TW201518433A - White thermocurable resin composition, cured product thereof and display component using the same - Google Patents

Abstract

To provide a white thermocurable resin composition which is capable of forming a white cured product and a display device having the cured product, the white thermocurable resin composition having insulation property and heat resistance and being able to attain adhesion and hardenability with a high standard and sufficient balance, and being excellent in surface evenness and elevated-temperature discoloration tolerance. A white thermocurable resin composition is characterized by comprising: (a) a copolymerization epoxy resin, of which the epoxy equivalent not having an aromatic ring is within the limit of less than 500, (b) an acid anhydride which does not have an aromatic ring as an epoxy curing agent, (c) an antioxidant, and (d) titanium dioxide. Preferably, the white thermocurable resin composition further comprises a silane coupling agent, and at least one of barium sulfate, silica, and talc.

Description

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

The present invention relates to a white thermosetting resin composition, a cured product thereof, and a member for display using the same, and more particularly, it is capable of achieving high level and balance with insulation and heat resistance. A thermosetting resin composition of a white cured product having excellent adhesion and curability, and having excellent surface flatness and high-temperature discoloration resistance, and a member for display having the cured product.

In recent years, a touch panel type input device (hereinafter simply referred to as "touch panel") has been introduced as an operation unit on a screen of various electronic devices, including a mobile phone, a personal mobile information terminal, and a notebook computer. In a liquid crystal display device including a touch panel, the touch panel is mounted and fixed after being aligned on a polarizing plate of a display panel of a liquid crystal display device. Further, in the mobile phone or tablet device, when the liquid crystal display portion is viewed from the user side, information or an image is not displayed on the entire transparent glass, and the display portion is displayed on the outer peripheral portion of the substrate. The way is done with a blackened or whitened frame and the information is displayed inside the frame.

This frame portion is called a decorative portion, but it is also provided with a portion that is desired to be not seen (a wiring portion for a touch panel, etc.) while the display portion is divided into a four-corner shape. The observed way to shield the function. Since the decorative part is a part that directly enters the line of sight, it is very important as an appearance device member of the display device of the portable terminal device, and particularly attention is paid to the design. Therefore, as the material, it is possible to form A thermosetting resin composition which is excellent in high-temperature insulation resistance, high-temperature insulation resistance, surface flatness, and high-temperature discoloration resistance, which is excellent in high-quality and high-temperature discoloration resistance Required.

Conventionally, as a thermosetting resin composition, for example, Patent Document 1 discloses a white coating agent containing a thermosetting resin, a white pigment, a curing agent, a curing catalyst, and an elastomer.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-278411

In recent years, the level of adhesion required for a curable resin composition containing an epoxy resin is improved, and in particular, a curable resin composition excellent in both curability and adhesion is required. However, the above special In the conventional curable composition described in the document 1, it is not possible to form a cured product which is excellent in surface adhesion and high-temperature discoloration resistance, and which can achieve adhesion and hardenability at a high level and balance.

Accordingly, an object of the present invention is to provide an insulating property and a heat resistance which are required in a process, and at the same time, it is possible to form a high level and a good balance to achieve adhesion and hardenability, and to have excellent surface flatness and high temperature discoloration resistance. A white thermosetting resin composition of a cured product, a cured product thereof, and a member for display 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 copolymerized epoxy resin, an acid anhydride having no aromatic ring, an antioxidant, and a titanium oxide has a desired insulation. The present invention has been completed in terms of properties, heat resistance, adhesion, hardenability, surface flatness, and high temperature discoloration resistance.

That is, the present invention provides the following (1) to (6).

(1) A white thermosetting resin composition comprising: (a) a copolymerized epoxy resin having an epoxy equivalent having an aromatic ring of not more than 500, and (b) having no aromatic ring An acid anhydride of an epoxy hardener, (c) an antioxidant, and (d) titanium dioxide.

(2) The white thermosetting resin composition according to the above (1), wherein the antioxidant (c) is a phenolic antioxidant.

(3) The white thermosetting resin composition according to the above (1) or (2), further comprising a decane coupling agent.

(4) The white thermosetting resin composition according to any one of the above (1), further comprising at least one selected from the group consisting of barium sulfate, cerium oxide and talc. Kind.

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

(6) A member for a display characterized by comprising the cured product according to (5) above.

According to the present invention, it is possible to provide a thermosetting resin which has insulating properties and heat resistance and which can form a white cured product which is excellent in surface adhesion and high-temperature discoloration resistance, and which is excellent in surface adhesion and high-temperature discoloration resistance. Composition. Further, the white curable resin composition of the present invention is suitable as a decorative ink for use in a display device.

