JP6627308B2 - Thermosetting composition - Google Patents

Description

  The present invention relates to the formation of an insulating film in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, an antireflection film, a flattening film, and an interlayer insulating film in a liquid crystal display element and a protective film for a color filter. The present invention relates to a thermosetting composition which can be used for a thermosetting composition which can be applied to a substrate having a high refractive index and a lower surface energy. The present invention further relates to an organic film formed using the thermosetting composition and an electronic component having the organic film.

  2. Description of the Related Art In an image display device such as a liquid crystal display, a touch panel display, and an organic EL display, an antireflection layer is provided on a display surface in order to prevent a decrease in visibility due to reflection. For this antireflection layer, a high refractive index material (for example, see Patent Document 1) has been required. In recent years, a high-refractive-index material is also required for a bone-prevention layer above a touch sensor and a light guide plate of an organic EL display.

  Hitherto, polymerizable compounds having a nitrogen-containing heterocyclic compound (see, for example, Patent Documents 2 and 3) have been proposed as thermosetting compositions in which the formed organic film has a high refractive index.

  In addition, as a method for applying the above-described thermosetting composition, there are spin coating, slit coating, and a printing method. However, depending on the electronic device, the base on which the organic film is formed may have low surface energy. In this case, the conventional thermosetting composition has a problem in that the thermosetting composition solution is repelled at the time of application, resulting in poor coating.

JP-A-11-038201 JP 2009/091462 JP-A-2012-092661

  An object of the present invention is to provide a thermosetting composition in which a formed organic film has a high refractive index and can be applied to a substrate having a low surface energy, and to provide an electronic component having the organic film. It is to be.

The present inventors have conducted intensive studies in order to solve the above-described problems, and as a result, an acrylic acid-based material having a dimethylsiloxane structure has been used as a raw material of a polymer component constituting a thermosetting composition having a high refractive index. The present inventors have found that the aforementioned problems can be solved by using a monomer and a monomer having a nitrogen-containing heterocyclic ring, and have completed the present invention.
The present invention includes the following configurations.

（式（１）中、Ｒ^１は水素又は−ＣＨ_３であり、Ｒ^２〜Ｒ^６はそれぞれ独立して炭素数１〜５のアルキル、炭素数１〜５のアルコキシ又は炭素数１〜３のアルキルを有するトリアルキルシロキシであり、ｍは１〜１０の整数であり、そして、ｎは０〜１５０の整数である。） [1] A monomer (a1) represented by the formula (1), a monomer (a2) having a heterocyclic ring, a monomer (a3) having a carboxyl group or a carboxylic anhydride group (—CO—O—CO—), and A polymer (A) obtained by copolymerizing another monomer (a4).

(In the formula (1), R ¹ is hydrogen or —CH ₃ , and R ^{2 to} R ⁶ are each independently an alkyl having 1 to 5 carbons, an alkoxy having 1 to 5 carbons or an alkoxy having 1 to 3 carbons. Trialkylsiloxy with alkyl, m is an integer from 1 to 10, and n is an integer from 0 to 150.)

（式（２）中、Ｘは単結合または−ＣＯＯ−であり、Ｙは単結合又は炭素数１〜５のアルキレンであり、Ｒ^７は水素又は−ＣＨ_３であり、Ｒ^８〜Ｒ^１５は、それぞれ独立して水素、ハロゲン、−ＣＮ、−ＣＦ_３、−ＯＣＦ_３、−ＯＨ、炭素数１〜９のアルキル、又は炭素数１〜９のアルコキシであり、前記炭素数１〜９のアルキルは任意の−ＣＨ_２−が−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−で置き換えられていてもよく、任意の水素がハロゲンで置き換えられていてもよく、前記炭素数１〜９のアルコキシは任意の水素がハロゲンで置き換えられていてもよい。なお、上記Ｘが−ＣＯＯ−であるとき、カルボニル基（−ＣＯ−）は二重結合に隣接する。） [2] The polymer (A) according to item [1], wherein the monomer (a2) having a heterocycle is a compound represented by the following formula (2).

(In the formula (2), X is a single bond or —COO—, Y is a single bond or an alkylene having 1 to 5 carbon atoms, R ⁷ is hydrogen or —CH ₃ , and R ^{8 to} R ¹⁵ are are each independently hydrogen, _halogen, -CN, -CF _3, -OCF 3, an -OH, alkyl of 1-9 carbon atoms, or alkoxy of 1 to 9 carbon atoms, said alkyl having 1 to 9 carbon atoms May have any of —CH ₂ — replaced with —COO—, —OCO—, or —CO—, any hydrogen may be replaced with halogen, and the alkoxy having 1 to 9 carbon atoms is optional. May be replaced by halogen. When X is -COO-, the carbonyl group (-CO-) is adjacent to the double bond.)

[3] The monomer (a1) is a compound represented by the formula (1), wherein R ¹ is —CH ₃ , R ^{2 to} R ⁵ are each —CH ₃ , R ⁶ is alkyl having 1 to 10 carbons, and m is 1 to 5 The polymer (A) according to the item [1] or [2], wherein the compound is a compound wherein n is an integer of 1 to 150.

[4] The monomer (a2) having a heterocyclic ring is a compound in which, in the formula (2), R ^{7 to} R ¹⁵ are all hydrogen and X and Y are both single bonds. [1] to [3] ] The polymer (A) according to any one of the above.

[5] The monomer (a3) having a carboxyl group or a carboxylic acid anhydride group (—CO—O—CO—) is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, and itaconic anhydride. The polymer (A) according to any one of [1] to [4].

[6] The other monomer (a4) is selected from the group consisting of benzyl acrylate, benzyl methacrylate, methyl benzyl methacrylate, naphthyl acrylate, naphthyl methacrylate, methyl naphthyl methacrylate, adamantyl acrylate, adamantyl methacrylate, methyl adamantyl methacrylate, and N-substituted maleimide. The polymer (A) according to any one of [1] to [5], which is at least one of the following:

[7] The content of the monomer (a1) represented by the formula (1) is 0.1 to 20 parts by weight when the total amount of the monomers is 100 parts by weight, [1] to [1]. 6] The polymer (A) according to any one of the above.

