JP5797716B2 - Thermosetting resin composition, cured product thereof, and display member using the same - Google Patents

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 silicone resin (A) having an alkenyl group and an alkoxy group at both ends, an organic titanium compound (B), and / or A curable resin composition containing a polysiloxane compound (C) having at least two Si-H bonds in one molecule and a hydrosilylation catalyst (D) is disclosed.

JP 2012-102177 A

In recent years, the level of adhesion required for a curable resin composition containing a silicone 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 silicone resin, a black colorant, and a specific insulating filler has insulating properties, heat resistance, adhesion, The present inventors have found that the solvent resistance is excellent and completed the present invention.
That is, the present invention provides the following (1) to (5).

(1) A thermosetting resin composition comprising (a) a silicone resin, (b) a black colorant, and (c) at least one selected from the group consisting of barium sulfate, silica, and talc. object.

（式中、Ｒがそれぞれ直鎖もしくは分岐鎖の炭素数１〜１２のアルキル基、又はフェニル基を示す。） (2) The thermosetting resin composition according to (1), wherein the silicone resin (a) has a structure represented by the following general formula (I).

(In the formula, each R represents a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group.)

(3) The thermosetting resin composition according to (1) or (2), further comprising (d) a colorant other than the black colorant.

(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”) comprises (a) a silicone resin, (b) a black colorant, and (c) barium sulfate, silica, and talc. And at least one selected from the group.
Hereinafter, each component used for the composition of this invention is demonstrated in detail.

（式中、Ｒがそれぞれ直鎖もしくは分岐鎖の炭素数１〜１２のアルキル基、またはフェニル基を示す。） [(A) Silicone resin]
The silicone resin contained in the thermosetting resin composition of the present invention is a component for imparting heat resistance, and is used regardless of whether it is linear or cross-linked, but preferably has a structure represented by the following general formula (1) Have

(In the formula, each R represents a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group.)

  Here, as specific examples of the alkyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl, propyl group, isopropyl group, butyl group, isobutyl group, heptyl group, isoheptyl group, pentyl group, isopentyl group, hexyl group, An isohexyl group etc. are mentioned, It is not limited to these specific examples. Among these, a methyl group and an ethyl group can be particularly preferably used.

The blending amount of such a silicone resin is preferably 15 to 50 parts by mass, more preferably 20 to 40 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 40 parts by mass or less, the viscosity becomes optimal and the applicability and the like are not lowered.
Moreover, although the mass mean molecular weight of the said silicone resin changes with resin frame | skeletons, what is generally in the range of 5000-50000, Furthermore, 10000-30000 is preferable. When the mass average molecular weight is 5000 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 50000 or less, it becomes possible to achieve better adhesion and curability.

[(B) Black colorant]
The black colorant contained in the composition of the present invention may be any black colorant as long as it exhibits sufficient black color and does not chemically react with the silicone resin. For example, carbon shown in CIPigment black 6, 7, 9 and 18 Black type colorant, graphite type colorant shown in CIPigment black 8, 10 etc., iron oxide type colorant shown in CIPigment black 11, 12 and 27, Pigment Brown 35 etc .: For example, KN- manufactured by Toda Kogyo Co., Ltd. 370 iron oxide, Mitsubishi Materials 13M titanium black, CIPigment black 20 and other anthraquinone colorants, CIPigment black 13, 25 and 29 and other cobalt oxide colorants, CIPigment black 15 and 28 Copper oxide colorants such as CIPigment black 14 and 26, manganese colorants such as CIPigment black 23, and antimony oxides such as CIPigment black 23 Colorants, nickel oxide colorants such as CIPigment black 30 etc., perylene colorants shown as CIPigment black 31 and 32, aniline pigments shown as Pigment Black 1, and molybdenum sulfide and bismuth sulfide are also suitable. It can be illustrated as a coloring agent. These pigments 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 1-20 mass parts with respect to 100 mass parts of non volatile matters of the thermosetting composition of this invention, More preferably, it is 2-15 mass parts.