The white curable resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") is a white thermosetting resin composition characterized by comprising: (a) an epoxy equivalent having no aromatic ring It is a copolymerized epoxy resin in the range of less than 500, (b) an acid anhydride of an epoxy hardener having no aromatic ring, (c) an antioxidant, and (d) titanium dioxide.

Hereinafter, the components contained in the composition of the present invention are detailed. Description.

[(a) Copolymerized epoxy resin without aromatic ring]

The copolymerized epoxy resin used in the composition of the present invention is a copolymerized epoxy resin having an aromatic ring having an epoxy equivalent of less than 500, for example, an epoxy group-containing unsaturated compound and an unsaturated group. A copolymerized epoxy resin of the compound. Further, from the viewpoint of further improving the adhesion between the glass substrate and the molded body, the epoxy compound is preferably an epoxy compound having an alicyclic skeleton or a glycidyl group which is not directly attached to the alicyclic ring. Oxygen resin. Further, an epoxy resin having no aromatic ring tends to be excellent in weather resistance, and it tends to be difficult to be colored, and an epoxy resin having no main chain in the main chain tends to have excellent heat resistance.

Examples of the above-mentioned copolymerized epoxy resin having no aromatic ring include, for example, CELLOXIDE 2021, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 2000, CELLOXIDE 3000, CYCLOMER A200, CYCLOMER M100, CYCLOMER M101, Epolead GT-301, Epolead GT-302, Epolead 401, Epolead 403, ETHB, Epolead HD300 (above, manufactured by Daicel Chemical Industry Co., Ltd.), KRM-2110, KRM-2199 (above, manufactured by ADEKA), DM 4500, DM 3450 An alicyclic epoxy resin such as (Double Bond Chemical Co., Ltd.), triglycidyl isocyanurate, (for example, TEPIC-H manufactured by Nissan Chemical Co., Ltd. (3 groups of epoxy groups for S-triazine ring bone surface) Structure that is bonded in the same direction β β), or TEPIC (a mixture of β and α, which has one epoxy group for the S-triazine ring bone surface to be bonded to the other two epoxy groups) Heterocyclic epoxy resin, or hydrogenated epoxy resin, epoxy resin containing amine group, rubber modified epoxy resin, epoxy group-containing (meth) acrylate resin, polyoxygen modified ring An epoxy resin such as an oxygen resin or an ε-caprolactone-modified epoxy resin or the like which is soluble in a diluent. These epoxy resins may be used alone or in combination of two or more.

Specific examples of such a copolymerized epoxy resin having no aromatic ring include hydrogenated bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane. Carboxylic acid ester, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl -6-Methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate Acid ester, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5 ,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methyl Cyclohexyl carboxylate, methylene bis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-double (3,4-epoxycyclohexyl)propane dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), epoxy hexahydrophthalate dioctyl ester, Epoxy hexahydrophthalic acid di-2-ethylhexyl phthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane Wait.

In addition, as long as the epoxy equivalent of the aromatic ring is not reached The copolymerized epoxy resin in the range of 500 is not limited to the above examples, and is not easily caused to change over time, and can be used without problems. Further, if the epoxy equivalent is less than 500, it does not cause discoloration over time. More preferably, the epoxy equivalent is 250 or less.

The blending amount of the copolymerized epoxy resin having an epoxy equivalent of not more than 500 in the range of not more than 500 is appropriately adjusted to be appropriately changed by imparting heat, and is not particularly limited. The content of the copolymerized epoxy resin in 100 parts by mass of the white thermosetting resin composition is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 40 parts by mass or less, and still more preferably 15 parts by mass or more and 35 parts by mass or less. When the blending amount of the copolymerized epoxy resin is in the range of 5 parts by mass or more and 50 parts by mass or less, the curable composition is more effectively cured by heating, and the heat resistance of the molded body is further improved.

[(b) Anhydride of an epoxy hardener without an aromatic ring]

From the viewpoint of further improving the adhesion between the glass substrate and the molded body, an acid anhydride curing agent is used as the curing agent in the white thermosetting resin composition of the present invention. As the acid anhydride hardener, an acid anhydride having an alicyclic skeleton can be used. Preferred acid anhydride hardeners include phthalic anhydride, maleic anhydride, cyclohexane dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydroortylene Dicarboxylic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like. Among these anhydrides, phthalic anhydride, cyclohexane dicarboxylic anhydride, succinic anhydride, and maleic anhydride are used as materials. It is better in terms of cost and cost.

Further, the acid anhydride hardener preferably has no double bond in the carbocyclic ring. The reason for this is that when an acid anhydride curing agent having a double bond of a carbocyclic ring is used, there is a fear that the high temperature discoloration resistance or the ultraviolet light discoloration resistance is lowered. As the preferred acid anhydride curing agent which does not have a double bond, for example, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride can be preferably used.