[8] The content of the monomer (a2) represented by the formula (2) is 40 parts by weight or more and 97.9 parts by weight or less when the total amount of the monomers is 100 parts by weight, [1] to [7]. ] The thermosetting composition polymer (A) of any one of the above.

[9] A thermosetting composition containing the polymer (A) according to any one of [1] to [8], a silane coupling agent (B), and an organic solvent (C).

[10] A cured product formed using the thermosetting composition according to the item [9].

[11] An organic film formed using the thermosetting composition according to the item [9].

  A (patterned) organic film such as a protective film and an insulating film formed using the thermosetting composition of the present invention has a high refractive index. Further, the thermosetting composition of the present invention shows low surface energy. As a result, the thermosetting composition of the present invention can form an organic film having a high refractive index on a substrate having a low surface energy.

1. Polymer (A) of the present invention
The polymer (A) of the present invention is a monomer (a1) represented by the formula (1), a monomer (a2) having a heterocyclic ring, a monomer having a carboxyl group or a carboxylic anhydride group (—CO—O—CO—). It is a polymer obtained by copolymerizing (a3) and other monomers (a4) other than (a1), (a2) and (a3). The method for producing the polymer (A) of the present invention by copolymerization is not particularly limited, but is preferably produced by radical copolymerization.

  The mixing ratio (weight ratio) of each component of the radical polymerizable monomer which is a raw material for producing the polymer (A) of the present invention is 0.1% when the total amount of the monomers is 100 parts by weight. ７８78 parts by weight, monomer (a2) is 40-97.9 parts by weight, monomer (a3) is 1-38.9 parts by weight, and monomer (a4) is 1-58.9 parts by weight. Part. The amount of the monomer (a1) is more preferably 0.1 to 20 parts by weight from the viewpoint of providing good coatability.

（式（１）中、Ｒ^１は水素又は−ＣＨ_３であり、Ｒ^２〜Ｒ^６はそれぞれ独立して炭素数１〜５のアルキル、炭素数１〜５のアルコキシ又は炭素数１〜３のアルキルを有するトリアルキルシロキシであり、ｍは１〜１０の整数であり、そして、ｎは０〜１５０の整数である。） 1-1. Monomer (a1)
One of the raw materials for obtaining the polymer (A) of the present invention is a monomer (a1) represented by the following formula (1).

(In the formula (1), R ¹ is hydrogen or —CH ₃ , and R ^{2 to} R ⁶ are each independently an alkyl having 1 to 5 carbons, an alkoxy having 1 to 5 carbons or an alkoxy having 1 to 3 carbons. Trialkylsiloxy with alkyl, m is an integer from 1 to 10, and n is an integer from 0 to 150.)

The monomer (a1) is specifically Silaplane FM-0711 (in the above formula (1), R ¹ = R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = -CH ₃ , m = 3, weight average The molecular weight is 1000.), Silaplane FM-0721 (in the above formula (1), R ¹ = R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = -CH ₃ , m = 3, weight average molecular weight 5000) ), Silaplane FM-0725 (in the above formula (1), R ¹ = R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = -CH ₃ , m = 3, weight average molecular weight 10000). ), Silaplane TM-0701 (in the above formula (1), R ¹ = -CH ₃ , R ² = R ³ = R ⁶ = trimethylsiloxy group, m = 3, n = 0) (all above) Trade name; manufactured by JNC Corporation), 3-methacryloyl Examples thereof include xypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane. These may be used alone or in combination of two or more.

  Among these, FM-0711 and FM-0721, which give good coating properties to the thermosetting resin composition, are preferable.

（式（２）中、Ｘは単結合または−ＣＯＯ−であり、Ｙは単結合又は炭素数１〜５のアルキレンであり、Ｒ^７は水素又は−ＣＨ_３であり、Ｒ^８〜Ｒ^１５は、それぞれ独立して水素、ハロゲン、−ＣＮ、−ＣＦ_３、−ＯＣＦ_３、−ＯＨ、炭素数１〜９のアルキル、又は炭素数１〜９のアルコキシであり、前記炭素数１〜９のアルキルは任意の−ＣＨ_２−が−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−で置き換えられていてもよく、任意の水素がハロゲンで置き換えられていてもよく、前記炭素数１〜９のアルコキシは任意の水素がハロゲンで置き換えられていてもよい。なお、上記Ｘが−ＣＯＯ−であるとき、カルボニル基（−ＣＯ−）は二重結合に隣接する。） 1-2. Monomer having heterocycle (a2)
One of the raw materials for obtaining the polymer (A) of the present invention is a monomer (a2) having a heterocyclic ring. The monomer (a2) is preferably a monomer having a nitrogen-containing heterocycle, and more preferably at least one selected from the group consisting of compounds represented by the following formula (2).

(In the formula (2), X is a single bond or —COO—, Y is a single bond or an alkylene having 1 to 5 carbon atoms, R ⁷ is hydrogen or —CH ₃ , and R ^{8 to} R ¹⁵ are are each independently hydrogen, _halogen, -CN, -CF _3, -OCF 3, an -OH, alkyl of 1-9 carbon atoms, or alkoxy of 1 to 9 carbon atoms, said alkyl having 1 to 9 carbon atoms May have any of —CH ₂ — replaced with —COO—, —OCO—, or —CO—, any hydrogen may be replaced with halogen, and the alkoxy having 1 to 9 carbon atoms is optional. May be replaced by halogen. When X is -COO-, the carbonyl group (-CO-) is adjacent to the double bond.)

