TWI612107B - Thermosetting resin composition, cured product thereof, and display member using the same - Google Patents

Abstract

An object of the present invention is to provide a hardened product which is excellent in insulation and heat resistance, and which can achieve surface flatness, adhesion, and hardening at a high level and balance, and has good solvent resistance and high-temperature insulation resistance. A thermosetting resin composition and a display including the cured product.

The solution of the present invention is a thermosetting resin composition, which is characterized by comprising: (a) a polysiloxane resin, (b) a black colorant, and (c) a barium sulfate, silicon dioxide, and talc powder. At least one selected from the group.

Description

Thermosetting resin composition, cured product thereof, and display member using the same

The present invention is to provide a thermosetting resin composition capable of forming a hardened product that can achieve surface flatness, adhesion, and hardening at a high level and in a good balance, and has both high temperature insulation resistance and solvent resistance, and A member for a display including the cured product.

In recent years, including a mobile phone, a personal mobile information terminal, and a notebook computer, a touch panel type input device (hereinafter, simply referred to as a "touch panel") has been introduced as an operation unit on the screens of various electronic devices. In a liquid crystal display device provided with a touch panel, the touch panel is mounted and fixed after being aligned on a polarizing plate of a display panel of the liquid crystal display device. In addition, in a mobile phone or a tablet device, if the liquid crystal display section is viewed from the user side, information or images are not displayed on the entire surface of the transparent glass, and there is a display section to distinguish the outer peripheral portion of the substrate The method is to make a black or white frame part, and the information is displayed inside the frame part.

This frame is called the decoration department, but it is The display section is divided into a quadrangular shape, and it also has the function of shielding parts that are not expected to be seen (wiring parts for touch panels, etc.) in a way that will not be observed. The decoration part is very important as the appearance device component of the display part of the portable terminal device as a part that directly enters the line of sight, and especially attaches great importance to design. Therefore, as a material, A thermosetting resin composition that achieves color, adhesion, and hardenability with a high level and good balance, and has both the high-temperature insulation resistance and the solvent-resistant hardened material required in the processing process is required.

Conventionally, as such a thermosetting resin composition, for example, Patent Document 1 discloses a curable resin composition containing a polysiloxane resin (A) having an alkenyl group and an alkoxy group at both ends. , An organic titanium compound (B), and / or a polysiloxane compound (C) having at least two Si-H bonds in one molecule and a catalyst (D) for a hydrosilylation reaction.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2012-102177

In recent years, the level of adhesion required for a curable resin composition containing a silicone resin has been improved, and in particular, a curability is required A curable resin composition that is excellent in both adhesiveness and adhesion, and can have both high-temperature insulation resistance and solvent resistance. However, the conventional curable composition described in the above-mentioned Patent Document 1 is not one capable of achieving high-level and well-balanced adhesion and hardening properties, and having both high-temperature insulation resistance and solvent resistance.

Therefore, an object of the present invention is to provide a high-temperature insulation resistance and resistance which are excellent in insulation and heat resistance, can achieve surface flatness, adhesion, and hardening at a high level and balance, and are required in the manufacturing process. A thermosetting resin composition excellent in both solvent properties, a cured product thereof, and a member for a display using the same.

As a result of efforts made by the present inventors to solve the above-mentioned problems, they have found that a composition containing a specific silicone resin, a black colorant, and a specific insulating filler is excellent in insulation, heat resistance, adhesion, and solvent resistance. Thus, the present invention has been completed.

That is, the present invention provides the following (1) to (4).

(1) A thermosetting resin composition, comprising: (a) a polysiloxane resin, (b) a black colorant, and (c) a group consisting of barium sulfate, silicon dioxide, and talc. At least one selected.

(2) The thermosetting resin composition according to (1), which further contains a coloring agent other than (d) a black coloring agent.

(3) A cured product, which is a cured product of the thermosetting resin composition according to (1) or (2), and is formed on a substrate.

(4) A member for a display, comprising The hardened material according to (3).

According to the present invention, it is possible to provide a hardened material which is excellent in insulation and heat resistance, and can achieve surface flatness, adhesion, and hardening at a high level and balance, and has both high-temperature insulation resistance and solvent resistance. Thermosetting resin composition. The curable resin composition of the present invention is suitable as a decorative ink for a display device.

