WO2014208348A1

WO2014208348A1 - Black resin composition for touch panels

Info

Publication number: WO2014208348A1
Application number: PCT/JP2014/065562
Authority: WO
Inventors: 涼介相原; 欣彦井上
Original assignee: 東レ株式会社
Priority date: 2013-06-24
Filing date: 2014-06-12
Publication date: 2014-12-31
Also published as: JP6569220B2; JPWO2014208348A1; TW201506091A

Abstract

The purpose of the present invention is to provide a black resin composition for touch panels, which is used for the formation of a light blocking film for touch panels, said light blocking film having high chemical resistance and capable of achieving high infrared light transmittance, while faultlessly blocking visible light. The present invention provides a black resin composition for touch panels, which contains a black pigment having a specific structure, a resin and a solvent.

Description

Black resin composition for touch panels

The present invention relates to a black resin composition for a touch panel.

Recently, a cover glass integrated touch panel in which a light shielding film, a conductive film and a sensor are directly formed on a cover glass has been proposed.

Many smartphones and tablet terminals equipped with a cover glass-integrated touch panel are equipped with proximity sensors for detecting the approach of an object. A function for switching the ON / OFF of is provided.

As the proximity sensor, a sensor composed of a light emitting element that transmits infrared light and a light receiving element that receives infrared light and converts it into an electric signal is widely used. In such a configuration, in order to further improve the appearance and yield of the touch panel, the light shielding film that separates the proximity sensor and the object may not inhibit transmission / reception of infrared rays, that is, transmit infrared rays. Is preferred. A method of applying an infrared transmitting ink to an infrared transmitting portion to match the color tone with the surrounding light shielding film is also conceivable. However, it is difficult to perfectly match the color tone, and it is more complicated to apply the ink to a narrow range. This is because the number of processes increases.

As a light-shielding film that transmits infrared rays, for example, a light-shielding film containing a perylene-based black pigment and carbon black (Patent Document 1) and a light-shielding film containing a blue pigment and a red pigment (Patent Document 2) are known.

JP 2012-68613 A International Publication No. 2012/157222

However, the conventional light-shielding film capable of transmitting infrared rays has a problem that infrared transmittance is not sufficient, or the process of producing the light-shielding film causes discoloration due to the influence of the etching solution.

Further, particularly in the light-shielding film containing a red pigment and a blue pigment, there is a problem that the reflection chromaticity is not neutral and visibility is deteriorated, and the pigment is sublimated by heating in the manufacturing process.

Accordingly, the present invention provides a black resin composition for a touch panel for forming a light-shielding film for a touch panel, which has high chemical resistance, sufficiently blocks visible light, and can achieve high infrared transmittance. With the goal.

(1) A black resin composition for a touch panel comprising a black pigment, a resin and a solvent represented by a general formula selected from the group consisting of the following general formulas (I) to (III).

(In the general formulas (I) to (III), R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ³ and R ⁴ each independently represent R ^{^{^{^{11, oR 11, SR 11,}}}} COR 11, CONR 12 R 13, NR 12 COR 11, OCOR 11, COOR 11, SCOR 11, OCSR 11, COSR 11, CSOR 11, CN, a halogen atom or a hydroxyl ^{group, R 11} , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or the number of carbon atoms 2 to 20 heterocyclic groups, a and b each independently represent an integer of 0 to 4)
(2) The black resin composition for a touch panel according to (1), further containing a pigment selected from the group consisting of a blue pigment, a green pigment, a yellow pigment, and a purple pigment.
(3) The black resin composition for a touch panel according to the above (1) or (2), further containing a photopolymerization initiator.
(4) A light shielding film for a touch panel, which is formed from the black resin composition for a touch panel according to any one of (1) to (3).
(5) A touch panel front plate comprising the touch panel light-shielding film according to (4).
(6) Use of a black resin composition containing a black pigment, a resin and a solvent represented by the general formula selected from the group consisting of the following general formulas (I) to (III) for forming a light-shielding film for a touch panel .