The blending ratio of the above (a) copolymerized epoxy resin and (b) hardener is not particularly limited. The blending amount of the curing agent is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, and particularly preferably 45 parts by mass based on 100 parts by mass of the copolymerized epoxy resin compound. The above is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less.

[(c) Antioxidants]

In order to prevent oxidation, the composition of the present invention may contain a radical scavenger such as to invalidate the generated radical, or decompose the generated peroxide into a harmless substance, thereby avoiding new generation. An antioxidant such as a peroxide decomposing agent for free radicals. The antioxidant used in the present invention can prevent oxidative degradation of an epoxy resin or the like and suppress yellowing. The antioxidant may be used singly or in combination of two or more.

Examples of the antioxidant include a phenol antioxidant, a phosphorus antioxidant, and an amine antioxidant. Among them, a phenolic antioxidant is particularly preferred.

Commercial products of phenolic antioxidants include: IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, and IRGANOX 295 (all of which are manufactured by BASF Corporation), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STABAO-60, ADK STAB AO-70 , ADK STAB AO-80, ADK STAB AO-90, and ADK STABAO-330 (all of which are manufactured by ADEKA), Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F) And Sumilizer GP (all of which are manufactured by Sumitomo Chemical Industries Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, and HOSTANOX O3 (all of which are manufactured by Clariant), ANTAGE BHT, ANTAGE W-300, and ANTAGE W-400 And ANTAGE W500 (all of which are manufactured by Kawaguchi Chemical Industry Co., Ltd.), CHINOX TP-10H (all of which are manufactured by Double Bond Chemical Co., Ltd.), and SEENOX 224M and SEENOX 326M (all of which are manufactured by SHIPRO Chemical Co., Ltd.) .

Examples of the phosphorus-based antioxidant include cyclohexylphosphine and triphenylphosphine. Commercial products of the above phosphorus-based antioxidants include: ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, and ADK STAB TPP (all of which are manufactured by ADEKA), Sandstab P-EPQ, and HOSTANOX PAR24 (above) , all made by Clariant), And JP-312L, JP-318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, and JPH-3800 (all of which are manufactured by Seongbuk Chemical Industry Co., Ltd.).

Examples of the amine-based antioxidants include triethylamine, melamine, ethyldiamine-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-. a base-S-triazine, a 2,4-diamino-6-mercapto-S-triazine, a quaternary ammonium salt derivative, and the like.

The amount of the antioxidant blended is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 40 parts by mass or less, more preferably 100 parts by mass of the (a) copolymerized epoxy resin. 30 parts by mass or less. When the content of the antioxidant is 5 parts by mass or more and 40 parts by mass or less, a molded article which is more excellent in heat resistance can be obtained.

[(d) Titanium Dioxide]

A molded article having a high whiteness can be obtained by a composition containing titanium oxide. Further, in the case where only a filler different from titanium dioxide is used, a molded body having a high light reflectance can be obtained by using titanium oxide. Titanium dioxide is not particularly limited. The titanium dioxide type may be used alone or in combination of two or more. In the white curable resin composition of the present invention, both anatase type titanium dioxide and rutile type titanium dioxide can be used as the titanium dioxide. Among them, anatase type titanium dioxide is more commonly used because it has a higher whiteness than rutile type. However, anatase type titanium dioxide has a photocatalytic activity and thus causes discoloration of the resin in the composition. In contrast, rutile titanium dioxide, compared to anatase Although the whiteness is slightly inferior, since it has almost no photoactivity, a stable cured film can be obtained.

The above rutile type titanium dioxide, specifically, may be listed as TIPAQUE R-820, TIPAQUE R-830, TIPAQUE R-930, TIPAQUE R-550, TIPAQUE R-630, TIPAQUE R-670, TIPAQUE R-680, TIPAQUE R-780, TIPAQUE R-850, TIPAQUE CR-50, TIPAQUE CR-57, TIPAQUE CR-80, TIPAQUE CR-90, TIPAQUE CR-93, TIPAQUE CR-95, TIPAQUE CR-97, TIPAQUE CR-60, TIPAQUE CR-63, TIPAQUE CR-67, TIPAQUE CR-58, TIPAQUE CR-85, TIPAQUE UT771 (above, Ishihara Sangyo Co., Ltd.), Ti-Pure R-100, Ti-Pure R-101, Ti-Pure R-102 , Ti-Pure R-103, Ti-Pure R-104, Ti-Pure R-105, Ti-Pure R-108, Ti-Pure R-900, Ti-Pure R-902, Ti-Pure R-960, Ti-Pure R-706, Ti-Pure R-931 (above, manufactured by Dupont), TITONR-25, TITON R-21, TITON R-32, TITON R-7E, TITONR-5N, TITON R-61N, TITON R-62N, TITON R-42, TITONR-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITONGTR-300, TITON D-918, TITON TCR-29, TITONTCR-52, TITON FTR-700 (above, manufactured by Dai Chemical Industry Co., Ltd.).