[(C) At least one of barium sulfate, silica, and talc]
At least one insulating filler selected from the group consisting of (c) 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 by use. 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 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 5.0 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 preferably 70 to 250 parts by mass with respect to 100 parts by mass of the silicone resin, since the high temperature insulation resistance and the high temperature crack resistance are further improved. More preferably, it is part by mass. 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.

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

[Light stabilizer]
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 these are manufactured by BASF Japan); MARK LA-57, LA-62, LA-67, LA-63, LA-68 ( These are all manufactured by ADEKA Corporation); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.).

[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 silicone resin or the like and 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.

  0.01 mass part-10 mass parts are preferable with respect to 100 mass parts of silicone resins, and, as for the compounding quantity in the case of using the said antioxidant, 0.1-8 mass parts is more preferable. When the blending amount of the antioxidant is 0.01 parts by mass or more, the effect of adding the antioxidant described above can be obtained more. Moreover, in the case of 10 mass parts or less, since a tackiness deterioration and a film | membrane physical property fall are not caused, it is preferable.

[Colorants other than black colorants]
Moreover, 1 or more types of colorants other than a black colorant can be used as needed. As the colorant other than the black colorant, 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 that are classified as pigments, and dyes that are classified as solvents. 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 series: 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 blending amount of the wetting and dispersing agent is preferably 0.01 to 10 parts by mass, more preferably 1 to 8 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. Examples of commercially available leveling agents include BYK-352 and BYK-354 manufactured by Big Chemie GMBH.

[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 silicone-based antifoaming agents include BYK (registered trademark) -063, -065, -066N, -067A, -077 manufactured by BYK Japan, and KS-66 manufactured by Shin-Etsu Silicone (trade name). ) And the like.
The blending amount of such an antifoaming agent is preferably 10 parts by mass or less, more preferably 1 to 8 parts by weight with respect to 100 parts by mass of the silicone resin.

〔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.

*1 YR3370、モメンティブ・パフォーマンス・マテリアルズ社製、有機珪素樹脂
*2 線状有機珪素樹脂
*3 1255、コロンビアケミカルカンパニー製
*4 B-30、堺化学工業（株）製 平均粒径：０．３μｍ
*5 Nipsil L300 、日本シリカ工業（株）製 平均粒径２．２μｍ
*6 KINSEI QZ CRYSTAL SQ-PL2、キンセイマテック（株）製、平均粒径１．０７μｍ
*7 SG-95、日本タルク（株）製 含水ケイ酸マグネシウム 平均粒径（Ｄ_５０）：２．５μｍ
*8 UNIDIC R-2000、DIC株式会社製変性エポキシ樹脂 酸価：５２〜５６ ＫＯＨｍｇ／ｇ
*9 PNE177、長春人造樹脂廠（股）製エポキシ樹脂 エポキシ当量：１７２〜１８２
*10 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
*11 BYK-142、BYK-ChemieGmbH製
*12 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
*13 CHINOX TP-10H、DOUBLEBOND CHEMICAL（股）製
*14 ジエチルグリコールｎ−ブチルエーテルアセテート
*15 DBAC (Diethyl Glycol n-Butyl Ether Acetate)、ダウ・ケミカル カンパニー製
*16 KS-66、オルガノポリシロキサン混合物、信越シリコーン社製
*17 Cromophtal Violet B、BASF社製
*18 OSTAPLAST YELLOW AGR、 Synthesia,a,s製、アントラキノン
*19 Irgazin DPP Red Ultra Opaque、BASF社製
*20 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 (Examples 1-8, Reference Examples and Comparative Examples 1-3)
The various components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1 and premixed with a stirrer, and then kneaded with a three-roll mill to prepare a thermosetting resin composition paste. .

