JP5670533B1 - Thermosetting resin composition, cured product thereof, and display member using the same - Google Patents

Abstract

An object of the present invention is to achieve excellent balance between insulation and heat resistance, surface flatness, adhesion and curability at a high level, as well as excellent high-temperature insulation resistance and solvent resistance required during the manufacturing process. A thermosetting resin composition, a cured product thereof, and a display member using the same are provided. At least selected from the group consisting of (a) a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, (c) a black colorant, and (d) barium sulfate, silica, and talc. 1 type of thermosetting resin composition characterized by including. [Selection figure] None

Description

  The present invention relates to a thermosetting resin composition that can achieve a high level of surface flatness, adhesion, and curability, and that can form a cured product that has both high-temperature insulation resistance and solvent resistance, and the cured product thereof. There is provided a display member comprising:

  2. Description of the Related Art In recent years, touch panel type input devices (hereinafter simply referred to as “touch panels”) are incorporated as operation units on the screens of various electronic devices such as mobile phones, personal portable information terminals, and notebook computers. In a liquid crystal display device including a touch panel, the touch panel is mounted and fixed on the polarizing plate of the display panel of the liquid crystal display device after alignment. By the way, when viewing the liquid crystal display from the user side on mobile phones and tablets, information or images are not displayed on the entire surface of the transparent glass, but are painted black or white so as to partition the display on the outer periphery of the substrate. There is a frame part, and information is displayed inside the frame part.

  Although this frame portion is called a decoration portion, it has a function of partitioning the display portion into a quadrangular shape and concealing it so that a portion that is inconvenient (such as a wiring portion for a touch panel) cannot be seen. The decoration part is also very important as an exterior decoration member of the portable terminal device display part as something that can be directly touched by the eyes. There is a need for a thermosetting resin composition that can achieve good balance at a high level and that can form a cured product that satisfies both high-temperature insulation resistance and solvent resistance required for processing.

  Conventionally, as such a thermosetting resin composition, for example, Patent Document 1 discloses a composition containing (A) a bismaleimide-triazine resin, (B) an epoxy resin, and (C) carbon black. Is disclosed.

JP-A-62-266805

In recent years, the level of adhesion required for a curable resin composition containing an epoxy resin has increased, and in particular, both curability and adhesion are excellent, and both high-temperature insulation resistance and solvent resistance are compatible. There has been a demand for a curable resin composition that can be used. However, the conventional curable composition described in Patent Document 1 can achieve adhesion and curability at a high level in a well-balanced manner, and does not achieve both high-temperature insulation resistance and solvent resistance.
Therefore, the present invention is excellent in insulation and heat resistance, can achieve surface flatness, adhesion and curability at a high level in a well-balanced manner, and has high temperature insulation resistance and solvent resistance required during the manufacturing process. It is an object of the present invention to provide an excellent thermosetting resin composition, a cured product thereof, and a display member using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a specific carboxyl group-containing resin, an epoxy resin, a black colorant, and a specific insulating filler is insulative and heat resistant. The present invention was completed by finding excellent adhesion and solvent resistance.
That is, the present invention provides the following (1) to (5).

(1) (a) at least one selected from the group consisting of a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, (c) a black colorant, and (d) barium sulfate, silica, and talc. A thermosetting resin composition comprising a seed.

(2) The thermosetting resin composition according to (1), further comprising (e) a colorant other than black.

(3) The thermosetting resin composition according to (1) or (2), further comprising a silane coupling agent.

(4) The cured product of the thermosetting resin composition according to any one of (1) to (3), which is formed on a substrate.

(5) A display member comprising the cured product according to (4).

  According to the present invention, heat that can form a cured product that is excellent in insulation, heat resistance, can achieve surface flatness, adhesion, and curability at a high level in a balanced manner, and that can achieve both high-temperature insulation resistance and solvent resistance. A curable resin composition can be provided. Moreover, the curable resin composition of this invention is suitable as decorating ink used for a display apparatus.

The curable resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) includes (a) a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, and (c) black. It contains a colorant and (d) at least one selected from the group consisting of barium sulfate, silica and talc (hereinafter also referred to as “insulating filler”).
Hereinafter, each component used for the composition of this invention is demonstrated in detail.