The curable resin composition of the present invention (hereinafter, also referred to as "the composition of the present invention") includes: (a) a polysiloxane resin, (b) a black colorant, and (c) a barium sulfate and a dioxide. At least one selected from the group consisting of silicon and talc.

Hereinafter, each component used for the composition of this invention is demonstrated in detail.

[(a) Silicone Resin]

The silicone resin contained in the thermosetting resin composition of the present invention is a component for imparting heat resistance, and can be used regardless of a linear shape or a crosslinked type.

The blending amount of such a silicone resin is preferably 15 to 50 parts by mass, and more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the non-volatile components of the entire composition. If it is 15 parts by mass or more, deep hardenability will be deteriorated It is more sufficient, and when it is 40 parts by mass or less, the viscosity is optimal without reducing the coatability and the like.

In addition, although the mass average molecular weight of the above-mentioned polysiloxane resin varies depending on the resin skeleton, it is generally in the range of 5,000 to 50,000, and more preferably in the range of 10,000 to 30,000. When the mass average molecular weight is 5,000 or more, the non-adhesive property is further improved, and the hardness of the cured product is also more sufficient. In addition, when the mass average molecular weight is 50,000 or less, adhesion and hardenability can be achieved in a better balance.

[(b) Black colorant]

The black colorant contained in the composition of the present invention is only required to show black sufficiently and not to react chemically with the above-mentioned silicone resin, for example, carbons shown in CIPigment black 6, 7, 9 and 18, etc. Black colorants, graphite colorants such as CIPigment black 8, 10, etc., iron oxide colorants such as CIPigment black 11, 12, and 27, Pigment Brown 35, etc .: For example, Toda Industries KN-370 iron oxide, 13M titanium black manufactured by Mitsubishi Materials, CIPigment black 20 and other anthraquinone-based colorants, CIPigment black 13, 25 and 29, and other cobalt oxide-based colorants, CIPigment black 15 and 28 and other acidified copper-based colorants, CIPigment black 14 and 26 and other manganese-based colorants, CIPigment black 23 and other antimony oxide-based colorants, CI Pigment black 30 and other nickel oxide-based colorants, CIPigment black 31 and 32-based nickel-based colorants, Pigment The aniline pigments shown in Black 1 and molybdenum sulfide or bismuth sulfide can also be exemplified as suitable coloring agents. These pigments can be used alone or in an appropriate combination. Particularly preferred is carbon black, and examples thereof include carbon black manufactured by Mitsubishi Chemical Corporation, M-40, M-45, M-50, MA-8, MA-100, and carbon black 1255 manufactured by Columbia Chemicals Company.

If the blending amount of the black colorant is too large, the insulation properties will be reduced and the cost will be increased. If it is too small, the color and opacity may become insufficient. It is preferably 1 to 20 parts by mass, and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the nonvolatile component of the thermosetting composition of the present invention.

[(c) at least one of barium sulfate, silica, and talc]

The (c) at least one type of insulating filler selected from the group consisting of barium sulfate, silicon dioxide, and talc used in the thermosetting resin composition of the present invention not only improves the high temperature of the cured product by using it Insulation resistance also improves surface flatness, suppresses deformation caused by heating in the processing process, and maintains surface flatness. In addition, it can effectively prevent scratches or microcracks. In particular, from the viewpoint that the flatness of the surface is also improved, the insulating filler preferably contains barium sulfate. On the other hand, from the viewpoint of preventing micro-cracks, the insulating filler preferably contains at least one of talc and silicon dioxide.

In terms of the particle diameter of the insulating filler, the average particle diameter of barium sulfate is preferably 0.05 to 5.0 μm, the average particle diameter of silicon dioxide is 0.1 to 5.0 μm, and the average particle diameter of talc is 0.1 to 5.0 μm. If insulating filler If the average particle diameter is less than the upper limit of the above range, the dispersibility or surface flatness will be further improved. Moreover, when the average particle diameter of an insulating filler is more than the lower limit of the said range, hardenability or high-temperature resistance will improve more.

From the viewpoint of further improving high-temperature insulation resistance or high-temperature crack resistance, the total blending amount of the above-mentioned insulating filler is preferably 70 to 250 parts by mass, and more preferably 100 to 100 parts by mass of the above-mentioned silicone resin. 200 parts by mass. In addition, commercially available barium sulfate, silicon dioxide, and talc can also be used.