* 1 YR3370, manufactured by Momentive Performance Materials, organic silicon resin
* 2 Linear organosilicon resin
* 3 1255, manufactured by Columbia Chemical Company
* 4 B-30, manufactured by Sakai Chemical Industry Co., Ltd. Average particle size: 0.3μm
* 5 Nipsil L300, manufactured by Nippon Silica Industry Co., Ltd. Average particle size 2.2μm
* 6 KINSEI QZ CRYSTAL SQ-PL2, manufactured by Kinsei Tech Co., Ltd., average particle size 1.07μm
* 7 SG-95, manufactured by Nippon Talc Co., Ltd. Hydrous magnesium silicate Average particle diameter (D ₅₀ ): 2.5 μm
* 8 UNIDIC R-2000, a modified epoxy resin manufactured by DIC Corporation Acid value: 52-56 KOHmg / g
* 9 PNE177, an epoxy resin made by Changchun Artificial Resin (Crotch) Epoxy equivalent: 172-182
* 10 TNK 110 Dyhard, ▲ Ning ▼ Natsuishi Foshan National Chemical Industry (Group) Ltd., Dicyandiamide
* 11 BYK-142, BYK-Chemie GmbH
* 12 BYK-183, BYK-Chemie GmbH, high molecular weight block copolymer with pigment affinity group
* 13 CHINOX TP-10H, DOUBLEBOND CHEMICAL
* 14 Diethyl glycol n-butyl ether acetate
* 15 DBAC (Diethyl Glycol n-Butyl Ether Acetate), manufactured by Dow Chemical Company
* 16 KS-66, organopolysiloxane mixture, manufactured by Shin-Etsu Silicone
* 17 Cromophtal Violet B, manufactured by BASF
* 18 OSTAPLAST YELLOW AGR, manufactured by Synthesia, a, s, anthraquinone
* 19 Irgazin DPP Red Ultra Opaque, manufactured by BASF
* 20 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 and Comparative Examples 1 to 3 was screen-printed using a 420 mesh screen, and the cured film thickness was about 6 μm after drying. The glass substrate (soda lime glass manufactured by Central Glass Co., Ltd., thickness 0.7 mm) was coated so that the glass substrate was coated, and the coated glass substrate was placed in an oven (DH-62 manufactured by Yamato Scientific Co., Ltd.) at 250 ° C. Then, baking was performed for 60 minutes to prepare an evaluation glass substrate on which a cured film of 6 μm 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 over 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 DEN YNG high-temperature oven (manufactured by Torigi Co., Ltd., model number: DH-400), heated at 280 ° C. for 1 hour, and electron microscope (50 times, manufactured by 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 50% ×: Crack generation rate is 50% 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 10 ¹⁰ Ω or more Δ: Resistance 10 ¹⁰ or less 10 ⁸ Ω or more ×: Resistance 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. Particularly when at least one of barium sulfate, silica, and talc is blended in a large amount, high-temperature crack resistance and high-temperature insulation resistance are obtained, and when a silicone resin having a structure represented by the general formula (1) is used, It was confirmed that the sulfuric acid resistance, hydrochloric acid resistance, and alkali resistance were further improved. On the other hand, as in the prior art, Comparative Examples 1 and 3 using a composition containing an epoxy resin or a carboxyl group-containing resin were all inferior in terms of high-temperature insulation resistance and hot water resistance. Moreover, although the comparative example 2 used the silicone resin which has a structure represented by this-application general formula (1), since it does not contain at least 1 sort (s) in any one of barium sulfate, a silica, and a talc, sufficient high temperature resistance Cracking properties and high-temperature insulation resistance were not obtained.

Claims (4)

A thermosetting resin composition for coating a glass substrate, comprising (a) a silicone resin which is a thermosetting resin , (b) a black colorant, and (c) barium sulfate. Furthermore, (d) The coloring agent other than said (b) and (c) is included, The thermosetting resin composition for glass substrate application | coating of Claim 1 characterized by the above-mentioned. A glass substrate, wherein the thermosetting resin composition for coating a glass substrate according to claim 1 or 2 is applied on a glass substrate and cured. A display member comprising the glass substrate according to claim 3.