The monomer (a2) is specifically 9-vinylcarbazole (in the formula (2), R ^{7 to} R ¹⁵ are each hydrogen and X and Y are both single bonds), 9-acrylcarbazole (formula In (2), R ^{7 to} R ¹⁵ are each hydrogen, X is —COO—, and Y is a single bond.), 9-methacrylcarbazole (in the formula (2), R ⁷ is —CH ₃ , R ^{8 to} R ¹⁵ are each hydrogen, X is —COO—, and Y is a single bond.), 3-chloro-9-vinylcarbazole (in the formula (2), R ⁷ To R ¹² and R ^{14 to} R ¹⁵ are each hydrogen, R ¹³ is chlorine, and X and Y are both single bonds, and 3-bromo-9-vinylcarbazole (in the formula (2), R ⁷ ~R ¹² Contact Fine ^R 14 ^{to R 15} are each ^{hydrogen, R 13} is bromine, those X and Y are both a single bond.), The 3-iodo-9-vinyl carbazole (formula ^{(2), R} 7 ~ R ¹² and R ^{14 to} R ¹⁵ are each hydrogen, R ¹³ is iodine, X and Y are both single bonds, and 3-nitro-9-vinylcarbazole (in the formula (2), ^{7 to} R ¹² and R ^{14 to} R ¹⁵ are each hydrogen, R ¹³ is a nitro group, and X and Y are both single bonds.), 9- (8-nonen-1-yl) -9 And carbazole (in the formula (2), each of R ^{7 to} R ¹⁵ is hydrogen, X is a single bond, and Y is alkylene having 6 carbon atoms). These may be used alone or in combination of two or more.

  Among these, 9-vinyl carbazole, 9-acryl carbazole, or 9-methacryl carbazole which gives the organic film after heat curing a high refractive index of 1.6 or more and a transparency of 80% or more in transmittance. preferable.

1-3. Monomer (a3) having a carboxyl group or a carboxylic anhydride group (—CO—O—CO—)
One of the raw materials for obtaining the polymer (A) of the present invention is a monomer (a3) having a carboxyl group or a carboxylic anhydride group (—CO—O—CO—). Preferred monomers (a3) are acrylic acid, methacrylic acid, maleic anhydride, α-ethylacrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and It is at least one selected from the group consisting of 2- (meth) acryloyloxyethyl phthalic acid. These may be used alone or in combination of two or more. Of these, methacrylic acid is more preferred.

1-4. Other monomer (a4)
As a raw material for obtaining the polymer (A) of the present invention, other monomers (a4) other than the monomers (a1), (a2) and (a3) are used. The monomer (a4) is not particularly limited as long as it is a polymerizable compound other than the above-mentioned monomer (a1), monomer (a2) and monomer (a3). Preferred monomers (a4) are alkyl, benzyl, cyclohexyl, tris- It is a compound having a polymerizable double bond having trimethylsiloxysilyl, dicyclopentanyl, maleimide, hydroxycarbonyl, or hydroxyphenyl. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryloyloxypropyl-tris-trimethylsiloxysilane, It is at least one selected from the group consisting of cyclopentanyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, and 4-hydroxyphenylvinylketone. These may be used alone or in combination of two or more. Among these, benzyl methacrylate is more preferred.

1-5. Method for Producing Polymer (A) The polymer (A) of the present invention is obtained by radical copolymerization of the above-mentioned monomer (a1), monomer (a2), monomer (a3) and monomer (a4). Although the method for producing the polymer of the present invention is not particularly limited, it can be produced by heating a mixture of the above monomers in the presence of a radical polymerization initiator. Organic peroxides, azo compounds, and the like can be used as the radical polymerization initiator. The reaction temperature of the radical copolymerization is not particularly limited, but is usually in the range of 50C to 150C. The reaction time is not particularly limited, but is usually in the range of 1 to 48 hours. In addition, the reaction can be performed under any of pressure, reduced pressure, or atmospheric pressure.

  As the solvent used for the above-mentioned radical copolymerization reaction, a solvent used for dissolving the monomer used and the produced polymer is used. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, acetone, 2-butanone, ethyl acetate, butyl acetate, propyl acetate, Tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , Methyl 3-methoxypropionate Ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone. The solvent may be one of these or a mixture of two or more of these. Of these, butyl acetate, propylene glycol monomethyl ether, and diethylene glycol methyl ethyl ether are more preferred.

  The polymer (A) of the present invention preferably has a weight-average molecular weight in the range of 500 to 100,000 determined by GPC analysis using polystyrene as a standard, because the film-forming properties are good. Further, it is more preferable that the weight average molecular weight is in the range of 1,500 to 50,000, since the substrate adhesion is good.

  The weight average molecular weight of the polymer (A) of the present invention can be determined by adding polystyrene having a molecular weight of 645 to 132,900 to standard polystyrene, for example, a polystyrene calibration kit (trade name: PL2010-0102, VARIAN), a column ( The trade name can be measured using PLgel MIXED-D (Varian, Inc.) and THF as a mobile phase.

2. Thermosetting composition of the present invention The thermosetting composition of the present invention is a polymer (A) obtained by copolymerizing the above-mentioned monomer (a1), monomer (a2), monomer (a3), and monomer (a4). , A silane coupling agent (B) and an organic solvent (C).

2-1. Thermal crosslinking agent The thermosetting composition of the present invention may use a thermal crosslinking agent. The thermal crosslinking agent is not particularly limited as long as it has good compatibility with other components forming the thermosetting composition of the present invention, but preferably a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic type Examples thereof include an epoxy resin, a polymer of a monomer having an epoxy group, and a copolymer of a monomer having an epoxy group with another monomer.

  Specific examples of the epoxy resin include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)]. Ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxyphenyl) ) -1-Methylethyl] phenyl] ethyl] phenoxy] -2-propanol and 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [ 4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane. As these epoxy resins, the following commercially available products can be used. Examples of commercially available products include TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER1032H60 (trade name; Japan Epoxy Resin Co., Ltd.) JER 157S65, 157S70 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 152, 154 (trade name; Japan Epoxy Resin Co., Ltd.) EOCN-102S, 103S, 104S, 1020 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (trade name; oil) Shell Epoxy Co., Ltd.), Epicoat 1004, Epiko 1256 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), Araldite CY177, Araldite CY184 (trade name; manufactured by Nippon Ciba Geigy Co., Ltd.), Celloxide 2021, and EHPE-3150 (trade name; manufactured by Daicel Chemical Industries, Ltd.) Is mentioned. The epoxy resin used in the present invention may be used as a mixture of two or more kinds.