(In the general formulas (I) to (III), R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ³ and R ⁴ each independently represent R ^{^{^{^{11, oR 11, SR 11,}}}} COR 11, CONR 12 R 13, NR 12 COR 11, OCOR 11, COOR 11, SCOR 11, OCSR 11, COSR 11, CSOR 11, CN, a halogen atom or a hydroxyl ^{group, R 11} , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or the number of carbon atoms 2 to 20 heterocyclic groups, a and b each independently represent an integer of 0 to 4)
(7) Use of the black resin composition according to the above (6), which further contains a pigment selected from the group consisting of a blue pigment, a green pigment, a yellow pigment and a purple pigment, for forming a light-shielding film for a touch panel.
(8) Use for forming the light shielding film for touchscreens of the black resin composition as described in said (6) or (7) containing a photoinitiator further.
(9) A touch panel front plate comprising a touch panel light-shielding film formed using the black resin composition according to any one of (6) to (8) above.

According to the black resin composition for a touch panel of the present invention, it forms a light-shielding film for a touch panel that has excellent chemical resistance, can sufficiently block visible light, and can transmit infrared light with high efficiency. be able to.

The black resin composition for a touch panel of the present invention is characterized by containing a black pigment, a resin and a solvent represented by a general formula selected from the group consisting of the above general formulas (I) to (III).

It is important that the black resin composition for a touch panel of the present invention contains a black pigment represented by a general formula selected from the group consisting of the above general formulas (I) to (III). In the above general formulas (I) to (III), R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, but this alkyl group may further have another substituent. The general formulas represented by the above general formulas (I) to (III) are related to cis-trans isomers. For example, the black pigment represented by the general formula (I) and the general formula (II) The black pigment represented by formula (III) or the black pigment represented by formula (III) may be used alone, or the black pigment represented by formula (I) and the black pigment represented by formula (II) A mixture of a plurality of types of black pigments may be used as in a combined mixture.

By using any of the black pigments represented by the above general formulas (I) to (III), it is possible to achieve both high light-shielding properties in the visible light region and high transmittance in the infrared light region, and high chemical resistance. It is possible to form a light shielding film having

The black pigments represented by the above general formulas (I) to (III) are known (Japanese Patent Publication No. 2012-515233) and are commercially available (for example, Irgaphor Black S0100CF; manufactured by BASF Corporation). .

Although the black pigments represented by the above general formulas (I) to (III) play a role as a light shielding material, the black resin composition for a touch panel of the present invention may contain other light shielding materials. Examples of other light shielding materials include carbon black, titanium black, chromium oxide, iron oxide, aniline black, perylene pigments, and C.I. I. Solvent black 123 may be mentioned.

The black resin composition for a touch panel of the present invention preferably further contains a pigment selected from the group consisting of a blue pigment, a green pigment, a yellow pigment and a purple pigment. By containing these pigments, the color of the formed light shielding film and the transmittance in the ultraviolet region can be further improved.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 or 79. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 or 60 is preferable. I. Pigment Blue 15: 6 is more preferable.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. I. Pigment Green 7, 36 or 58 is preferable.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207 or 208, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferable. I. Pigment Yellow 83, 138, 139, 150 or 180 is more preferable.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 or 50. I. Pigment Violet 19 or 23 is preferred, and C.I. I. Pigment Violet 23 is more preferable.

In addition, the black resin composition for a touch panel of the present invention may further contain other color pigments such as a red pigment and an orange pigment.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275 or 276. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 is preferred, and C.I. I. Pigment Red 177, 209, 224, 242 or 254 is more preferable.

Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79. I. Pigment Orange 38 or 71 is preferred.

The black resin composition for a touch panel of the present invention contains a resin. Examples of the resin include an epoxy resin, a cardo resin, an acrylic resin, a siloxane resin, or a polyimide resin, and an acrylic resin or a polyimide resin that is excellent in heat resistance of the coating film and storage stability of the black resin composition is preferable. .