In addition, the anatase type titanium dioxide may be, for example, TA-100, TA-200, TA-300, TA-400, TA-500 (above, manufactured by Fuji Titanium Industries Co., Ltd.), TIPAQUE A-100, TIPAQUE A-220, TIPAQUE W-10 (above, Ishihara Sangyo Co., Ltd.), TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA-5 (above, TAYCA), KRONOS KA-10, KRONOS KA-15, KRONOS KA-20, KRONOS KA-30 (above, Titan Industrial Co., Ltd.), A-100, A-100, A-100, SA-1, SA-1L (above, 堺Chemical Industries, Inc.) Wait.

The amount of the titanium dioxide to be added is preferably 80 to 250 parts by mass based on 100 parts by mass of the total of the (a) copolymerized epoxy resin and the (b) curing agent. When the blending amount of the titanium dioxide is 250 parts by mass or less, the curability of the white curable resin composition of the present invention is further improved, and the depth of hardening is increased, which is preferable. In addition, when the amount of the titanium dioxide is 80 parts by mass or more, the white curable resin composition of the present invention has a stronger shielding power, and a cured product excellent in both curability and adhesion can be obtained. .

Titanium dioxide is preferably a rutile-type titanium oxide comprising a surface treated with an aluminum oxide. The content of the rutile-type titanium oxide surface-treated with the aluminum oxide is preferably 10 parts by mass or more, more preferably 30 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the titanium dioxide. It is also possible that the total amount of the above titanium oxide is the rutile titanium dioxide surface-treated with the above aluminum oxide. The heat resistance of the molded body is further improved by using the above-described rutile-type titanium oxide surface-treated with an aluminum oxide.

The rutile-type titanium oxide surface-treated with the above-mentioned aluminum oxide may, for example, be rutile-type dioxide which is surface-treated with alumina. Titanium R-KB-6 (manufactured by Bayer AG), rutile, chlorine, titanium dioxide, orthochemicals, product number: CR-58, CR-90, or rutile sulfuric acid Product number: R-630 and so on.

[At least one of barium sulfate, cerium oxide, and talc]

In the present invention, it is preferred to contain at least one insulating filler selected from the group consisting of barium sulfate, cerium oxide and talc. By using at least one of the above-mentioned copolymerized epoxy resin, barium sulfate, cerium oxide, and talc, the high-temperature insulation resistance of the cured product can be improved, and the surface flatness can be improved to suppress the heating by the processing process. The resulting deformation maintains surface flatness, and in addition, it can effectively prevent scratches or microcracks.

In terms of the particle diameter of the insulating filler, the average particle diameter of barium sulfate is preferably 0.05 to 5.00 μm, the average particle diameter of ceria is 0.1 to 5.0 μm, and the average particle diameter (D50) of talc is 0.1 to 5.0. Mm. When the average particle diameter of the insulating filler is at most the upper limit of the above range, the dispersibility or surface flatness is further improved. Further, when the average particle diameter of the insulating filler is at least the above lower limit value, the hardenability or high-temperature electrical resistance is further improved.

The blending amount of the insulating filler is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, per 100 parts by mass of the total of the (a) copolymerized epoxy resin and the (b) curing agent. . Further, barium sulfate, cerium oxide, and talc may be used commercially.

Commercially available products of barium sulfate include: sedimentary barium sulfate #100, sedimentary barium sulfate #300, sedimentary 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 Sigma Chemical Industry Co., Ltd.), surface treatment of barium sulfate B-30, B-34 (堺Chemical Industry) Company system), W-1, W-6, W-10, C-300 (made by Takehara Chemical Industry Co., Ltd.).

Commercial products of cerium oxide include AEROSIL 50, AEROSIL 200, AEROSIL 380, AEROSIL A300, etc. A series, RY300 and other RY series (Japan AEROSIL (share) system); WACKER HDK S13, WACKER HDK V15, WACKER HDK N20 (all manufactured by Asahi Kasei Corporation); "Finesil B" (product name, manufactured by Tokuyama Co., Ltd.), "Finesil" (manufactured by Tokuyama Co., Ltd.), "Sylysia" (manufactured by Fuji Silysia Chemical Co., Ltd.), SNOWTEX UP, SNOWTEX OUP ( Nissan Chemical Co., Ltd., Megasil 950 manufactured by SIBELCO ASIA, Nipsil L-300 manufactured by Nippon Silica Industries, and Nipsil KQ.