  Further, specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate. Among these, glycidyl methacrylate is preferred because it can provide an organic film having good transparency.

  Specific examples of other monomers that copolymerize with a monomer having an epoxy group include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate , Iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methyl Examples include styrene, chloromethylstyrene, and N-phenylmaleimide. Among these, methyl (meth) acrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl in which the obtained copolymer has excellent compatibility with the polyester amide acid used in the present invention. (Meth) acrylates and styrene are preferred.

  Preferred specific examples of the polymer of the monomer having an epoxy group and the copolymer of the monomer having an epoxy group and another monomer include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, and benzyl methacrylate-glycidyl methacrylate copolymer. Coalescent, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer.

2-2. Silane coupling agent (B)
The silane coupling agent (B) is used for improving the adhesion between the thermosetting composition and the substrate. One or more silane coupling agents may be used. A silane-based compound can be used as the silane coupling agent. Examples of such a coupling agent include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane (S510; trade name, JNC Corporation) Manufactured). Among these, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving the adhesion.

  It is preferable that the silane coupling agent (B) is used in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the polymer (A) from the viewpoint of increasing the adhesion of the organic film obtained from the thermosetting composition of the present invention. preferable.

2-3. Solvent (C)
The solvent (C) used in the thermosetting composition of the present invention is preferably a compound having a boiling point of 100C to 300C. Specific examples of the solvent having a boiling point of 100 ° C to 300 ° C include butyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl methoxyacetate, methyl methoxyacetate, and butyl methoxyacetate. , Methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl lopionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyruvate Methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, dioxane, ethylene glycol, diethylene glycol, triethylene glycol Ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol Methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, 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, diethylene glycol methyl ethyl ether, toluene, xylene, γ-butyl Rorakuton, or N, N-dimethylacetamide. These may be used alone or in combination of two or more.

  The solvent (C) may be a mixed solvent containing 20% by weight or more of these solvents having a boiling point of 100 to 300 ° C. As the solvent other than the solvent having a boiling point of 100 to 300 ° C. in the mixed solvent, a known solvent can be used.

  As the solvent (C), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether It is preferable to use at least one selected from diethylene glycol methyl ethyl ether, ethyl lactate and butyl acetate since the coating uniformity is improved. Furthermore, when at least one selected from propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, ethyl lactate, and butyl acetate is used, the coating of the thermosetting composition is uniform. It is preferable from the viewpoint of enhancing the safety and safety to the human body.

  It is preferable to use 10 to 10000 parts by weight of the solvent (C) based on 100 parts by weight of the polymer (A) from the viewpoint of improving the coating property of the coating film obtained from the thermosetting composition of the present invention.

  As the solvent (C), the solvent used at the time of synthesizing the polymer (A) may be used as it is, but a solvent may be further added to adjust the viscosity, coatability, etc. of the thermosetting composition. In this specification, the solvent thus added may be referred to as a “diluting solvent”. After the synthesis of the polymer (A), the reaction solvent may be distilled off under reduced pressure, and the polymer (A) and other solids may be dissolved again in the solvent at the time of preparing the thermosetting composition.

  Further, the thermosetting composition of the present invention may further contain other components other than the above as long as the effects of the present invention can be obtained.

3. Other Components Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity and adhesiveness. Additives include anionic, cationic, nonionic, fluorine-based or silicon-based leveling agents / surfactants, ultraviolet absorbers such as alkoxybenzophenones, crosslinking agents such as epoxy compounds, melamine compounds or bisazide compounds, and many others. Examples thereof include hardening agents such as polyvalent carboxylic acids and phenol compounds, and antioxidants such as hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds.

3-1. Surfactant A surfactant can be added to the thermosetting composition of the present invention in order to improve coating uniformity. Examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, polyflow no. 90, polyflow no. 95 (trade name; manufactured by Kyoeisha Chemical Industry Co., Ltd.), BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346 (tradename; manufactured by BYK Japan KK), KP-341, KP-358, KP-368 , KF-96-50CS, KF-50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon S-420, Surflon S-611, Surflon S-651, Surflon SC-101, Surflon KH-40 ( (Trade name: AGC Seimi Chemical Co., Ltd.), FUTAGENT 222F, FUTAGENT 250, FUTAGENTO 251, FUTAGENT 208G, FUTAGENTO 310, FTX-218 (trade name; manufactured by Neos Co., Ltd.), EFTOP EF-351 , EFTOP EF-352, EFT PEF-601, EFTOP EF-801, EFTOP EF-802 (trade name; manufactured by Mitsubishi Materials Corporation), MegaFac F-171, MegaFac F-177, MegaFac F-475, MegaFac F-556, Megafax R-30, Megafax DS-21 (trade name; manufactured by DIC Corporation), TEGOFlow370, TEGOGlide420, TEGOGlide450, TEGOWet260, TEGOrad2100, TEGOTwin4000, TEGOTwin4100 (tradename; manufactured by Evonik Degussa), fluoroalkylbenzene , Fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl Sulfonate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, poly Oxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxy Ethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sol Tanoleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, or alkyl diphenyl ether disulfonic acid And the like. It is preferable to use at least one selected from these as the additive.

Among these additives, Megafac F-556, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, Surflon S-611, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfone Acid surfactant, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, or fluoroalkylaminosulfonic acid salt, or a fluorine-based surfactant such as BYK306, BYK342, BYK346, KP-341, or KP-358. Or the addition of at least one selected from silicon-based additives such as KP-368 is preferable because the coating uniformity of the thermosetting composition becomes high.
Further, the content of the surfactant in the thermosetting composition of the present invention is usually preferably from 0.01 to 10% by weight.