As the acrylic resin, an acrylic resin having a carboxyl group is preferable. As the acrylic polymer having a carboxyl group, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferable. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and vinyl acetic acid. Examples of the ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, and n-acrylate. Butyl, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, N-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and other unsaturated carboxylic acid alkyl esters, styrene, p-methylstyrene, o- Aromatic vinyl compounds such as til styrene, m-methyl styrene or α-methyl styrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate or glycidyl methacrylate, vinyl acetate or propionic acid Carboxylic acid vinyl esters such as vinyl, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile or α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene or isoprene, polystyrene having an acryloyl group or a methacryloyl group at each end , Polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate or polybutyl methacrylate.

Among them, a quaternary copolymer of methacrylic acid and / or acrylic acid and a monomer selected from the group consisting of methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate and styrene has a weight average molecular weight (Mw). ) Is 2,000 to 100,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve), and a resin having an acid value of 70 to 150 (mgKOH / g) It is preferable because it has an appropriate solubility in an alkali developer.

Further, an acrylic resin having an ethylenically unsaturated group in the side chain is preferable if the sensitivity during exposure and development is improved. In this case, the ethylenically unsaturated group that the side chain has is preferably an acryl group or a methacryl group. Such an acrylic resin can be obtained by addition-reacting an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to a carboxyl group of an acrylic resin having a carboxyl group.

As an acrylic resin having an ethylenically unsaturated group in the side chain, an acrylic resin described in known literature (for example, Japanese Patent No. 3120476 or JP-A-8-262221) or a commercially available “Cyclomer (registered trademark)” P (Daicel Chemical Industries, Ltd.) or alkali-soluble cardo resin is mentioned.

The black resin composition for a touch panel of the present invention may further contain a monomer. As the monomer, for example, a polyfunctional or monofunctional acrylic monomer or oligomer can be used. Examples of polyfunctional acrylic monomers include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylic acid Esters, propylene oxide (phthalate) anhydride (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, publicly known literature (for example, Japanese Patent No. 3621533) Or a full orange acrylate oligomer described in JP-A-8-278630), tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate, 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [4- (3-Acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4,4′-bis [4- (3- [Chryloxy-2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (3-acryloxy- 2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol Examples include full orange acrylate or biscresol full orange methacrylate. In order to further improve sensitivity, a monomer having 3 or more functional groups is preferable, and a monomer having 5 or more functional groups is more preferable. More preferred is pentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate.

The black resin composition for a touch panel of the present invention preferably further contains a photopolymerization initiator. As a resin contained in the black resin composition for a touch panel of the present invention, a photosensitive resin typified by an acrylic resin is used, and a photopolymerization initiator is combined with this to make the black resin composition for a touch panel of the present invention photosensitive. Can be granted. As a result, a desired light-shielding film can be easily and precisely formed by photolithography, that is, exposure and development processes. When the black resin composition for a touch panel of the present invention is photosensitive and contains a pigment selected from the group consisting of a blue pigment, a green pigment, a yellow pigment and a violet pigment, light during exposure and development It becomes possible to further improve the sensitivity of curing.

Examples of the photopolymerization initiator include benzophenone compounds, acetophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, oxime ester compounds, carbazole compounds, triazine compounds, and phosphorus compounds. Or inorganic type photoinitiators, such as titanate, are mentioned.

More specifically, for example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, Benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane “Irgacure®” 369, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, “Irgacure®” 379, 2- (dimethylamino) -2 -[(4 Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, “Irgacure®” 907, 2-methyl-1- [4- (methylthio) phenyl] -2- Morphonopropan-1-one, CGI-113 2- [4-methylbenzyl] -2-dimethylamino-1- (4-morpholinophenyl) -butanone, “Irgacure®” OXE01 , 2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], “Irgacure®” OXE02, ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) or CGI-242, ethanone, 1- [9-ethyl- -(2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (both manufactured by Ciba Specialty Chemicals), t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (Trichloromethyl) -s-triazine, a carbazole compound Some “ADEKA (registered trademark) optomer” N-1818 or oxime ester compounds “ADEKA ARKLES” NCI-831 or NCI-930 (both manufactured by ADEKA Corporation), PBG304 or PBG305 (both are Changzhou Strong Electronics) In order to improve sensitivity further, "Irgacure (registered trademark)" 379, "Irgacure (registered trademark)" OXE02, "Adeka (registered trademark) Optomer" N-1919, " It is preferable to use two types selected from the group consisting of Adeka Arcles “NCI-831 and PBG304” in combination.