[(A) Carboxyl group-containing resin as thermosetting component]
The carboxyl group-containing resin contained in the thermosetting resin composition of the present invention is a component for thermosetting reaction with an epoxy resin, and specific examples thereof include the resins listed below.
(1) a carboxyl group-containing copolymer resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond;
(2) Glycidyl (meth) acrylate or 3,4-epoxycyclohexyl is a copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond. A carboxyl group-containing resin obtained by adding an ethylenically unsaturated group as a pendant by a compound having an epoxy group and an unsaturated double bond, such as methyl (meth) acrylate, or (meth) acrylic acid chloride,
(3) Copolymerization of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound having an unsaturated double bond other than that A carboxyl group-containing resin obtained by reacting an unsaturated carboxylic acid such as (meth) acrylic acid with the coalescence and reacting the resulting secondary hydroxyl group with a polybasic acid anhydride,
(4) To a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having an unsaturated double bond other than that, a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; A carboxylic acid-containing resin obtained by reacting a compound having an unsaturated double bond;
(5) a carboxyl group-containing resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(6) After reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative, the resulting carboxylic acid is reacted with a compound having an epoxy group and an unsaturated double bond in one molecule. Carboxyl group-containing resin obtained by
(7) a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule, and a compound having one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group A carboxyl group-containing resin obtained by reacting a reaction product with a saturated or unsaturated polybasic acid anhydride,
(8) Saturated or unsaturated polybasic with respect to the primary hydroxyl group in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in one molecule. A carboxyl group-containing resin obtained by reacting an acid anhydride, and (9) a carboxylic acid-containing resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional epoxy resin and then reacting with a polybasic acid anhydride. Furthermore, examples include, but are not limited to, a carboxyl group-containing resin obtained by reacting a compound having one oxirane ring and one or more ethylenically unsaturated groups in the molecule.

  Among these examples, preferred are the carboxyl group-containing resins (2), (5), (7), and (9), and particularly the carboxyl group-containing resin (5) is thermosetting. From the viewpoint of cured film characteristics, it is preferable. Here, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  The acid value of the carboxyl group-containing resin is preferably in the range of 10 to 150 mgKOH / g, more preferably in the range of 30 to 100 mgKOH / g. When the acid value of the carboxyl group-containing resin is 10 mgKOH / g or more, the adhesion becomes better, and when it is 150 mgKOH / g or less, the thermal stability of the cured product is further improved.

  Moreover, although the mass average molecular weight of the said carboxyl group-containing resin changes with resin frame | skeleton, generally what is in the range of 1000-30000, Furthermore, 5000-20000 is preferable. When the mass average molecular weight is 1000 or more, tack-free performance is further enhanced, and the hardness of the cured product is further sufficient. Further, when the mass average molecular weight is 20000 or less, it becomes possible to achieve better adhesion and curability.

  The blending amount of such a carboxyl group-containing resin is preferably 15 to 60 parts by mass, more preferably 25 to 50 parts by mass with respect to 100 parts by mass of the nonvolatile content of the entire composition. When the amount is 15 parts by mass or more, the deep-part curability becomes more sufficient, and when the amount is 50 parts by mass or less, the viscosity becomes optimal and the applicability is not lowered.

[(B) Epoxy resin]
The (b) epoxy resin used in the thermosetting resin composition of the present invention is a component for imparting heat resistance, and preferably contains an epoxy compound having an aromatic skeleton. As for the epoxy compound which has an aromatic skeleton, only 1 type may be used and 2 or more types may be used together. Moreover, it is preferable that an epoxy compound contains the epoxy compound which has an alicyclic skeleton from a viewpoint of improving the adhesiveness of a glass base material and a molded object further. As for the epoxy compound which has alicyclic skeleton, only 1 type may be used and 2 or more types may be used together. Further, a modified epoxy resin may be used in combination.

Examples of the epoxy compound having an aromatic skeleton include bisphenol A type epoxy compound, bisphenol F type epoxy compound, cresol novolac type epoxy compound, phenol novolac type epoxy compound, polybasic acid compound having aromatic skeleton and epichlorohydrin. Examples thereof include a glycidyl ester type epoxy compound obtained by reaction and a glycidyl ether type epoxy compound having an aromatic skeleton. From the viewpoint of further enhancing the strength and heat resistance of the molded article, the epoxy compound having an aromatic skeleton preferably has a bisphenol skeleton or a novolak skeleton.
The epoxy equivalent of the epoxy compound having an aromatic skeleton is preferably 100 or more and 1000 or less. When the epoxy equivalent is 100 or more, the moldability of the curable composition is further improved. When the epoxy equivalent is 1000 or less, the strength of the molded product is further increased.