Commercial products of talc powder include LMS-100, LMS-200, LMS-300, LMS-3500, LMS-400, LMP-100, PKP-53, PKP-80, PKP-81 (FUJI TALC Industry) Company system), D-600, D-800, D-1000, P-2, P-3, P-4, P-6, P-8, SG-95 (manufactured by Nippon Talc Co., Ltd.). These may be used singly or in combination.

Further, in the white thermosetting resin composition of the present invention, the following additives may be contained as needed.

[decane coupling agent]

The white curable resin composition of the present invention preferably further contains a decane coupling agent. By using a coupling agent, not only the adhesion to the glass substrate which can withstand boiling water for 1 hour can be obtained, but also the adhesion between the thermosetting component and the titanium oxide in the molded body is good. The decane coupling agent may be used alone or in combination of two or more.

The decane coupling agent is not particularly limited, and examples thereof include a general epoxy decane coupling agent, an amino decane coupling agent, a cationic decane coupling agent, a vinyl decane coupling agent, a decyl methacrylate coupling agent, and a decyl decane. A coupling agent and a composite coupling agent thereof.

The blending amount of the decane coupling agent is preferably 0.1 parts by mass or more and 15 parts by mass or less based on 100 parts by mass of the total of the (a) copolymerized epoxy group and the (b) curing agent. When the amount is 0.1 part by mass or more, the effect is remarkable. When the amount is 15 parts by mass or less, the white curable resin composition is not thickened, and the cost is also advantageous. It is preferably 10 parts by mass or less.

Commercial products of the decane coupling agent include, for example, 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 are trade names, manufactured by Shin-Etsu Silicone Co., Ltd.) Silquest A-186, Silquest A-187, Y-9805 (all are trade names, manufactured by Momentive Performance Materials). These may be used alone or in combination of two or more.

[Dispersant]

The dispersing agent can be blended for the purpose of improving the dispersibility and sedimentation property of the titanium dioxide. Further, the dispersant is used to adjust the filling property of the minute concave portion of the composition, the surface smoothness of the cured film, the defoaming property of the composition, or the surface tension.

This dispersant is ANTI-TERRAU, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109 DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK -166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-2000, DISPERBYK- 2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (BYK-Chemie.JAPAN), DISPARLON 2150, DISPARLON 1210, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON 7004, DISPARLON 1830, DISPARLON 1860, DISPARLON 1850, DISPARLON DA-400N, DISPARLON PW-36 , DISPARLON DA-703-50 (made by Nanben Chemical Co., Ltd.), Flowlen G-450, Flowlen G-600, Flowlen G-820, Flowlen G-700, Flowlen DOPA-44, Flowlen DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.) )Wait.

In order to achieve the above object, the blending amount of the dispersing agent may be 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the titanium oxide.

[light stabilizer]

Further, in the white curable resin composition of the present invention, a hindered amine light stabilizer can be blended for the purpose of reducing photodegradation of the cured product.

Examples of the hindered amine light stabilizers include: TINUVIN 622LD, TINUVIN 144; CHIMASSORB944LD, CHIMASSORB 119FL (all of which are manufactured by BASF JAPAN); MARK LA-57, LA-62, LA-67, LA-63, LA -68 (all above are ADEKA Company system); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.).

The blending amount of the hindered amine light stabilizer is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total of the (a) copolymerized epoxy and the (b) curing agent.

Further, in the composition of the present invention, a photopolymerization sensitizer such as a thioxanthone or the like, a polymerization inhibitor, a tackifier, a leveling agent, a coupling agent, a flame retardant auxiliary or the like may be blended.

[Adhesion promoter]

The composition of the present invention may contain a conventionally used mercapto compound or adhesion promoter as needed to enhance the adhesion to a substrate such as polyimide. The mercapto compound may, for example, be 2-mercaptopropionic acid, trimethylolpropane gin (2-thiopropionate), 2-mercaptoethanol, 2-aminothiophenol, 3-mercapto-1, A decane coupling agent containing a mercapto group such as 2,4-triazole or the like. Adhesion promoter, for example, benzimidazole, benzo Oxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoene Oxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2- Mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, benzotriazole containing an amine group, vinyltriazine, and the like. These may be used alone or in combination of two or more.

[Colorant]

Further, the white curable resin composition of the present invention may further contain other coloring agents. As the coloring agent to be used, a conventionally known coloring agent such as red, blue, green, yellow or white may be used, and any of a pigment, a dye, and a coloring matter may be used. Specific examples include those in which a color index (C.I.; The Society of Dyers and Colourists) is added as follows.

Red colorant:

The red coloring agent is a monoazo type, a bisazo type, an azo lake type, a benzimidazolone type, an anthracene type, a diketopyrrolopyrrole type, a condensed azo type, an anthraquinone type, and a quinine type. Specific examples of the anthrone and the like include the following.