The black resin composition for a touch panel of the present invention may contain an adhesion improving agent in order to improve adhesion to an inorganic material such as a glass plate or a silicon wafer. Examples of the adhesion improving agent include a silane coupling agent or a titanium coupling agent. The addition amount of the adhesion improving agent is usually about 0.2 to 20% by mass with respect to the resin.

The black resin composition for a touch panel of the present invention may contain a polymer dispersant in order to improve the dispersion stability of the light shielding material and the pigment. Examples of the polymer dispersant include a polyester polymer dispersant, an acrylic polymer dispersant, a carbodiimide dispersant, a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, and a polyallylamine polymer dispersant. Is mentioned. These polymer dispersants may be appropriately selected in consideration of the type of light shielding material and pigment to be dispersed. The polymer dispersant is classified into a dispersant having only an amine value, a dispersant having only an acid value, a dispersant having an amine value and an acid value, or a dispersant having neither an amine value nor an acid value. However, in order to make the effect of the present invention more remarkable, a dispersant having an amine value is preferable, and a polymer dispersant having only an amine value is more preferable.

Examples of the dispersant having only an amine value include Dispersic 102, 160, 161, 162, 2163, 2164, 166, 167, 168, 2000, 2050, 2150, 2155, LPN6919, LPN21116, LPN21234, 9075 or 9077 ( As described above, all are manufactured by Big Chemie), EFKA 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403 or 4800 (all are manufactured by BASF) Alternatively, Azisper PB711 (manufactured by Ajinomoto Fine Techno Co., Ltd.) can be mentioned, but Dispersic LPN6919 or LPN21116 which is a polymer dispersant having a tertiary amino group is preferable.

Examples of the polymer dispersant having an amine value and an acid value include Dispersic 142, 145, 2001, 2010, 2020, 2025, or 9076 or Anti-Terra-205 (all of which are manufactured by BYK Chemie), Solsperse 24000 ( Lubrizol Co., Ltd.) or Azisper PB821, PB880 or PB881 (all of which are manufactured by Ajinomoto Fine Techno Co., Ltd.).
These polymer dispersants are preferably added to such an extent that adhesion and photosensitivity are not reduced, and the amount of the polymer dispersant added is usually about 1 to 40% by mass with respect to the light shielding material and the pigment.

In the black resin composition for a touch panel of the present invention, the mass ratio of the light shielding material and the pigment / resin, the monomer and the polymer dispersant is 60/40 to 5 / A range of 95 is preferable, and a range of 50/50 to 10/90 is more preferable. If the amount of resin, monomer and polymer dispersant is too small, the reflectivity will increase. On the other hand, if the amount of the light shielding material and the pigment is too small, the optical density per unit thickness (OD value / μm) becomes low, and it is necessary to increase the film thickness.

The black resin composition for a touch panel of the present invention contains a solvent. As the solvent, water or an organic solvent may be appropriately selected in consideration of the dispersion stability of the pigment to be dispersed and the solubility of the resin to be added. Examples of the organic solvent include esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents, or lactone polar solvents.

Examples of the organic solvent for dissolving the acrylic resin include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. Mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono -N-butyl ether, dipropylene glyco (Poly) alkylene glycol mono, such as dimonomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether Alkyl ethers, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 1,3-butylene glycol diacetate, propylene glycol monomethyl ether acetate (hereinafter, “PMA”) (Poly) alkylene glycol monoalkyl ether acetates such as dipropylene glycol methyl ether acetate or propylene glycol monoethyl ether acetate, other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or tetrahydrofuran, methyl ethyl ketone, cyclohexanone, Ketones such as 2-heptanone or 3-heptanone, alkyl lactates such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethyl Ethyl toxipropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate , Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid -Other esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate, aromatics such as toluene or xylene Hydrocarbons or N-methylpyrrolidone, N, N-dimethyl Formamide or N, such as amides such as N- dimethylacetamide.