  Specific examples of the epoxy compound having the alicyclic skeleton include 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxy. Cyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, dicyclopentadiene dioxide, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9-diepoxy limonene, ε -Caprolactone-modified tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, etc. Can be mentioned. From the viewpoint of further improving the heat resistance of the molded product, an epoxy compound having an alicyclic skeleton is an addition of 1,2-epoxy-4- (2-oxiranyl) cyclohexane to 2,2-bis (hydroxymethyl) -1-butanol. Things are preferred.

  Examples of commercially available epoxy compounds having an alicyclic skeleton include PNE-177 (phenol novolac epoxy resin), CNE-200EL (cresol novolac epoxy resin), BNE200D75 (bisphenol) manufactured by Changchun Artificial Resin Co., Ltd. A-type novolac epoxy resin), Daicel Chemical Company's Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000, and a cyclo (cyclo) which is a (meth) acrylate compound having an epoxy group And methacrylate having a methyl glycidyl group such as MER A200, CYCLOMER M100, and MGMA, and Syracure manufactured by Dow Chemical Company. It is not limited to these.

  The compounding quantity of an epoxy compound is suitably adjusted so that it may harden | cure moderately by provision of heat, and is not specifically limited. The blending amount of the epoxy compound is preferably 10 parts by mass or more and 60 parts by mass or less, more preferably 20 parts by mass or more and 50 parts by mass or less, and further preferably 25 parts by mass with respect to 100 parts by mass of the (a) carboxyl group-containing resin. It is 45 parts by mass or more. When the blending amount of the epoxy compound is in the above range, the curable composition is more effectively cured by heating, and the heat resistance of the molded body is further increased.

[(C) Black colorant]
The black colorant contained in the composition of the present invention may be any black colorant as long as it is sufficiently black and does not chemically react with the carboxyl group-containing resin or epoxy resin. For example, CIPigment black 6, 7, 9 and 18 Carbon black colorants such as CIPigment black 8, 10 etc., iron colorants such as CIPigment black 11, 12 and 27, Pigment Brown 35 etc .: for example Toda KN-370 iron oxide manufactured by Kogyo Co., Ltd., 13M titanium black manufactured by Mitsubishi Materials, anthraquinone-based colorant represented by CIPigment black 20, etc., cobalt oxide-based colorants represented by CIPigment black 13, 25, 29, etc. Copper oxide colorants such as CIPigment black 15 and 28, manganese colorants such as CIPigment black 14 and 26, CIPigment black 23, etc. Antimony oxide colorant shown, nickel oxide colorant shown as CIPigment black 30, etc., perylene colorant shown as CIPigment black 31, 32, aniline colorant shown as Pigment Black 1, and sulfurized Molybdenum and bismuth sulfide can also be exemplified as suitable colorants. These colorants are used alone or in appropriate combination.

Particularly preferred is carbon black, such as carbon black manufactured by Mitsubishi Chemical Corporation, M-40, M-45, M-50, MA-8, MA-100, carbon black 1255 manufactured by Columbia Chemical Company, etc. Can be mentioned.
If the blending amount of the black colorant is too large, the insulating property is lowered, leading to an increase in cost, and if it is too small, the color or non-transparency may be insufficient. Preferably, it is 1-25 mass parts with respect to 100 mass parts of non volatile matters of the thermosetting composition of this invention, More preferably, it is 3-20 mass parts.

[(D) At least one of barium sulfate, silica, and talc]
(D) At least one insulating filler selected from the group consisting of barium sulfate, silica and talc used in the thermosetting resin composition of the present invention improves the high-temperature insulation resistance of the cured product. In addition to increasing the surface flatness, suppressing deformation due to heating in the processing process and maintaining the surface flatness, it is possible to effectively prevent scratches and microcracks. In particular, from the viewpoint of improving surface flatness, the insulating filler preferably contains barium sulfate. On the other hand, from the viewpoint of preventing microcracks, the insulating filler more preferably contains at least one of talc and silica.

As the particle size of the insulating filler, the average particle size of barium sulfate is 0.05 to 5.00 μm, the average particle size of silica is 0.1 to 5.0 μm, and the average particle size of talc is It is preferable that it is 0.1-5.0 micrometers. When the average particle size of the insulating filler is not more than the upper limit of the above range, dispersibility and surface flatness are further improved. Moreover, sclerosis | hardenability and high temperature resistance improve more that the average particle diameter of an insulating filler is more than the lower limit of said range.
The total blending amount of the insulating filler is 30 to 70 parts by mass because the high-temperature insulation resistance is further improved with respect to 100 parts by mass in total of the (a) carboxyl group-containing resin and (b) the epoxy resin. It is preferable that it is 40-60 mass parts. Commercially available barium sulfate, silica, and talc may be used.