3-2. UV absorber The thermosetting composition of the present invention may further contain an ultraviolet absorber from the viewpoint of further improving the ability of the cured film to prevent deterioration of the cured film. From such a viewpoint, the content of the ultraviolet absorber is preferably from 0.01 to 10% by weight, more preferably from 0.05 to 8% by weight, based on the total amount of the thermosetting composition. , 0.1 to 5% by weight.

  Examples of such an ultraviolet absorber include Tinuvin P, Tinuvin 120, Tinuvin 144, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 571, and Tinuvin 765 (trade name; manufactured by BASF Japan Ltd.). Among these, Tinuvin P, Tinuvin 120 and Tinuvin 326 are preferable from the viewpoint of transparency and compatibility.

3-3. Crosslinking Agent The thermosetting composition of the present invention may further contain a crosslinking agent from the viewpoint of further improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity. From such a viewpoint, the content of the crosslinking agent is preferably 20 to 150 parts by weight based on the total amount of the thermosetting composition. The crosslinking agent may be a thermal crosslinking agent that is crosslinked by heat or a photocrosslinking agent that is crosslinked by light irradiation.

  Examples of such a thermal crosslinking agent include jER807, jER815, jER825, jER827, jER828, jER190P and jER191P (trade names, manufactured by Mitsubishi Chemical Corporation), jER1004, jER1256, YX8000 (all trade names; Mitsubishi Chemical Corporation) Araldite CY177, Araldite CY184 (trade name, manufactured by Huntsman Japan KK), Celoxide 2021P, celoxide 3000, EHPE-3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.), Techmore VG3101L (or more) All are trade names; manufactured by Printtech Corporation), Nikarac MW-30HM, Nikarac MW-100LM, Nikarac MW-270, Nikarac MW-280, Nikarac MW-290, Nikarac MW-390, MW-750LM, (trade name; manufactured by Sanwa Chemical Co., Ltd.), HP4700, HP7200 (trade name; manufactured by DIC Corporation), Ogsol EG-200, on-coat EX-1020, on-coat EX-1040 ( (Trade name; manufactured by Osaka Gas Chemical Co., Ltd.).

  Examples of such a photocrosslinking agent include 4,4′-diazidostilbene-2,2′-disodium sulfonate and 4,4′-diazidobenzalacetone-2,2′-disulfonate sulfonate. Sodium salt, 1,3-bis (4′-azido-2′-sulfobenzylidene) butanone disodium salt, 2,6-bis (4′-azido-2′-sulfobenzylidene) cyclohexanone disodium salt, 2,6 -Bis (4'-azido-2'-sulfobenzylidene) -4-methylcyclohexanone disodium salt, 2,5-bis (4'-azido-2'-sulfobenzylidene) cyclopentanone disodium salt, 4,4 '-Diadocinamylideneacetone-2,2'-disodium sulfonate, 2,6-bis (4'-azido-2'-sulfosinamylidene) cyclo Cyclohexanone disodium salt, 2,5-bis (4'-azido-2'-sulfo Sina millimeter den) cyclopentanone disodium salt.

3-4. Curing agent The thermosetting composition of the present invention may further contain a curing agent from the viewpoint of adjusting thermosetting properties. From such a viewpoint, the content of the curing agent is preferably 10% by weight or less based on the total amount of the thermosetting composition. On the other hand, the content is more preferably 0.01% by weight or more.

  Examples of such a curing agent include SMA17352 (trade name, manufactured by SARTOMER Co., Ltd.) as a polyvalent carboxylic acid, SMA1000, SMA2000, SMA3000 (trade name, manufactured by SARTOMER Co., Ltd.) as an acid anhydride, and maleic anhydride. , Tetrahydrophthalic anhydride, hexahydrophthalic acid, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, hexahydrotrimellitic anhydride , Methyl nadic anhydride, hydrogenated methyl nadic anhydride, dodecenyl succinic anhydride, pyromellitic dianhydride, hexahydropyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, TMEG, TMTA-C, TMEG -500, TME -600, (trade name; manufactured by Shin Nippon Rika Co., Ltd.), Epiclon B-4400 (trade name; manufactured by DIC Corporation), YH-306, YH-307, YH-309 (trade name; Mitsubishi Chemical Corporation) ), SL-12AH, SL-20AH, IPU-22AH (trade name; manufactured by Okamura Oil Co., Ltd.), OSA-DA, DSA, PDSA-DA (trade name; manufactured by Sanyo Chemical Co., Ltd.), phenol compounds 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,3 ′, 4-tetrahydroxybenzophenone, 2,3 , 4,4'-Tetrahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydrido) (Xyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methyl Ethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene- 5,6,7,5 ', 6', 7'-hexanol or 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like.

  When the polyvalent carboxylic acid or the phenol compound is added to the thermosetting composition of the present invention, the thermosetting property can be adjusted. By increasing the curability, heat resistance and chemical resistance can be further improved.

3-5. Antioxidant An antioxidant such as a hindered phenol compound, a hindered amine compound, a phosphorus compound or a sulfur compound can be added to the thermosetting composition of the present invention. Among them, hindered phenols are particularly preferred from the viewpoint of weather resistance. Specific examples, Irganox1010, IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (trade name; BASF Japan Co., Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STA BAO-60, ADK STAB AO-70, and ADK STAB AO-80 (trade name; manufactured by ADEKA Corporation). Among them, Irganox 1010 is preferable. The content of the antioxidant is preferably 0.01 to 10% by weight based on the total amount of the thermosetting composition.

4. Storage of thermosetting composition The thermosetting composition of the present invention is preferably stored at a temperature in the range of -30 ° C to 25 ° C, because the composition has good stability over time. If the storage temperature is -20 ° C to 10 ° C, it is more preferable that there is no precipitate.