Furthermore, as the substrate becomes larger, application by a die coating apparatus has become mainstream, and in order to achieve appropriate volatility and drying properties, 30 to 75% by mass of a solvent having a boiling point of 170 ° C. or higher is contained. Furthermore, it is more preferable to contain 1 to 20% by mass of a solvent having a boiling point of 200 ° C. or higher in order to reduce foreign matter defects in a die coating apparatus and drying-induced defects in a vacuum drying apparatus. In such a case, it is preferable to use a mixed solvent composed of at least two kinds.

The black resin composition for a touch panel of the present invention may contain a surfactant in order to perform Benard cell while ensuring applicability and smoothness of the colored film. The addition amount of the surfactant is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass with respect to the light shielding material and the pigment.

Examples of the surfactant include an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine, a cationic surfactant such as stearylamine acetate or lauryltrimethylammonium chloride, lauryldimethylamine oxide, or lauryl. Amphoteric surfactants such as carboxymethylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate, and silicone-based interfaces mainly composed of polydimethylsiloxane An activator or a fluorosurfactant may be used.

As solid content concentration which combined the resin component (components also including additives, such as a monomer, an oligomer, and a photoinitiator except a solvent) in the black resin composition for touchscreens of this invention, and a coloring material, coating property is set. From the viewpoint of dryness, it is preferably 2 to 30% by mass, more preferably 5 to 20% by mass.

As a method for producing the black resin composition for a touch panel of the present invention, for example, a method of directly dispersing a pigment in a resin solution using a disperser, or a method of dispersing a pigment in water or an organic solvent using a disperser. A method of preparing a pigment dispersion and then mixing the pigment dispersion and a resin solution can be mentioned. Examples of the pigment dispersion method include a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill. From the viewpoint of dispersion efficiency and fine dispersion, a bead mill is preferable. Examples of the bead mill include a coball mill, a basket mill, a pin mill, and a dyno mill. As beads of the bead mill, for example, titania beads, zirconia beads, or zircon beads are preferable. The bead diameter used for dispersion is preferably 0.01 to 5.0 mm, and more preferably 0.03 to 1.0 mm. When the primary particle size of the pigment and the secondary particle size formed by agglomeration of the primary particles are small, the bead size used for dispersion is preferably a fine dispersed bead of 0.03 to 0.10 mm. In this case, it is preferable to disperse using a bead mill having a separator by a centrifugal separation method capable of separating fine dispersed beads and a dispersion. On the other hand, when a pigment containing coarse particles of about submicron is dispersed, dispersed beads having a bead diameter of 0.10 mm or more are preferable in order to obtain a sufficient grinding force.

The light-shielding film for a touch panel of the present invention is formed from the black resin composition for a touch panel of the present invention. The example of the manufacturing method of the light shielding film for touchscreens of this invention is shown below. Examples of a method for applying the black resin composition for a touch panel of the present invention on a substrate include, for example, a dipping method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, a method of immersing a substrate in a solution, or a solution. There is a method of spraying on the substrate. Examples of the substrate on which the black resin composition for a touch panel of the present invention is applied include, for example, quartz glass, borosilicate glass, aluminosilicate glass, inorganic glass such as soda lime glass or chemically tempered glass coated with silica, or organic plastic. Film or sheet. In addition, when apply | coating the black resin composition for touchscreens of this invention on a board | substrate, by processing the board | substrate surface with adhesion aids, such as a silane coupling agent, an aluminum chelating agent, or a titanium chelating agent, a coating film and The adhesive force with the substrate can be improved.

After applying the black resin composition for a touch panel of the present invention on a substrate, the coating film is heated and dried and cured by air drying, heat drying or vacuum drying to form a dry film. In order to suppress drying unevenness and transport unevenness when forming a film, the substrate coated with the black resin composition for a touch panel of the present invention is dried under reduced pressure with a vacuum dryer equipped with a heating device, and then heated and cured. Is preferred.