Commercial products of barium sulfate include, for example, sedimentary barium sulfate # 100, sedimentary barium sulfate # 300, sedimentary barium sulfate SS-50, BARIACE B-30, BARIACE B-31, BARIACE B-32, and BARIACE. B-33, BARIACE B-34, BARIFINE BF-1, BARIFINE BF-10, BARIFINE BF-20, BARIFINE BF-40 (manufactured by Sakai Chemical Industry Co., Ltd.), surface treatment barium sulfate B-30, B-34 (Sakai Chemical Industrial company), W-1, W-6, W-10, C-300 (manufactured by Takehara Chemical Industry Co., Ltd.), etc.

Commercial products of silicon dioxide can be listed: AEROSIL 50, AEROSIL 200, AEROSIL 380, AEROSIL A300 and other A series, RY300 and other RY series (made by Japan AEROSIL company); WACKER HDK S13, WACKER HDK V15, WACKER HDK N20 (All manufactured by Asahi Kasei Corporation); "FINESILB" (trade name, manufactured by TOKUYAMA), "FINESIL" (made by TOKUYAMA), "SYLYSIA" (made by FUJI SILYSIA Chemical Company), SNOWTEX UP, SNOWTEX OUP (Nissan Chemical Industry Company) system), Nipsil L-300, Nipsil KQ (manufactured by NIPPON SILICA Industrial Co., Ltd.), and the like.

Talc products sold in the market can be listed as: LMS-100, LMS-200, LMS-300, LMS-3500, LMS-400, LMP-100, PKP-53, PKP-80, PKP-81 (FUJI TALC Industrial Corporation) ), D-600, D-800, D-1000, P-2, P-3, P-4, P-6, P-8, SG-95 (manufactured by Nippon Talc), and the like. These systems can be used alone or in combination.

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

[Light stabilizer]

In the thermosetting resin composition of the present invention, a hindered amine-based light stabilizer is blended for the purpose of reducing the photodeterioration of the cured product.

The hindered amine light stabilizers can be listed as: TINUVIN 622LD, TINUVIN 144; CHIMASSORB944LD, CHIMASSORB 119FL (the above are all made by BASF JAPAN); MARK LA-57, LA-62, LA-67, LA-63, LA -68 (the above are all made by ADEKA); sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all are made by Sankyo Lifetech) and so on.

[Adhesion promoter]

唑、苯并噻唑、2-巰基苯并咪唑、2-巰基苯并

唑、2-巰基苯并噻唑(商品名：川口化學工業公司製ACCEL M)、3-嗎啉甲基-1-苯基-三唑-2-硫酮、5-胺基-3-嗎啉甲基-噻唑-2-硫酮、2-巰基-5-甲硫基-噻二唑、三唑、四唑、苯并三唑、羧基苯并三唑、含有胺基之苯并三唑、矽烷偶合劑等。此等，係可分別單獨使用，亦可2種以上組合使用。 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 adhesion promoters include benzimidazole and benzo

Azole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzo

Azole, 2-mercaptobenzothiazole (trade name: ACCEL M manufactured by Kawaguchi Chemical Co., Ltd.), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholine Methyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, Silane coupling agents, etc. These can be used individually or in combination of two or more kinds.

[Antioxidants]

In order to prevent oxidation, the curable resin composition of the present invention may contain a radical scavenger such as to invalidate generated radicals, or decompose the generated peroxides into harmless substances to avoid generation. Antioxidants such as new radical peroxide decomposers. The antioxidant used in the present invention can prevent oxidative degradation of polysiloxane resin and the like, and inhibit yellowing. Examples of the antioxidants include phenol-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among them, particularly preferred is a phenolic antioxidant. The antioxidants may be used alone or in combination of two or more.

The blending amount when using the antioxidant is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 8 parts by mass, relative to 100 parts by mass of the silicone resin. When the blending amount of the antioxidant is 0.01 parts by mass or more, the effect of the aforementioned addition of the antioxidant can be more obtained. In addition, in the case of 10 parts by mass or less, it is preferable because the viscosity does not deteriorate and the physical properties of the film do not decrease.