Monoazo systems: 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.

Bisazo: 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.

Department: 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 system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

蒽醌: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

The blue coloring agent is a compound classified into a pigment (Pigment), specifically: 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.

For dye systems, 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. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:

Green colorants are similarly available in the phthalocyanine, lanthanide, and lanthanide systems. Specifically, they can be used: Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green. 28 and so on. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

The yellow coloring agent is a monoazo type, a disazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, an anthraquinone type, etc., and specifically, the following are mentioned.

Lanthanum: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensed azo system: 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.

Monoazo system: 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.

Bisazo series: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

White coloring agent:

Examples of the white colorant include alumina, magnesia, ammonium oxide, aluminum hydroxide, magnesium carbonate, barium carbonate, and magnesium hydroxide.

In addition, in the purpose of adjusting the color tone, a coloring agent such as purple, orange, brown, or black may be added.

Specifically, there are: PigmentViolet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI color orange 1, CI color orange 5, CI color orange 13, CI color Orange 14, CI color orange 16, CI color orange 17, CI color orange 24, CI color orange 34, CI color orange 36, CI color orange 38, CI color orange 40, CI color orange 43 , CI color orange 46, CI color orange 49, CI color orange 51, CI color orange 61, CI color orange 63, CI color orange 64, CI color orange 71, CI color orange 73, CI Color brown 23, CI color brown 25, CI color black 1, CI color black 7, and the like.

The blending amount of the colorant is not particularly limited, as compared with the aforementioned oxidation 100 parts by mass of titanium, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

[Organic solvents]

Further, the thermosetting resin composition of the present invention can be used as a diluent for the dilution of the composition or the viscosity adjustment applied to the substrate or the carrier film.

Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 赛路苏, methyl 赛苏苏, 丁Kesailusu, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Glycol ethers; esters of ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc. An alcohol such as ethanol, propanol, ethylene glycol or propylene glycol; an aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum ether, naphtha, hydrogenated naphtha or solvent naphtha. These organic solvents may be used singly or in combination of two or more. The amount of the organic solvent to be used is not particularly limited and may be appropriately added as needed.

The thermosetting resin composition of the present invention can be adjusted, for example, to a viscosity suitable for a coating method by using the above organic solvent, and by a dip coating method, a shower coating method, a roll coating method, or a bar coating method. Screen printing method, A method such as a curtain coating method is applied to a substrate, and the organic solvent contained in the composition is volatilized and dried (precure) at a temperature of about 50 to 300 ° C to form a non-tacky coating film.

[Leveling agent]

The leveling agent may, for example, be a polyacrylate polymer, a polyether modified dimethyl polyoxyalkylene copolymer, a polyester modified dimethyl polyoxyalkylene copolymer, or a polyether modified methyl group. An alkyl polyoxyalkylene copolymer, an aralkyl modified methyl alkyl polyoxyalkylene copolymer, a polyether modified methyl alkyl polyoxyalkylene copolymer, and the like. The leveling agents may be used singly or in combination of two or more. A commercially available product of a leveling agent, for example, BYK-Chemie. BYK-352, BYK-354, etc. manufactured by GMBH. The blending amount of the leveling agent is preferably 0.01 to 10 parts by mass, more preferably 1 to 8 parts by mass, per 100 parts by mass of the copolymerized epoxy resin.

[antifoaming agent]

Specific examples of the antifoaming agent, commercially available as an antifoaming agent composed of a non-polyoxynoxy-based foaming polymer solution, are exemplified by BYK-Chemie. BYK (registered trademark) - 054, -055, -057, -1790, etc. manufactured by JAPAN Co., Ltd., as a defoaming agent for polyfluorene-based system, can be cited as BYK-Chemie. BYK (registered trademark) -063, -065, -066N, -067A, -077, and dimethyl phthalate SH200 series manufactured by Dow Corning Toray Silicon Co., Ltd., manufactured by JAPAN.

[substrate]

Examples of the substrate used in the present invention include a resin film such as a polyimide film or a PET film, a glass substrate, a ceramic substrate, a metal substrate, and a wafer plate. Among them, a resin film such as a polyimide film or a PET film or a glass substrate can be preferably used. The material and shape of the substrate are selected depending on the intended use or performance of the molded article, and two or more materials and shapes may be used alone or in combination. Further, from the viewpoint of adhesion, a glass substrate is more preferable.

[manufacturing / mixing method]

The white thermosetting resin composition of the present invention can be produced by uniformly mixing the above-mentioned essential components and other additive components used as needed. As the mixing method, a well-known method can be used, and it is not specifically limited. It can be a method of mixing without using a disperser, or a method of mechanically mixing by various dispersers such as a kneader, a roll, an attritor, or a bead mill.