The obtained coating film is usually subjected to pattern processing using a method such as photolithography after forming an oxygen blocking film as necessary. Thereafter, if necessary, after removing the oxygen blocking film, the film is further heat-dried and cured to obtain a light shielding film. The thermosetting conditions vary depending on the resin, but when an acrylic resin is used, it is generally heated at 200 to 250 ° C. for 1 to 60 minutes.

The touch panel front plate of the present invention includes the touch panel light shielding film of the present invention. The touch panel front plate can be composed of a transparent substrate and the light shielding film of the present invention formed on a partial region of the transparent substrate.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Evaluation method>
[Sublimation]
A light-shielding film having a desired film thickness is formed on a 0.7 mm thick chemically strengthened glass (Gorilla (registered trademark); manufactured by Corning), heated in a hot air oven at 280 ° C. for 30 minutes, and then the surface of the coating film is a white cloth. Then, it was visually observed whether or not the pigment-derived sublimate adhered. A white cloth colored by adhesion of a pigment-derived sublimate was judged as B, and a white cloth was judged as A.

[Transmissivity]
A light-shielding film having an OD value of 3 is formed on a chemically strengthened glass having a thickness of 0.7 mm, and a spectrophotometer (UV-2500PC; Shimadzu Corporation, measurement wavelength region: 280 to 1000 nm, sampling pitch: 1.0 nm) , Scanning speed: low speed, slit width: 2.0 nm).

[Reflection chromaticity]
A light-shielding film having a desired film thickness is formed on a chemically tempered glass having a thickness of 0.7 mm, and using a spectroscopic clock (MPC-2200; manufactured by Shimadzu Corporation), the reflected chromaticity (reflectance R, A * and b *) of the L * a * b color system were measured. (Measurement wavelength region: 380 to 780 nm, sampling pitch: 1.0 nm, scan speed: low speed, slit width: 2.0 nm). The value of b *, which is the index of blueness (the blueness becomes stronger as it goes in the negative direction) is −0.3 or less, A is −0.2 to 0.2, B is 0.3 to 0 .7 was judged as C, and 0.8 or more was judged as D.

[OD value]
A light-shielding film having a film thickness of 1.0 μm is formed on a chemically strengthened glass having a thickness of 0.7 mm, and the intensity of each of incident light and transmitted light is measured using an X-rite 361T (visual) densitometer. Calculated from 1).
OD value = log ₁₀ (I ₀ / I) (1)
I ₀ : Incident light intensity I: Transmitted light intensity [PAN resistance]
A PAN solution (HNO ₃ / H ₃ PO ₄ / CH ₃ COOH / H ₂ O = mass ratio 5 /) is formed by forming a light-shielding film having a desired film thickness on a chemically strengthened glass having a thickness of 0.7 mm and heating to 50 ° C. 68/12/15) for 2 minutes, and the OD value change before and after the PAN solution treatment was measured.

(Synthesis of acrylic polymer (P-1))
After synthesizing methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30/40/30) by the method described in the literature (Japanese Patent No. 3120476; Example 1), 40 parts by mass of glycidyl methacrylate was added, By reprecipitation with purified water, filtration, and drying, an acrylic polymer (P-1) powder having a weight average molecular weight (Mw) of 10,000 and an acid value of 110 (mgKOH / g) was obtained.

(Production of black pigment dispersion Bk-1)
Black pigment 1 ("Irgaphor Black S0100CF" manufactured by BASF): 600.0 g of acrylic resin (P-1) in propylene glycol monomethyl ether acetate 35% by mass (321.4 g), polymer dispersant (BYK21116; BYK Chemie) 93.8 g) and propylene glycol monoethyl ether acetate (1984. 8 g) were charged into a tank and stirred for 1 hour with a homomixer (manufactured by Tokushu Kika) to obtain a preliminary dispersion 1. Thereafter, the preliminary dispersion 1 was supplied to an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 70% of 0.10 mmφ zirconia beads (manufactured by Toray), and dispersed for 2 hours at a rotational speed of 8 m / s. Then, a black pigment dispersion Bk-1 having a solid content concentration of 25 mass% and a pigment / resin (mass ratio) of 80/20 was obtained.