Commercially available products of barium sulfate include precipitated barium sulfate # 100, precipitated barium sulfate # 300, precipitated barium sulfate SS-50, BARIACE B-30, BARIACE B-31, BARIACE B-32, BARIACE B-33, BARIACE B-34, BARIFINE BF-1, BARIFINE BF-10, BARIFINE BF-20, BARIFINE BF-40 (manufactured by Sakai Chemical Industry), surface-treated barium sulfate B-30, B-34 (manufactured by Sakai Chemical Industry) , W-1, W-6, W-10, C-300 (manufactured by Takehara Chemical Industry Co., Ltd.) and the like.
As silica commercial products, Aerosil 50, Aerosil 200, Aerosil 380, Aerosil A300 and other A series, RY300 and other RY series (made by Nippon Aerosil Co., Ltd.); WACKER HDK S13, WACKER HDK V15, WACKER HDK N20 (all Asahi Kasei) “Fine Seal B” (trade name, manufactured by Tokuyama), “Fine Seal” (manufactured by Tokuyama), “Siricia” (manufactured by Fuji Silysia Chemical), Snowtex UP, Snowtex OUP (Nissan Chemical Industries) Nipsil L-300, Nipsil KQ (manufactured by Nippon Silica Kogyo Co., Ltd.) and the like.
As a commercial item of talc, LMS-100, LMS-200, LMS-300, LMS-3500, LMS-400, LMP-100, PKP-53, PKP-80, PKP-81 (manufactured by Fuji Talc Industrial Co., Ltd.), D-600, D-800, D-1000, P-2, P-3, P-4, P-6, P-8, SG-95 (made by Nippon Talc Co., Ltd.), etc. are mentioned. These can be used alone or in combination.

〔Silane coupling agent〕
The thermosetting resin composition of the present invention preferably further contains a silane coupling agent. Use of the coupling agent not only provides adhesion to a glass substrate that can withstand boiling water for 1 hour, but also improves adhesion between the thermosetting component and the insulating filler in the molded body. As for a silane coupling agent, only 1 type may be used and 2 or more types may be used together.
Although it does not specifically limit as a silane coupling agent, For example, generally an epoxy silane coupling agent, an aminosilane coupling agent, a cationic silane coupling agent, a vinyl silane coupling agent, an acrylic silane coupling agent, a mercaptosilane System coupling agents and composite coupling agents of these.

It is preferable that the compounding quantity of a silane coupling agent is 0.1-10 mass parts with respect to a total of 100 mass parts of said (a) carboxyl group containing resin and (b) epoxy resin. When the amount is 0.1 parts by mass or more, the effect becomes more apparent. When the amount is 10 parts by mass or less, the thermosetting resin composition does not increase in viscosity and is advantageous in terms of cost. More preferably, it is 8 mass parts or less, More preferably, it is 1-5 mass parts.
Examples of commercially available silane coupling agents include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM- 503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all trade names, manufactured by Shin-Etsu Silicone), Silquest A-186, Silquest A-187 (any Product name, Momentive performance Materials Co., Ltd.) and the like. These can be used alone or in combination of two or more.

  In addition, the composition of the present invention may contain the following additives as necessary in order to adjust the desired physical properties or production conditions used in the production process.

[Curing catalyst]
In order to accelerate the curing rate or to lower the heating temperature, a curing catalyst can be blended. Examples of the curing catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Examples include amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available curing catalysts include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U- CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), ▲ Ning ▼ NNK 110 Dyhard (Dicyandiamide), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic) Amidine compounds and salts thereof). These may be used alone or in admixture of two or more.

[Light stabilizer]
Furthermore, a hindered amine light stabilizer can be blended with the thermosetting resin composition of the present invention for the purpose of reducing photodegradation of the cured product.
As this hindered amine light stabilizer, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by BASF Japan); MARK LA-57, LA-62, LA-67, LA-63, LA-68 ( These are all manufactured by ADEKA); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are manufactured by Sankyo Lifetech).

[Adhesion promoter]
In the thermosetting resin composition of the present invention, an adhesion promoter can be used in order to improve adhesion between layers or adhesion to a substrate such as polyimide. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Co., Ltd.), 3-morpholino. Methyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group Examples thereof include benzotriazole and silane coupling agents. These may be used alone or in combination of two or more.

