a polymer concentration of 40% by mass. The Mw of the polymer in P5 was 95,000.

[2] Preparation of a resin composition for forming a cured film [Example 1]
250 parts by mass of the polymer solution P1 obtained in Production Example 1 (100 parts by mass as a polymer), 55 parts by mass of BPFDA as a fluorene compound, 55 parts by mass of TMPTA as a polyfunctional (meth) acrylate, 6 parts by mass of MBT as an ion trapping agent, and silane coupling. 0.1 part by mass of APTES as an agent, 0.65 part by mass of A771 as a defoaming agent, 6.4 parts by mass of I184 as a radical polymerization initiator, and 70 parts by mass of PGDA as a solvent were mixed. This mixture was stirred and defoamed at 2,000 rpm for 10 minutes to prepare a varnish having a solid content concentration of 50% by mass. Here, the solid content refers to all the components except the solvent.

[Examples 2 to 4, Comparative Examples 1 to 2]
Each varnish was prepared in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 1.

[3] Preparation and evaluation of cured film [Refractive index evaluation]
The varnishes of Examples 1 to 4 and Comparative Examples 1 and 2 were each applied by spin coating on a glass substrate and prebaked in an oven at 110 ° C. for 10 minutes. The obtained coating film was exposed to UV (exposure amount 800 mJ / cm ² ) and further post-baked in an oven at 110 ° C. for 30 minutes to prepare a cured film having a thickness of about 5 μm.
The refractive index and total light transmittance of the obtained cured film at a wavelength of 633 nm were measured. The results are also shown in Table 2.

As shown in Table 2, the cured film obtained from the composition of the present invention had a high refractive index of 1.56 or more at a wavelength of 633 nm (Examples 1 to 4). On the other hand, the cured film using a polymer having no aromatic group (Comparative Example 1) and the cured film not containing a fluorene compound (Comparative Example 2) had low refractive indexes of 1.557 and 1.540, respectively. rice field.

Claims (13)

(A) A fluorene compound represented by the formula [1], (b) a repeating unit derived from an aliphatic (meth) acrylate compound (excluding those having a silane structure in the side chain), and polymerizable di. In contact with the electrode and / or wiring on a substrate on which a metal electrode and / or metal wiring is formed, which comprises an aromatic ring-containing polymer containing only repeating units derived from an aromatic ring-containing compound containing a heavy bond. A resin composition for forming a high refractive index cured film used for forming a high refractive index cured film to be formed.

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently contain a phenylene group or a substituent which may contain a substituent. May represent a naphthalenediyl group, L ³ and L ⁴ independently represent an alkylene group having 1 to 6 carbon atoms, and m and n are 0 ≦ m ≦ 40, 0 ≦ n ≦ 40 and 0 ≦. Represents an integer that satisfies m + n ≦ 40.) The resin composition for forming a high refractive index cured film according to claim 1, further comprising (c) a solvent. The resin composition for forming a high refractive index cured film according to claim 1 or 2, further comprising (d) a monofunctional (meth) acrylate compound. The resin composition for forming a high refractive index cured film according to any one of claims 1 to 3, further comprising (e) a polyfunctional (meth) acrylate compound. (E) A claim that the polyfunctional (meth) acrylate compound comprises at least one selected from the group consisting of a compound containing three (meth) acryloyl groups and a compound containing four (meth) acryloyl groups in one molecule. 4. The resin composition for forming a high refractive index cured film according to 4. The resin composition for forming a high refractive index cured film according to any one of claims 1 to 5, further comprising (f) an ion trapping agent. (F) The resin composition for forming a high refractive index cured film according to claim 6, wherein the ion trapping agent contains a benzo-1H-triazole compound. The resin composition for forming a high refractive index cured film according to any one of claims 1 to 7, further comprising (g) a silane coupling agent. (G) The resin composition for forming a high refractive index cured film according to claim 8, wherein the silane coupling agent contains a silane compound represented by the formula [4].

(In the formula, R ⁶ represents a methyl group or an ethyl group, X represents a hydrolyzable group, Y represents a reactive functional group, and L ⁷ is a single bond or an alkylene having 1 to 10 carbon atoms. Represents a group, where a represents an integer of 0 to 2.) The resin composition for forming a high refractive index cured film according to any one of claims 1 to 9, further comprising (h) a radical polymerization initiator. The resin composition for forming a high refractive index cured film according to any one of claims 1 to 10, which is used for a screen printing method. A high refractive index cured film obtained from the resin composition for forming a high refractive index cured film according to any one of claims 1 to 11. The high refractive index cured film according to claim 12, wherein a base material on which a metal electrode and / or a metal wiring is formed and a high refractive index cured film formed on the base material so as to be in contact with the electrode and / or the wiring are provided. Element.