In a particularly preferred method, the insulating filler, the solvent, and the dispersing agent are blended in advance, and the dispersion liquid dispersed by a disperser such as a rolling mill is mixed with another curable resin component, and the roller is reused as needed. a method in which the rolling mill is dispersed, or a part of the resin component, the insulating filler, the solvent, and the dispersing agent are blended in advance, and the dispersion liquid dispersed by a disperser such as a rolling mill is mixed with another curable resin component, and A method obtained by dispersing a roll mill again in response to the need.

In addition, in the case of adding a coloring agent, it is preferable to add or mix in a water or an organic solvent, and to dissolve or finely disperse in a mixed liquid in which a powder such as a coloring agent is dispersed. A liquid made up of a toner dispersant.

[Coating method]

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

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In addition, unless otherwise indicated, "part" means a mass part, and "%" means a mass %.

(Examples 1 to 8 and Comparative Examples 1 and 2)

The components shown in the following Table 1 were blended in the ratio (parts by mass) shown in Table 1, and the mixture was preliminarily mixed by a stirrer, and then kneaded by a 3-roll mill to prepare a thermosetting resin composition. Paste.

(Evaluation of the production of glass substrates)

The paste of the thermosetting resin composition obtained in the above Examples 1 to 8 and Comparative Examples 1 and 2 was screen-printed using a 420 mesh screen to dry the film thickness of the cured film to about 18 μm. The method was applied to a glass substrate (Gorilla Glass, Corning International Co., Ltd., thickness: 0.7 mm), and the coated glass substrate was placed in an oven (manufactured by Yamato Scientific Co., Ltd., DH-62), and baked at 80 ° C for 10 minutes. Thereafter, the glass substrate was cooled to room temperature. After the above-mentioned coating, heat baking, and cooling were repeated three times, they were again placed in an oven, and baked by heating at 220 ° C for 40 minutes to prepare an evaluation glass substrate having a cured film of 18 μm.

The glass substrate on which the cured film of each thermosetting resin composition was formed was evaluated by the following method with respect to various characteristics as follows.

<Solvent resistance>

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

○: No change was confirmed.

△: A slight change was confirmed.

×: The film was peeled off.

<sulfur resistance>

The glass substrate was immersed in a 10 vol% sulfuric acid aqueous solution at 25 ° C for 30 minutes, washed with water, and then water was removed, and water immersion or film dissolution was visually observed. Then, a transparent adhesive tape (manufactured by NICHIBAN Co., Ltd., horizontal 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.

△: A slight change was confirmed.

×: The immersion of water 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, washed with water, and then water was removed, and water immersion or dissolution of the film was visually confirmed. Then, a transparent adhesive tape (manufactured by NICHIBAN Co., Ltd., horizontal 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.

△: A slight change was confirmed.

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

<Alkaline resistance>

The glass substrate was immersed in a 10 vol% aqueous NaOH solution at 25° C. for 30 minutes, washed with water, and then water was removed to visually confirm the infiltration of water or the dissolution of the film. Then, a transparent adhesive tape (manufactured by NICHIBAN Co., Ltd., horizontal 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.

△: A slight change was confirmed.

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

<High temperature insulation resistance>

The glass substrate was baked in an oven at 230 ° C for 60 minutes, and a resistance meter (manufactured by Agilent Technologes, high resistance meter 4339B, component test fixture (component), respectively, so that the distance between the positive electrode and the negative electrode became 0.5 cm. The positive electrode and the negative electrode of the test fixture) 16339A) were sandwiched between the film of the glass substrate, and the electric resistance of the film was measured under the conditions of a voltage of 500 V and a time of 60 seconds, and the electric resistance of the film was evaluated as follows.

○: Resistance exceeds 10 ¹⁰ Ω

△: The electric resistance is 10 ⁸ or more and 10 ¹⁰ or less.

×: The resistance is less than 10 ⁸ Ω

<Light shielding (OD value)>

The film side of the glass substrate was placed on a measuring instrument and attached to a transmission densitometer (manufactured by SAKATA INX ENG, model: X-Rite 361T, light source wavelength: 400 to 800 nm), and the OD value was evaluated as follows.

○: OD value exceeds 0.7

△: The OD value is 0.5 or more and 0.7 or less.

×: OD value is less than 0.5

<Adhesiveness (checkerboard adhesion test method)>

According to JIS K5400, 100 pieces (10×10) of 1 mm checkerboard were made on the film of the sample, so that the transparent adhesive tape was completely attached to the checkerboard (manufactured by NICHIBAN, width: 18 mm), and one end of the tape was directly applied to the glass. The substrate was peeled off at a right angle, and the number of checkers remaining without being completely peeled off was investigated.