[Antioxidant]
In order to prevent oxidation, the curable resin composition of the present invention decomposes the generated radical scavenger and the generated peroxide into harmless substances so as not to generate new radicals. Antioxidants such as peroxide decomposers can be included. The antioxidant used in the present invention can prevent oxidative deterioration of a carboxyl group-containing resin or an epoxy resin, and can suppress yellowing. Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. Of these, phenolic antioxidants are particularly preferred. An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

[Colorants other than black colorants]
Moreover, 1 or more types of coloring agents other than a black coloring agent can be added as needed. As other colorants, known and commonly used colorants can be used, and any of pigments, dyes, and pigments may be used. For example, a blue colorant, a red colorant, a purple colorant, a yellow colorant, a green colorant, a white colorant, an orange colorant, and a brown colorant can be used. As a particularly preferable one, at least one or both of a blue colorant and a red colorant can be used.

Blue colorants include compounds such as pigments such as phthalocyanine and anthraquinone pigments, and compounds classified as solvent and dyes. Specifically, the color index numbers are as follows: Can be mentioned.
Pigment systems: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60;
Dye system: Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 ;
Etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. The ones with the correct color index numbers.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269;
Disazo: Pigment Red 37, 38, 41;
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1, 68
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208;
Perylenes: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224;
Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272;
Condensed azo: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242;
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207;
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

  Specific examples of purple colorants include Pigment Violet 19, 23, 29, 32, 36, 37, 38, 42; Solvent Violet 13, 36; CIPigment brown 25; CIPigment black 1, CI Pigment black 7, Pigment Violet 37 (dioxazine type) etc. are mentioned.

Examples of the yellow colorant include monoazo series, disazo series, condensed azo series, benzimidazolone series, isoindolinone series, anthraquinone series and the like, and specific examples include the following colorants. Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183;
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198;
Condensed azo: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180;
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181;
Isoindolinone: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185;
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

  Examples of the green colorant include phthalocyanine series and anthraquinone series. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

  Specific examples of the orange colorant include CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, and CI Pigment Orange. 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI pigment orange 71, CI pigment orange 73, and the like.

  Specific examples of the brown colorant include C.I. Pigment Brown 23 and C.I. Pigment Brown 25.

  Examples of the white colorant include zinc oxide shown in CI Pigment White 4, titanium oxide shown in CI Pigment White 6, and zinc sulfide shown in CI Pigment White 7, but particularly from the viewpoint of coloring power and non-toxicity. Preferred is titanium oxide, for example, TR-600, TR-700, TR-750, TR-840, Ishihara Sangyo R-550, R-580, R-630, R-820, CR manufactured by Fuji Titanium Industry Co., Ltd. -50, CR-60, CR-90, rutile titanium oxide such as KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd., TA-100, TA-200, TA-300 manufactured by Fuji Titanium Industry Co., Ltd. TA-500, A100, A220 manufactured by Ishihara Sangyo Co., Ltd., KA-15, KA-20, KA-35, KA-90 manufactured by Titanium Industry Co., Ltd. Emissions, and the like.

[Organic solvent]
Furthermore, the thermosetting resin composition of this invention can use an organic solvent as a diluent for the dilution of a composition, or the viscosity adjustment for apply | coating to a board | substrate or a carrier film.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture. The blending amount of the organic solvent is not particularly limited, and may be appropriately added as necessary.

  The thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing method A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 50 to 300 ° C. by volatile drying (temporary drying).

[Wet dispersant]
The thermosetting resin composition of the present invention contains a wetting and dispersing agent in order to adjust the filling property of the composition into the minute recesses, the surface smoothness of the cured film, the defoaming property or surface tension of the composition. be able to. Examples of the commercially available products include BYK-110, BYK-111, BYK-183, etc. manufactured by Big Chemie GMBH. The wetting and dispersing agents may be used alone or in combination of two or more. The amount of the wetting and dispersing agent is preferably 0.01 to 5 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the total composition (solid content).

[Leveling agent]
Examples of leveling agents include polyacrylate polymers, polyether-modified dimethylpolysiloxane copolymers, polyester-modified dimethylpolysiloxane copolymers, polyether-modified methylalkylpolysiloxane copolymers, and aralkyl-modified methylalkylpolysiloxane copolymers. Examples thereof include a polymer and a polyether-modified methyl alkyl polysiloxane copolymer. Leveling agents may be used alone or in combination of two or more. As a compounding quantity of a leveling agent, Preferably it is 0.01-5 mass parts with respect to a total of 100 mass parts of said (a) carboxyl group containing resin and (b) epoxy resin, More preferably, it is 1-5 mass parts. is there.