[Colorants other than black colorants]

In addition, one or more coloring agents other than the black coloring agent may be used as required. As a coloring agent other than a black coloring agent, a well-known person can be used, and any one of a pigment, a dye, and a pigment can 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. Particularly preferred is at least one of a blue colorant and a red colorant, and both may be used.

Blue colorants, pigments based on phthalocyanine, anthraquinone, etc. are classified as pigments, and dyes are classified as solvents (Solvent). Specific examples include the following: Those who are like color index number.

Available pigments: 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; Dyes: 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 ;Wait. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Red colorants, including: monoazo, diazo, azo lake, benzimidazolone, hydrazone, diketopyrrolopyrrole, Specific examples of the condensed azo-based, anthraquinone-based, and quinacridone-based systems include those with color index numbers as follows.

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; Diazo: Pigment Red 37,38,41; Monoazo lake system: 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; Actinides: 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 Department: 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; quinacridone: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Purple colorants, specifically, can be listed: Pigment Violet 19, 23, 29, 32, 36, 37, 38, 42; Solvent Violet 13, 36; CIPigment brown 25; Cipigment black 1, Cipigment black 7 , Pigment Violet 37 (dioxazine series) and the like.

Yellow colorants include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based. 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; Diazo: 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: 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: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Green colorants include phthalocyanine and anthraquinone. 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, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Orange colorants, specifically, CI colorant orange 1, CI colorant orange 5, CI colorant orange 13, CI colorant orange 14, CI colorant orange 16, CI colorant orange 17, CI Pigment Orange 24, 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 color orange 61, CI color orange 63, CI color orange 64, CI color orange 71, CI color orange 73 and the like.

Specific examples of brown colorants include C.I. colorant brown 23, C.I. colorant brown 25, and the like.

White coloring agents 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 they are coloring and non-toxic. From a viewpoint, titanium oxide is particularly preferred, and examples thereof include: TR-600, TR-700, TR-750, TR-840, Ishihara Industries R-550, R-580, and R-630 manufactured by Fuji Titanium Industries. , R-820, CR-50, CR-60, CR-90, KR-270, KR-310, KR-380 and other rutile titanium oxide manufactured by Titan Industries, TA-100, TA manufactured by Fuji Titanium Industries -200, TA-300, TA-500, A100, A220 manufactured by Ishihara Industries, KA-15, KA-20, KA-35, KA-90 and other anatase titanium oxide manufactured by Titan Industries.

[Organic solvents]

Furthermore, the thermosetting resin composition of the present invention may use an organic solvent as a diluent for dilution of the composition or adjustment of viscosity for coating on a substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Kiselox, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Glycol ethers; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, and the like ; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane, decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, etc. Such organic solvents may be used alone or as a mixture of two or more. The blending amount of the organic solvent is not particularly limited, and may be appropriately added according to needs.

The thermosetting resin composition of the present invention can be adjusted, for example, to a viscosity suitable for a coating method by using the organic solvent, and can be immersed by dipping. The coating method, the shower coating method, the roll coating method, the bar coating method, the screen printing method, the curtain coating method, etc. are applied to the substrate, and the composition is applied at a temperature of about 50 to 300 ° C. The contained organic solvent is evaporated to dryness (precure) to form a non-sticky coating film.

[Wetting dispersant]

The thermosetting resin composition of the present invention may contain a wetting and dispersing agent in order to adjust the filling properties of the minute recesses of the composition, the surface smoothness of the cured film, the defoaming property, or the surface tension of the composition. The commercially available products include, for example, wetting and dispersing agents BYK-110, BYK-111, and BYK-183 manufactured by BYK-Chemie GMBH. The wetting and dispersing agents can be used alone or in combination of two or more. The blending amount of the wet dispersant is preferably 0.01 to 10 parts by mass, and more preferably 1 to 8 parts by mass, with respect to 100 parts by mass of the entire composition (solid content).

[Leveling agent]

Examples of leveling agents include polyacrylate polymers, polyether modified dimethylpolysiloxane copolymers, polyester modified dimethylpolysiloxane copolymers, and polyether modified methyl esters. Alkyl polysiloxane copolymers, aralkyl modified methyl alkyl polysiloxane copolymers, and polyether modified methyl alkyl polysiloxane copolymers. The leveling agents can be used alone or in combination of two or more. Examples of commercially available leveling agents include BYK-352 and BYK-354 manufactured by BYK-Chemie‧GMBH.