In Table 2 below, the number of remaining checkerboards is taken as a numerator, and the total number (100 pieces) of the checkerboard is used as a denominator to record the result.

○: The checkerboard is 100% residual.

△: The checkerboard remains 95~99%.

×: The checkerboard residue is less than 95%.

<High temperature discoloration tolerance>

The glass substrate was placed in a DENG YNG high-temperature oven (manufactured by Dentsu Instruments Co., Ltd., model: DH-400), baked at 300 ° C for 1 hour, and a glass substrate was measured using a spectrophotometer (manufactured by KONICA MINOLTA Co., Ltd., CM-2600). The degree of discoloration (ΔE) of the surface of the coating film, as follows estimate.

○: △E is less than 1.2

△: △E is 1.2 or more, and is less than 1.5.

×: △E is 1.5 or more

<UV radiation discoloration tolerance>

An ultraviolet irradiation apparatus (Kwan Yi Industry Co., Ltd., Model: GUC-384), to the ultraviolet irradiation energy becomes embodiment 2000mJ / cm ^2, the irradiation was repeated two times for the substrate, the coating film was measured before and after irradiation of discoloration (△ E ), as assessed in the following manner.

○: △E is less than 1.2

△: △E is 1.2 or more, and is less than 1.5.

×: △E is 1.5 or more

<High temperature crack resistance>

The glass substrate was placed in a DENG YNG high-temperature oven (manufactured by Dengying Instruments Co., Ltd., model: DH-400), and heated at 230 ° C for 1 hour using an electron microscope (50 times, manufactured by OLYMPUS, model: MEASURING MICROSCOPE STM-MJS2). The surface flatness of the coating film of the glass substrate was evaluated in the following manner.

○: no crack

△: The crack occurrence rate is 0% or more and less than 50%.

×: The crack occurrence rate is 50% or more

<Hot water resistance (hot water test)>

After the glass substrate was immersed in boiling water at 100 ° C for 60 minutes, water on the surface was taken out and removed, and water immersion or precipitation of the film was visually confirmed. Then, a transparent adhesive tape (manufactured by NICHIBAN Co., Ltd., horizontal 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.

△: A slight change was confirmed.

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

<surface flatness>

Using a surface roughness meter (manufactured by Kosaka Laboratory, model: SE3500), measuring length: 2.5 mm, longitudinal magnification: 1000, horizontal magnification: 100, cutoff: 0.8 mm, speed: 0.5 mm/s The thickness of the surface of the film (maximum height of the peak, RmaxD) was measured 3 times under conditions, and evaluated as follows.

○: RmaxD is less than 2 μm

△: RmaxD is 2 μm or more and less than 3 μm

×: RmaxD is 3 μm or more

<Pencil hardness test>

According to JIS K5400 (1990 edition), a pencil of 4B~9H which has been ground to make the front end of the refill flat is pressed at a pencil angle of about 45°. The glass substrate of each meter (Toyo Seiki, model: C221A) was recorded, and the hardness of the pencil which did not peel off the film was recorded.

The results of the above various evaluation tests are shown in Table 2.

As shown in Table 2, in any of Examples 1 to 8 of the present embodiment, adhesion, surface flatness, and hardenability, high-temperature discoloration resistance, and ultraviolet ray discoloration can be achieved at a high level and balance. Excellent resistance and surface flatness. It was confirmed that the hot water resistance became more excellent especially when the decane coupling agent was blended. On the other hand, in the viewpoint of high-temperature discoloration resistance and surface flatness, Comparative Example 1 using a composition containing a copolymerized epoxy resin having an epoxy equivalent of more than 500 was inferior. Further, in the same manner as in the present embodiment, Comparative Example 2 containing a composition of a copolymerized epoxy having an epoxy equivalent of less than 500 is excellent in surface flatness, but the curing agent to be used has a curing agent for an aromatic ring. Therefore, high temperature discoloration resistance and ultraviolet light discoloration resistance are not sufficient.

Claims (6)

A white thermosetting resin composition characterized by comprising: (a) a copolymerized epoxy resin having an epoxy equivalent having an aromatic ring of not more than 500, and (b) an epoxy hardening having no aromatic ring Anhydride of the agent, (c) an antioxidant, and (d) titanium dioxide. The white thermosetting resin composition according to claim 1, wherein the antioxidant (c) is a phenolic antioxidant. The white thermosetting resin composition according to claim 1 or 2, further comprising a decane coupling agent. The white thermosetting resin composition according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of barium sulfate, cerium oxide and talc. A cured product of the white thermosetting resin composition according to any one of claims 1 to 4, which is formed on a substrate. A member for a display characterized by comprising the cured product according to claim 5.