[Defoamer]
Specific examples of the antifoaming agent include BYK (registered trademark) -054, -055, -057, and -1790 manufactured by Big Chemie Japan Co., Ltd. as an antifoaming agent comprising a commercially available non-silicone-based foam-breaking polymer solution. Examples of the silicone-based antifoaming agent include BYK (registered trademark) -063, -065, -066N, -067A, -077 manufactured by Big Chemie Japan, and dimethyl manufactured by Toray Dow Corning Silicone. Silicone oil SH200 series, etc. are mentioned.

〔substrate〕
As a board | substrate used for this invention, resin films, such as a polyimide film and PET film, a glass substrate, a ceramic substrate, a metal substrate, a wafer board, etc. can be mentioned. Among these, a polyimide film, a resin film such as a PET film, and a glass substrate can be preferably used. The material and shape of the substrate are selected depending on the intended use and performance of the molded product, and if necessary, two or more kinds of materials and shapes can be combined. From the viewpoint of adhesion, a glass substrate is more preferable.

[Production / mixing method]
The thermosetting resin composition of the present invention can be produced by uniformly mixing the above essential components and other additive components used as necessary. A known method can be used as the mixing method, and is not particularly limited. Any of a method of mixing without using a disperser and a method of mechanically mixing with various dispersers such as a kneader, a roll, an attritor, and a bead mill may be used.
As a particularly preferable method, the insulating filler, a solvent, and a dispersing agent are blended in advance, and the dispersion liquid dispersed with a disperser such as a roll mill is mixed with other curable resin components, or, if necessary, a roll mill again. A method obtained by dispersing, or by mixing a part of the resin component, the insulating filler, the solvent, and a dispersing agent in advance and dispersing with a dispersing machine such as a roll mill, or other curable resin component, or The method of obtaining by roll mill dispersion again as needed is mentioned.
In addition, when adding the colorant, from the viewpoint of dispersibility, the colorant dispersant is dissolved or finely dispersed in a mixed liquid in which powders such as the colorant are previously dispersed in water or an organic solvent. It is preferable to add and mix the solution.

[Coating method]
Thus, after preparing a thermosetting resin composition with a predetermined composition, it adjusts to the viscosity suitable for the coating method with an organic solvent, for example, on a base material, for example, a dip coat method, a flow coat method, a roll It can be applied by a method such as a coating method, a bar coater method, a screen printing method, or a curtain coating method. Among these, the flow coating method, the roll coating method, the bar coater method, and the screen printing method are preferably used, and the screen printing method is particularly preferably used.

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited only to these Examples. In the following description, “part” means part by mass and “%” means mass% unless otherwise specified.

(Examples 1-8, Reference Example 1 and Comparative Examples 1-3)
Various components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a thermosetting resin composition paste.

*1 UNIDIC R-2000、DIC株式会社製カルボキシル基含有樹脂 酸価：５２〜５６ＫＯＨｍｇ／ｇ、固形分：６５％
*2 PNE177、長春人造樹脂廠（股）製エポキシ樹脂 エポキシ当量：１７２〜１８２
*3 BNE200D75、長春人造樹脂廠（股）製エポキシ樹脂（固形分75％） エポキシ当量：１９８〜２１８
*4 1255、コロンビアケミカルカンパニー製
*5 B-30、堺化学工業社製 平均粒径：０．３μｍ 表面処理硫酸バリウム
*6 Nipsil L300 、日本シリカ工業社製 平均粒径２．２μｍ
*7 SG-95、日本タルク社製 含水ケイ酸マグネシウム 平均粒径（Ｄ５０）：２．５μｍ
*8 TNK 110 Dyhard、▲寧▼夏石嘴山民族化工（集団）公司製、ジシアンジアミド
*9 BYK-183、BYK-ChemieGmbH製、顔料親和性基をもつ高分子量ブロックコポリマー
*10 BYK-110、BYK-ChemieGmbH製、酸性基含有共重合体
*11 DEAC、Polynt UKLtd.製 ジエチレングリコールモノエチルエーテルアセテート
*12 BYK-354、BYK-ChemieGmbH製、ポリアクリレート系レベリング剤
*13 Silquest A-187 モメンティブ・パフォーマンス・マテリアルズ社製、有機シラン
*14 Cromophtal Violet B、BASFジャパン社製、紫色着色剤（Pigment Violet 37）
*15 OSTAPLAST YELLOW AGR、 Synthesia,a,s製、アントラキノン、黄色着色剤
*16 Irgazin DPP Red Ultra Opaque、BASFジャパン社製、赤色着色剤
*17 R-KB-6、バイエルＡＧ社製、アルミナにより表面処理されたルチル型酸化チタン