[Defoaming agent]

A specific example of the defoaming agent is commercially available as a defoaming agent composed of a non-silicone-based defoaming polymer solution. Examples of the defoaming agent include BYK (registered trademark) -054 manufactured by BYK-Chemie, Japan. , -055, -057, -1790, etc., as examples of polysiloxane-based defoamers, BYK (registered trademark) -063, -065, -066N, --067A, BYK-Chemie, JAPAN, -077, and KS-66 (trade name) manufactured by Shin-Etsu Silicone.

The blending amount of such an antifoaming agent is preferably 10 parts by mass or less, more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the aforementioned silicone resin.

[Substrate]

Examples of the substrate used in the present invention include resin films such as polyimide films and PET films, glass substrates, ceramic substrates, metal substrates, and wafer plates. Among them, resin films such as polyimide films, PET films, and glass substrates can be preferably used. The material and shape of the substrate are selected according to the purpose or performance of the intended molded article, and can be used alone or in combination of two or more materials and shapes. From the viewpoint of adhesion, a glass substrate is more preferred.

[Manufacturing / mixing method]

The thermosetting resin composition of the present invention can be prepared by uniformly mixing the above-mentioned essential components and other additive components used as required. Made. The mixing method is not particularly limited, and a known method can be used. Either a method of mixing without using a dispersing machine, or a method of mechanically mixing using various dispersing machines such as a kneader, a roll, a mill, a bead mill, or the like may be used.

A particularly good method is to mix the aforementioned insulating filler, solvent, and dispersant in advance, mix the dispersion liquid dispersed with a disperser such as a rolling mill with other hardening resin components, and reuse the roller as needed. A method in which a rolling mill is dispersed, or a part of a resin component, the aforementioned insulating filler, a solvent, and a dispersant are blended in advance, and a dispersion liquid dispersed by a disperser such as a rolling mill is mixed with other hardening resin components, and If necessary, the method of dispersing by a rolling mill is used again.

In addition, when adding a colorant, from the viewpoint of dispersibility, it is preferable to add and mix in water or an organic solvent, etc., to dissolve or finely disperse it in a mixed solution in which the powder and the like are dispersed. Liquid made of toner dispersant.

[Coating method]

After the thermosetting resin composition is prepared with a specific composition as described above, for example, the viscosity can be adjusted to an appropriate coating method with an organic solvent, and for example, a dip coating method, a shower coating method, a roll coating method, A method such as a doctor blade coating method, a screen printing method, or a curtain coating method is applied to the substrate. Among them, a shower coating method, a roll coating method, a bar coating method, and a screen printing method are more suitable for use, and a screen printing method is particularly suitable for use.

[Example]

Hereinafter, although the present invention is specifically described with reference to the examples, the present invention is not limited to these examples. In addition, unless otherwise specified, "part" means mass part, and "%" means mass%.

(Examples 1 to 9 and Comparative Examples 1 to 3)

Each component shown in the following Table 1 was blended in the proportion (parts by mass) shown in Table 1, and after preliminary mixing with a stirrer, it was kneaded with a 3-roller rolling mill to prepare a thermosetting resin composition. The paste.

* 1 YR3370, made by Momentive Performance Materials, silicone resin

* 2 Linear silicone resin

* 3 1255, manufactured by Columbia Chemicals Company

* 4 B-30, manufactured by Sakai Chemical Industry Co., Ltd. Average particle size: 0.3 μm

* 5 Nipsil L300, Nippon Silica Industrial Co., Ltd. average particle size 2.2 μm

* 6 KINSEI QZ CRYSTAL SQ-PL2, KINSEI MATEC (strand), average particle size 1.07 μm

* 7 Average particle diameter (D ₅₀ ) of SG-95, hydromagnesium silicate made by Nippon Talc (strand): 2.5 μm

* 8 Modified epoxy resin manufactured by UNIDIC R-2000 and DIC Co., Ltd. Acid value: 52 ~ 56KOHmg / g

* 9 PNE177, epoxy resin made by Changchun Artificial Resin Factory (shares) Epoxy equivalent: 172 ~ 182

* 10 TNK 110 Dyhard, manufactured by Ningxia Shizuishan National Chemical (Group) Company, dicyandiamine