5. Use of thermosetting composition The thermosetting composition of the present invention is suitable for forming a transparent organic film, and is most suitable for forming a transparent insulating film and an antireflection film. Here, the insulating film refers to, for example, a film (interlayer insulating film) provided for insulating between wirings arranged in layers. Further, the antireflection film refers to, for example, a film provided on the surface of the base material for reducing reflected light. The insulating film and the antireflection film refer to a solid film applied by a known method such as spin coating, roll coating, slit coating, or a pattern formed by a photolithography method or a printing method.

  A method for forming a transparent organic film on a substrate having a low surface energy using the thermosetting composition of the present invention is as follows, for example.

  First, the thermosetting composition of the present invention is applied to a base having a low surface energy by a known method such as spin coating, roll coating, slit coating and the like. Examples of the base include a substrate coated with a silicone-based material or a fluorine-based material, and a printing blanket cylinder made of silicone.

  For example, in the case of a substrate to which a silicone material is applied, after applying the thermosetting composition to the substrate, the substrate is treated at 80 ° C. to 120 ° C. for about 1 to 5 minutes by a hot plate or an oven, and the solvent is evaporated and dried. .

  The dried film is heat-cured in an oven at 120 ° C. to 250 ° C. for about 10 minutes to 60 minutes. Thus, a transparent organic film can be obtained.

  On the other hand, in the case of flexographic printing, the thermosetting composition supplied to the anilox roll is attached to a relief plate made of rubber or plastic and transferred to a film substrate or the like having a lower surface energy.

  The coating thus obtained is treated on a hot plate or oven at 80 ° C. to 120 ° C. for about 1 to 5 minutes, and the solvent is evaporated to dryness.

  The dried film is heat-cured in an oven at 120 ° C. to 250 ° C. for about 10 minutes to 60 minutes. Thus, a transparent organic film can be obtained.

  In the case of gravure offset printing, of the thermosetting composition supplied to the entire plate cylinder having projections and depressions, the thermosetting composition in the convex portions is removed by a doctor blade. Further, the thermosetting composition remaining in the concave portion of the plate cylinder is transferred to a substrate having a low surface energy.

  The coating thus obtained is treated on a hot plate or oven at 80 ° C. to 120 ° C. for about 1 to 5 minutes, and the solvent is evaporated to dryness.

  The dried film is heat-cured in an oven at 120 ° C. to 250 ° C. for about 10 minutes to 60 minutes. Thus, a transparent organic film can be obtained.

  Further, in the case of reverse offset printing, a thermosetting composition is applied to a silicone blanket cylinder by a slit coat, and a waiting time is allowed to dry the solvent to a predetermined level. After that, a blanket is pressed against a glass cliche having an uneven pattern formed on the surface, and unnecessary portions are transferred to the cliche and removed. Further, the thermosetting composition remaining on the blanket is transferred to a glass substrate or the like.

  The coating thus obtained is treated on a hot plate or oven at 80 ° C. to 120 ° C. for about 1 to 5 minutes, and the solvent is evaporated to dryness.

  The dried film is heat-cured in an oven at 120 ° C. to 250 ° C. for about 10 minutes to 60 minutes. Thus, a transparent organic film can be obtained.

  After the transparent organic film formed as described above, a transparent electrode may be formed as an upper layer, and after performing patterning by etching, a film for performing an alignment treatment may be formed.

  The transparent organic film is used for a display element using a liquid crystal or the like. For example, a liquid crystal display element, an element substrate having a transparent organic film provided on a substrate as described above, and a color filter substrate, which is a counter substrate, are pressure-bonded in alignment, and then heat-treated to combine and face each other. It is manufactured by injecting liquid crystal between substrates and sealing the injection port.

  Alternatively, after the liquid crystal is sprayed on the element substrate, the element substrate can be manufactured by overlapping the element substrates and sealing the liquid crystal so that the liquid crystal does not leak. The display element is a display element manufactured in this manner. You may.

  In this manner, the transparent organic film having a high refractive index, formed of the thermosetting composition of the present invention, can be used for a liquid crystal display device. The liquid crystal used in the liquid crystal display device of the present invention, that is, the liquid crystal compound and the liquid crystal composition are not particularly limited, and any liquid crystal compound and liquid crystal composition can be used.

  Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.

[Synthesis Example 1] Synthesis of polymer (A1) In a four-necked flask equipped with a stirrer, propylene glycol monomethyl ether as a solvent, FM-0721 as monomer (a1), 9-vinylcarbazole as monomer (a2), and monomer (a3) And benzyl methacrylate as the monomer (a4) at the following weight and heated at 110 ° C. for 2 hours to carry out polymerization. As the polymerization initiator, 2,2′-azobis (2,4-dimethylvaleronitrile) was used.
Propylene glycol monomethyl ether 30.00g
FM-0721 (a1) 0.15 g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
5.25 g of benzyl methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The solution was cooled to room temperature to obtain a polymer (A1) solution.

  A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A1) was 13,700.

[Synthesis Example 2] Synthesis of Polymer (A2) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
FM-0721 (a1) 0.75 g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
4.65 g of benzyl methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A2) solution. The weight average molecular weight of the obtained polymer (A2) determined by GPC analysis (polystyrene standard) was 12,000.

[Synthesis Example 3] Synthesis of polymer (A3) Propylene glycol monomethyl ether 30.00 g
FM-0721 (a1) 3.00 g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
Benzyl methacrylate (a4) 2.40 g
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A3) solution. The weight average molecular weight of the obtained polymer (A3) determined by GPC analysis (polystyrene standard) was 12,500.

[Synthesis Example 4] Synthesis of polymer (A4) Propylene glycol monomethyl ether 30.00 g
FM-0721 (a1) 0.15 g
9-vinylcarbazole (a2) 6.00 g
Methacrylic acid (a3) 2.10 g
6.75 g of benzyl methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A4) solution. The weight average molecular weight of the obtained polymer (A4) determined by GPC analysis (polystyrene standard) was 13,000.