* 1 UNIDIC R-2000, DIC Corporation carboxyl group-containing resin Acid value: 52-56 KOHmg / g, solid content: 65%
* 2 PNE177, Changchun Artificial Resin (Crotch) epoxy resin Epoxy equivalent: 172-182
* 3 BNE200D75, an epoxy resin made by Changchun Plastic Resin Co., Ltd. (solid) (solid content 75%) Epoxy equivalent: 198-218
* 4 1255, manufactured by Columbia Chemical Company
* 5 B-30, manufactured by Sakai Chemical Industry Co., Ltd. Average particle size: 0.3 μm Surface-treated barium sulfate
* 6 Nipsil L300, Nippon Silica Kogyo Co., Ltd. average particle size 2.2μm
* 7 SG-95, manufactured by Nippon Talc Co., Ltd. Hydrous magnesium silicate Average particle diameter (D50): 2.5μm
* 8 TNK 110 Dyhard, ▲ Ning ▼ Natsuishi Foshan Ethnic Chemicals (Group) Ltd., Dicyandiamide
* 9 BYK-183, BYK-Chemie GmbH, high molecular weight block copolymer with pigment affinity group
* 10 BYK-110, BYK-Chemie GmbH, acidic group-containing copolymer
* 11 Diethylene glycol monoethyl ether acetate manufactured by DEAC, Polynt UK Ltd.
* 12 BYK-354, BYK-Chemie GmbH, polyacrylate leveling agent
* 13 Silquest A-187 Momentive Performance Materials, Organosilane
* 14 Cromophtal Violet B, manufactured by BASF Japan, purple colorant (Pigment Violet 37)
* 15 OSTAPLAST YELLOW AGR, manufactured by Synthesia, a, s, anthraquinone, yellow colorant
* 16 Irgazin DPP Red Ultra Opaque, manufactured by BASF Japan, red colorant
* 17 R-KB-6, manufactured by Bayer AG, rutile titanium oxide surface-treated with alumina

(Production of evaluation glass substrate)
The paste of the thermosetting resin composition obtained in Examples 1 to 8, Reference Example 1 and Comparative Examples 1 to 3 was screen printed using a 420-mesh screen, and the thickness of the cured film was about after drying. It is applied to a glass substrate (Soda Lime Glass manufactured by Central Glass Co., Ltd., thickness 0.7 mm) so as to be 6 μm, and the coated glass substrate is placed in an oven (DH-62 manufactured by Yamato Scientific Co., Ltd.) Baking was performed at 150 ° C. for 30 minutes to prepare an evaluation glass substrate on which a 6 μm cured film was formed.
Using the glass substrate on which the cured film of each thermosetting resin composition was formed, the following various properties were evaluated by the following methods.

<Light shielding (OD value)>
The glass substrate was attached to a transmission densitometer (manufactured by Sakata Inx Engineering, model number: X-Rite 361T, light source wavelength: 400-800 nm) with the film side facing the measuring device, and the OD value was evaluated as follows.
○: OD value is more than 4 △: OD value is 3 or more and 4 or less ×: OD value is less than 3

<Hot water resistance (hot water test)>
After immersing the glass substrate in boiling water at 100 ° C. for 60 minutes, the glass substrate was taken out and the surface moisture was removed, and then water intrusion or film deposition was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) is completely attached to the film side of the evaluation glass substrate, and immediately pulled apart while keeping one end of the tape at right angles to the glass substrate. The film was evaluated as follows.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: Water permeation or film peeling was confirmed.

<High temperature crack resistance>
The glass substrate is placed in a DENG YNG high-temperature oven (manufactured by Torigi Kikai Co., Ltd., model number: DH-400), heated at 280 ° C. for 1 hour, and electron microscope (50 times, Olympus, model number: MEASURING MICROSCOPE STM-MJS2). ) And the film surface of the glass substrate was evaluated as follows.
○: No crack △: Crack generation rate is more than 0 and less than 10% ×: Crack generation rate is 10% or more

<High temperature insulation resistance>
The glass substrate was baked in an oven at 280 ° C. for 60 minutes, and the positive electrode and negative electrode of the resistance meter (manufactured by Agilent Technologies, high resistance meter 4339B, component test fixture 16339A) were separated by a distance of 0.5 cm between the positive electrode and the negative electrode. The film resistance was measured under the conditions of voltage: 500 V, time: 60 seconds, and the film resistance was evaluated as follows.
○: Resistance of more than 10 ¹⁰ Ω Δ: Resistance of 10 ¹⁰ or more and 10 ⁸ Ω or less ×: Resistance of less than 10 ⁸ Ω