* 11 BYK-142, BYK-ChemieGmbH,

* 12 BYK-183, BYK-Chemie GmbH, high molecular weight block copolymer with pigment affinity group

* 13 CHINOX TP-10H, DOUBLEBOND CHEMICAL (share) system

* 14 Diethylene glycol n-butyl ether acetate,

* 15 DBAC (Diethyl Glycol n-Butyl Ether Acetate), By Dow Chemical Company

* 16 KS-66, organic polysiloxane mixture, manufactured by Shin-Etsu Silicone

* 17 Cromophtal Violet B, made by BASF

* 18 OSTAPLAST YELLOW AGR, Synthesia, a, s, anthraquinone

* 19 Irgazin DPP Red Ultra Opaque, manufactured by BASF

* 20 R-KB-6, rutile-type titanium oxide manufactured by Bayer AG and surface-treated with alumina

(Evaluation of the production of glass substrates)

The paste of the thermosetting resin composition obtained in the above Examples 1 to 9 and Comparative Examples 1 to 3 was screen-printed using a 420-mesh screen to make the film thickness of the cured film dry to about 6 μm. It was coated on a glass substrate (sodium-lime glass manufactured by Central Glass Co., Ltd. with a thickness of 0.7 mm), the coated glass substrate was placed in an oven (DH-62 manufactured by Yamato Scientific Co., Ltd.), and heated and baked at 250 ° C. 60 In minutes, an evaluation glass substrate having a cured film having a thickness of 6 μm was produced.

The glass substrate on which the cured film of each thermosetting resin composition was formed was used to evaluate various characteristics as described below by the following method.

<Light-shielding property (OD value)>

With the coating side of the glass substrate facing the measuring device, install the transmission densitometer (manufactured by SAKATA INX ENG, model: X-Rite 361T, light source wavelength: 400 ~ 800nm), and evaluate the OD value as follows.

○: The OD value exceeds 4

△: OD value is 3 or more and 4 or less

×: OD value is less than 3

<Hot water resistance (hot water test)>

After the glass substrate was immersed in boiling water at 100 ° C for 60 minutes, the surface moisture was taken out and removed, and the immersion of water or the precipitation of the film was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Company, width: 18 mm) was completely attached to the film side of the evaluation glass substrate, and one end of the tape was directly peeled off while maintaining a right angle to the glass substrate, and the film was visually evaluated as follows.

○: No change was confirmed.

△: Slight change was confirmed.

×: The immersion of effluent or the peeling of the film was confirmed.

<High temperature crack resistance>

The glass substrate was placed in a DENG YNG high temperature oven (manufactured by Dengying Instrument Co., Ltd., model: DH-400), heated at 280 ° C for 1 hour, using an electron microscope (50 times, manufactured by OLYMPUS, model: MEASURING MICROSCOPE STM-MJS2), The film surface of the glass substrate was evaluated as follows.

○: No crack

△: The occurrence rate of cracks exceeds 0 and less than 50%

×: Crack occurrence rate is 50% or more

<High temperature insulation resistance>

The glass substrate was baked in an oven at 280 ° C. for 60 minutes, and a resistance meter (manufactured by Agilent Technologes, high resistance meter 4339B, and component test fixture) was made so that the distance between the positive electrode and the negative electrode became 0.5 cm. The test fixture) 16339A) was sandwiched between the positive and negative electrodes of the glass substrate, and the resistance of the film was measured under the conditions of voltage: 500V and time: 60 seconds, and the resistance of the film was evaluated as follows.

○: Resistance exceeds 10 ¹⁰ Ω

△: Resistance is 10 ⁸ or more and 10 ¹⁰ or less

×: Resistance does not reach 10 ⁸ Ω

<Surface flatness>

Using a surface roughness meter (manufactured by Kosaka Laboratories, model: SE3500), the measurement length was 2.5 mm, vertical magnification: 1000, horizontal magnification: 100, cutoff: 0.8 mm, speed: 0.5 mm / s The roughness (maximum height of the peak, RmaxD) of the film surface was measured three times under the conditions, and the evaluation was performed as follows.