[Synthesis Example 5] Synthesis of polymer (A5) Propylene glycol monomethyl ether 30.00 g
FM-0721 (a1) 0.15 g
7.50 g of 9-vinylcarbazole (a2)
Acrylic acid (a3) 2.10 g
5.25 g of benzyl methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A5) solution. The weight average molecular weight of the obtained polymer (A5) determined by GPC analysis (polystyrene standard) was 11,800.

[Synthesis Example 6] Synthesis of polymer (A6) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
FM-0721 (a1) 0.15 g
7.50 g of 9-vinylcarbazole (a2)
Maleic anhydride (a3) 2.10 g
5.25 g of benzyl methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A6) solution. The weight average molecular weight of the obtained polymer (A6) determined by GPC analysis (polystyrene standard) was 12,300.

[Synthesis Example 7] Synthesis of polymer (A7) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
FM-0721 (a1) 0.15 g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
5.25 g of naphthol methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A7) solution. The weight average molecular weight of the obtained polymer (A7) determined by GPC analysis (polystyrene standard) was 12,300.

[Synthesis Example 8] Synthesis of polymer (A8) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
FM-0721 (a1) 0.15 g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
Adamantyl methacrylate (a4) 5.25 g
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A8) solution. The weight average molecular weight of the obtained polymer (A8) determined by GPC analysis (polystyrene standard) was 12,300.

[Synthesis Example 9] Synthesis of polymer (A9) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
FM-0711 (a1) 0.75 g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
4.65 g of benzyl methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A9) solution. The weight average molecular weight of the obtained polymer (A9) determined by GPC analysis (polystyrene standard) was 12,300.

[Synthesis Example 10] Synthesis of polymer (A10) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was carried out.
Propylene glycol monomethyl ether 30.00g
FM-0725 (a1) 0.04 g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
5.36 g of benzyl methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A10) solution. The weight average molecular weight of the obtained polymer (A10) determined by GPC analysis (polystyrene standard) was 12,300.

[Synthesis Example 11] Synthesis of polymer (A11) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
TM-0701 (a1) 0.75 g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
4.64 g of benzyl methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (A11) solution. The weight average molecular weight of the obtained polymer (A11) determined by GPC analysis (polystyrene standard) was 12,300.

[Comparative Synthesis Example 1] Synthesis of polymer (B1) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
Benzyl methacrylate (a4) 5.40 g
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (B1) solution. The weight average molecular weight of the obtained polymer (B1) determined by GPC analysis (polystyrene standard) was 9,100.

[Comparative Synthesis Example 2] Synthesis of polymer (B2) In the same manner as in Synthesis Example 1, the following components were charged at the following weight and polymerized. Propylene glycol monomethyl ether 30.00 g
FM-0721 (a1) 0.20 g
Methacrylic acid (a3) 2.10 g
12.80 g of benzyl methacrylate (a4)
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (B2) solution. The weight average molecular weight of the obtained polymer (B2) determined by GPC analysis (polystyrene standard) was 10,200.

[Comparative Synthesis Example 3] Synthesis of Polymer (B3) In the same manner as in Synthesis Example 1, the following components were charged at the following weight and polymerized. Propylene glycol monomethyl ether 30.00 g
7.50 g of 9-vinylcarbazole (a2)
Acrylic acid (a3) 2.10 g
Benzyl methacrylate (a4) 5.40 g
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (B3) solution. The weight average molecular weight of the obtained polymer (B3) determined by GPC analysis (polystyrene standard) was 10,800.

[Comparative Synthesis Example 4] Synthesis of polymer (B4) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
7.50 g of 9-vinylcarbazole (a2)
Maleic anhydride (a3) 2.10 g
Benzyl methacrylate (a4) 5.40 g
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (B4) solution. The weight average molecular weight of the obtained polymer (B4) determined by GPC analysis (polystyrene standard) was 11,300.

[Comparative Synthesis Example 5] Synthesis of polymer (B5) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
Naphthol methacrylate (a4) 5.40 g
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (B5) solution. The weight average molecular weight of the obtained polymer (B5) determined by GPC analysis (polystyrene standard) was 12,700.

[Comparative Synthesis Example 6] Synthesis of polymer (B6) In the same manner as in Synthesis Example 1, the following components were charged at the following weights, and polymerization was performed.
Propylene glycol monomethyl ether 30.00g
7.50 g of 9-vinylcarbazole (a2)
Methacrylic acid (a3) 2.10 g
Adamantyl methacrylate (a4) 5.40 g
0.80 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

  The same treatment as in Synthesis Example 1 was performed to obtain a polymer (B6) solution. The weight average molecular weight of the obtained polymer (B6) determined by GPC analysis (polystyrene standard) was 12,700.

[Example 1]
[Production of thermosetting composition]
Propylene glycol monomethyl ether and butyl acetate were used as diluting solvents, and the polymer (A1) obtained in Synthesis Example 1 was mixed and dissolved at the following weight to obtain a thermosetting composition having a solid content of 20% by weight. Components other than the solvent and the diluting solvent used in the synthesis of the polymer were defined as solids.
Propylene glycol monomethyl ether 0.33 g
3.66 g of butyl acetate
5.00 g of polymer (A1) solution
VG3101L 0.17g
S510 0.17g
S-611 0.01 g

[Examples 2 to 11 and Comparative Examples 1 to 6] Production of thermosetting compositions Examples 2 to 11 were prepared by mixing and dissolving each component according to Table 1 in the same manner as in Example 1, and Comparative Examples 1 to 6 In the same manner as in Example 1, the components were mixed and dissolved in accordance with Table 2 to obtain a thermosetting composition having a solid content of 20%. When adding a surfactant, 1000 ppm was added to the total amount of the mixed composition.

表１および表２中の数値は、界面活性剤以外は重量部である。ポリマーの重量は各ポリマー溶液の固形分濃度を３３重量％として計算した固形分の重量部である。

The numerical values in Tables 1 and 2 are parts by weight except for the surfactant. The weight of the polymer is a part by weight of the solid content calculated on the assumption that the solid content concentration of each polymer solution is 33% by weight.