<Surface flatness>
Using a surface roughness meter (manufactured by Kosaka Laboratory, model number: SE3500), measurement length: 2.5 mm, longitudinal magnification: 1000, lateral magnification: 100, cutoff: 0.8 mm, speed: 0.5 mm / The surface roughness (maximum peak height, RmaxD) was measured three times under the condition of s, and evaluated as follows.
○: RmaxD is less than 1.5 μm Δ: RmaxD is 1.5 or more and less than 2 μm ×: RmaxD is 2 μm or more

<Pencil hardness test>
In accordance with JIS K5400 (1990 version), a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd., model number: C221A) about 4B to 9H pencil sharpened on each glass substrate so that the tip of the core becomes flat, Pressing at an angle of 45 °, the hardness of the pencil at which no film peeling occurred was recorded.

<Sulfuric acid resistance>
After immersing the glass substrate in a 10 vol% sulfuric acid aqueous solution at 25 ° C. for 30 minutes and washing with water, the moisture was removed, and the intrusion of water or the elution of the film was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) is completely attached to the film side of the evaluation glass substrate, and immediately pulled apart while keeping one end of the tape at right angles to the glass substrate. The film was evaluated as follows.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: Water permeation or film peeling was confirmed.

<Hydrochloric acid resistance>
The glass substrate was immersed in a 10 vol% hydrochloric acid aqueous solution at 25 ° C. for 30 minutes and washed with water. Then, the water was removed, and water intrusion or film elution was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) is completely attached to the film side of the evaluation glass substrate, and immediately pulled apart while keeping one end of the tape at right angles to the glass substrate. The film was evaluated as follows.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: Water permeation or film peeling was confirmed.

<Alkali resistance>
After immersing the glass substrate in a 10 vol% NaOH aqueous solution at 25 ° C. for 30 minutes and washing with water, the water was removed, and water permeation or film elution was confirmed visually. Next, a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) is completely attached to the film side of the evaluation glass substrate, and immediately pulled apart while keeping one end of the tape at right angles to the glass substrate. The film was evaluated as follows.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: Water permeation or film peeling was confirmed.

<Solvent resistance>
Use a lens paper to which a small amount of alcohol (95 vol%), dipropylene glycol monomethyl ether (DPM) (100 vol%), isopropyl alcohol (IPA) (100 vol%) is attached to a lens paper made by Kimberly Clark. After the glass substrate film was wiped about 20 times repeatedly, the surface of the film was visually observed.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: The film peeled off.

<Adhesion (cross-cut adhesion test method)>
In accordance with JISK5400, 100 1 mm grids (10 × 10) are made on the sample film, and a transparent adhesive tape (Nichiban Co., Ltd., width: 18 mm) is completely adhered on the grids. While keeping one end at a right angle to the glass substrate, it was pulled away instantaneously, and the number of grids remaining without being completely peeled was examined.
Table 2 below shows the results with the number of remaining grids as the numerator and the total number of grids (100) as the denominator.
○: 100% of the grid pattern remained.
(Triangle | delta): 95% or more and less than 100% remain | survived.
X: A grid of less than 95% remained.
The results of each evaluation test are summarized in Table 2.

  As shown in Table 2, all of Examples 1 to 8 according to this embodiment can achieve adhesion, surface flatness, and curability at a high level in a well-balanced manner, and achieve both high-temperature insulation resistance and solvent resistance. It was something to do. It is confirmed that the high-temperature insulation resistance is further improved particularly when the blending amount of barium sulfate is a specific amount (30 to 70 parts by mass with respect to 100 parts by mass of the total amount of the carboxyl group-containing resin and the epoxy resin). It was done. Meanwhile, Comparative Example 1 using a composition containing no carboxyl group-containing resin, Comparative Example 2 using a composition containing no barium sulfate, and Comparative Example 3 using a composition containing no epoxy resin are all used. In addition, adhesion, surface flatness, and curability cannot be achieved in a well-balanced manner at a high level, and high-temperature insulation resistance and solvent resistance cannot be achieved at the same time.

Claims (4)

(A) a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, (c) a black colorant, and (d) at least one selected from the group consisting of barium sulfate, silica and talc, A thermosetting resin composition for decorating a frame portion of a glass substrate for display , comprising a silane coupling agent. Furthermore, (e) coloring agents other than black are included, The thermosetting resin composition for decorating with respect to the frame part of the glass substrate for displays of Claim 1. The cured product of the thermosetting resin composition for decoration on the frame portion of the glass substrate for display according to claim 1 or 2, wherein the cured product is formed on a substrate.   A display member comprising the cured product according to claim 3.