○: RmaxD is less than 1.5 μm

△: RmaxD is 1.5 or more and less than 2 μm

×: RmaxD is 2 μm or more

<Pencil hardness test>

According to JIS K5400 (1990 version), a 4B-9H pencil that has been ground to make the tip of the refill flat is pressed against each glass substrate of a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd .: C221A) at an angle of about 45 °. The hardness of the pencil causing peeling of the film.

<Sulfuric acid resistance>

The glass substrate was immersed in a 10 vol% sulfuric acid aqueous solution at 25 ° C for 30 minutes, and then washed with water, and then the water was removed. The immersion of water or the dissolution of the film was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Company, width: 18 mm) was completely attached to the film side of the evaluation glass substrate, and one end of the tape was directly peeled off while maintaining a right angle to the glass substrate, and the film was visually evaluated as follows.

○: No change was confirmed.

△: Slight change was confirmed.

×: The immersion of effluent or the peeling of the film 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 after washing with water, the water was removed, and the immersion of water or the dissolution of the film was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) was completely attached to the film of the evaluation glass substrate. On the side, directly peel off one end of the tape while keeping a right angle to the glass substrate, and visually evaluate the film as follows.

○: No change was confirmed.

△: Slight change was confirmed.

×: The immersion of effluent or the peeling of the film was confirmed.

<Alkali resistance>

The glass substrate was immersed in a 10 vol% NaOH aqueous solution at 25 ° C for 30 minutes, and after washing with water, the water was removed, and the immersion of water or the dissolution of the film was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Company, width: 18 mm) was completely attached to the film side of the evaluation glass substrate, and one end of the tape was directly peeled off while maintaining a right angle to the glass substrate, and the film was visually evaluated as follows.

○: No change was confirmed.

△: Slight change was confirmed.

×: The immersion of effluent or the peeling of the film was confirmed.

<Solvent resistance>

Add a small amount of ethanol (95vol%), dipropylene glycol monomethyl ether (DPM) (100vol%), isopropyl alcohol (IPA) (100vol%) to lens paper made by Kimberly-Clark. After the lens paper of the solvent was repeatedly wiped about 20 times on the film of the glass substrate, the surface of the film was visually observed.

○: No change was confirmed.

△: Slight change was confirmed.

×: The film was peeled.

<Adhesion (checkerboard adhesion test method)>

According to JISK5400, 100 checkerboard grids (10 × 10) with a thickness of 1 mm were made on the film of the sample, and the transparent adhesive tape was completely attached to the checkerboard grid (NICHIBAN, width: 18mm). The substrate was peeled off while keeping the right-angled side, and the number of checkerboard cells that were not completely peeled off was investigated.

In Table 2 below, the number of remaining checkerboard cells is used as the numerator, and the total number of checkerboard cells (100) is used as the denominator, and the results are described.

○: 100% of checkerboard remains.

△: The checkerboard residue is more than 95% and less than 100%.

×: The checkerboard residue does not reach 95%.

The results of the aforementioned evaluation tests are summarized and shown in Table 2.

As shown in Table 2, each of Examples 1 to 9 of this embodiment is capable of achieving high-level and well-balanced adhesion, surface flatness, and hardening properties, as well as high-temperature insulation resistance and Solvent resistant. It was confirmed that especially when at least one of barium sulfate, silicon dioxide, and talc is blended in a large amount, it has high temperature crack resistance and high temperature insulation resistance, and when polysiloxane resin is used, it is resistant to sulfuric acid and hydrochloric acid. Better resistance to alkali and alkali it is good. On the other hand, from the viewpoints of high-temperature insulation resistance and hot water resistance, as in the prior art, any of Comparative Examples 1 and 3 using a composition containing an epoxy resin or a carboxyl group-containing resin was inferior. In Comparative Example 2, although the same polysiloxane resin as in Examples 1 to 9 was used, it did not contain at least one of barium sulfate, silicon dioxide, and talc, so sufficient high temperature cracks could not be obtained. And high temperature insulation resistance.

Claims (4)

A thermosetting resin composition, comprising: (a) a silicone resin with a thermosetting component, (b) a black colorant, and (c) a barium sulfate, silicon dioxide, and talc powder. At least one selected from the group. The thermosetting resin composition according to claim 1, which further contains (d) a coloring agent other than a black coloring agent. A cured product is a cured product of a thermosetting resin composition according to claim 1 or 2, and is formed on a substrate. A member for a display, comprising a hardened body as described in claim 3.