[Method of evaluating thermosetting composition]
1) Formation of transparent film and measurement of film thickness after drying The thermosetting composition was spin-coated on a glass substrate at 500 rpm for 10 seconds, and dried on a hot plate at 80 ° C for 2 minutes. This substrate was post-baked in an oven at 150 ° C. for 30 minutes to form a transparent film having a thickness of 1.0 ± 0.2 μm. The film thickness was measured using a stylus type film thickness meter (trade name: P-16 +, KLA-Tencor Japan Co., Ltd.), and the average of three measurements was taken as the film thickness.

2) Transparency The thermosetting composition was applied on a glass substrate by a spin coater so that the film thickness after firing was 1.0 μm, and then heated at 150 ° C. for 30 minutes to obtain a cured film. To obtain a glass substrate. On the glass substrate with the cured film, the light transmittance of the cured film alone at a wavelength of 400 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (trade name: V-670 JASCO Corporation). When the light transmittance was 95% or more, it was determined that the transparency was good.

3) Absolute refractive index Using a reflection spectral thickness meter (trade name: FE-3000; Otsuka Electronics Co., Ltd.), a glass substrate on which a transparent film is formed is prepared, and a reflection spectrum in a wavelength range of 380 to 800 nm is measured. And a refractive index at 589 nm (absolute refractive index) was derived. When the absolute refractive index was less than 1.6, the evaluation was x, and when the absolute refractive index was 1.6 or more, the evaluation was o.

4) Surface tension The surface tension of the composition was measured by a pendant drop method (hanging drop method) using a surface tensiometer (trade name: Dropmaster DM-500, Kyowa Interface Science Co., Ltd.).

5) Silicone plate applicability The applicability to a substrate having low surface energy was confirmed by the applicability to a silicone blanket. The thermosetting composition was applied to the blanket, and the presence or absence of repelling was visually checked. When the sheet was repelled, the result was ×, and when the film was uniformly applied, the result was ○.

  Tables 3 and 4 show the results obtained by the above evaluation methods for the thermosetting compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 6.

  As is clear from Tables 3 and 4, Examples 1 to 11 can apply an organic film having a higher refractive index on the silicone plate as compared with Comparative Examples 1 to 6.

  According to the above results, by using an acrylic polymer material having a nitrogen-containing heterocyclic compound and a dimethylsiloxane structure, the heat which can be applied to a substrate having a high refractive index and a low surface energy can be formed on the formed organic film. The results show that a curable composition can be provided, which demonstrates the rationality and significance of the configuration of the present invention and the superiority over the prior art.

  The thermosetting composition of the present invention can be used, for example, for forming an insulating film or an antireflection film used for a liquid crystal display device.

Claims (8)

A monomer (a1) represented by the formula (1), a monomer (a2) having a heterocyclic ring represented by the formula (2), and a monomer having a carboxyl group or a carboxylic anhydride group (—CO—O—CO—) (A3) and a polymer (A) obtained by copolymerizing other monomers (a4) other than (a1), (a2), and (a3 ) ;
Here, when the total amount of the monomers is 100 parts by weight, the proportion of the monomer (a1) represented by the formula (1) is 0.1 to 20 parts by weight, which is represented by the formula (2). The proportion of the monomer (a2) to be contained is 40 to 50 parts by weight .

(In the formula (1), R ¹ is hydrogen or —CH ₃ , and R ^{2 to} R ⁶ are each independently an alkyl having 1 to 5 carbons, an alkoxy having 1 to 5 carbons or an alkoxy having 1 to 3 carbons. Trialkylsiloxy with alkyl, m is an integer from 1 to 10, and n is an integer from 0 to 150.)

(In the formula (2), X is a single bond or —COO—, Y is a single bond or an alkylene having 1 to 5 carbon atoms, R ⁷ is hydrogen or —CH ₃ , and R ^{8 to} R ¹⁵ are are each independently hydrogen, _halogen, -CN, -CF _3, -OCF 3, an -OH, alkyl of 1-9 carbon atoms, or alkoxy of 1 to 9 carbon atoms, said alkyl having 1 to 9 carbon atoms May have any of —CH ₂ — replaced with —COO—, —OCO—, or —CO—, any hydrogen may be replaced with halogen, and the alkoxy having 1 to 9 carbon atoms is optional. May be replaced by halogen. When X is -COO-, the carbonyl group (-CO-) is adjacent to the double bond.) In the formula (1), the monomer (a1) is a compound represented by the formula (1), wherein R ¹ is —CH ₃ , R ^{2 to} R ⁵ are each —CH ₃ , R ⁶ is alkyl having 1 to 10 carbons, m is an integer of 1 to 5, The polymer (A) according to claim 1, wherein n is an integer of 1 to 150. Monomers having a heterocyclic ring (a2) is, in the formula (2), both the R ⁷ to R ¹⁵ are hydrogen, X and Y are both compounds is a single bond, a polymer according to claim 1 or 2 (A). The monomer (a3) having a carboxyl group or a carboxylic anhydride group (—CO—O—CO—) is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, and itaconic anhydride. The polymer (A) according to any one of claims 1 to 3 . The other monomer (a4) is at least one selected from the group consisting of benzyl acrylate, benzyl methacrylate, methyl benzyl methacrylate, naphthyl acrylate, naphthyl methacrylate, methyl naphthyl methacrylate, adamantyl acrylate, adamantyl methacrylate, methyl adamantyl methacrylate, and N-substituted maleimide. The polymer (A) according to any one of claims 1 to 4 , which is one of: A thermosetting composition comprising the polymer (A) according to any one of claims 1 to 5 , a silane coupling agent (B), and an organic solvent (C). A cured product formed using the thermosetting composition according to claim 6 . An organic film formed using the thermosetting composition according to claim 6 .