(Production of organic pigment dispersion DB-1)
Organic pigment dispersion DB-1 was obtained in the same manner as black pigment dispersion Bk-1, except that organic pigment PB15: 6 (manufactured by Toyo Ink Co., Ltd.) was used instead of black pigment 1.

(Production of organic pigment dispersion DG-1)
Organic pigment dispersion DG-1 was obtained in the same manner as black pigment dispersion Bk-1, except that organic pigment PG58 (manufactured by DIC Corporation) was used in place of black pigment 1.

(Production of organic pigment dispersion DY-1)
An organic pigment dispersion DY-1 was obtained in the same manner as the black pigment dispersion Bk-1, except that an organic pigment PY150 (manufactured by LANXESS) was used instead of the black pigment 1.

(Production of organic pigment dispersion DV-1)
Organic pigment dispersion DV-1 was obtained in the same manner as black pigment dispersion Bk-1, except that organic pigment PV23 (manufactured by Clariant Co., Ltd.) was used instead of black pigment 1.

(Production of organic pigment dispersion DR-1)
Organic pigment dispersion DR-1 was obtained in the same manner as black pigment dispersion Bk-1, except that organic pigment PR254 (manufactured by BASF) was used instead of black pigment 1.

(Production of organic pigment dispersion DR-2)
Organic pigment dispersion DR-2 was obtained in the same manner as black pigment dispersion Bk-1, except that organic pigment PR177 (manufactured by BASF) was used instead of black pigment 1.

(Production of black pigment dispersion Bk-2)
A black pigment dispersion Bk-2 was obtained in the same manner as the black pigment dispersion Bk-1, except that titanium nitride (manufactured by Nissin Engineering Co., Ltd.) was used instead of the black pigment 1.

(Production of black pigment dispersion Bk-3)
A black pigment dispersion Bk-3 was obtained in the same manner as the black pigment dispersion Bk-1, except that carbon black (TPX1291; manufactured by CABOT) was used instead of the black pigment 1.

(Example 1)
0.38 g of Adeka Arcles (registered trademark) NCI-831 as a photopolymerization initiator was added to 29.52 g of PMA, and the mixture was stirred until the solid content was dissolved.

Furthermore, 16.03 g of a 35% by weight PMA solution of acrylic polymer (P-1), 3.38 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, and silicone-based surfactant as a surfactant 0.24 g of a PMA 10 mass% solution of the agent BYK333 was added and stirred at room temperature for 1 hour to obtain a photosensitive resist. By adding 10.46 g of black pigment dispersion Bk-1 to this photosensitive resist, a photosensitive black resin composition having a total solid content concentration of 20% by mass, pigment / resin (mass ratio) = 18/82, and black pigment = 100 Product A-1 was prepared.

The prepared photosensitive black resin composition 1 is filtered through a 2 μm Teflon (registered trademark) filter, and then a spin coating apparatus 1H-DS manufactured by Mikasa Co., Ltd. is formed on the substrate so that the film thickness becomes 1 μm (after post-baking). The substrate thus coated was heated for 2 minutes with pin-shaped protrusions on a hot plate at 90 ° C., and further pre-baked by leaving the substrate directly on the hot plate for 2 minutes. The coating film was exposed to ultraviolet rays at an exposure dose of 200 mJ / cm ² through a mask for resolution test using a mask aligner PEM-6M manufactured by Union Optics.

Next, a patterning substrate was obtained by developing with an alkali developer of 0.1% by mass tetramethylammonium hydroxide aqueous solution, followed by washing with pure water. The obtained patterning board | substrate was hold | maintained for 30 minutes at 230 degreeC in hot air oven, and the light-shielding board | substrate 1 was obtained by performing a post-baking.

(Example 2)
The mass ratio of the pigment used as the colorant is black pigment 1 / blue pigment PB15: 6 = 80/20 (8.37 g of the above dispersion BK-1 and 2.09 g of pigment dispersion DB-1 are added to the photosensitive resist. Except for the above, a photosensitive black resin composition A-2 was obtained in the same manner as in Example 1. Using the obtained photosensitive resin composition A-2, a light shielding substrate 2 was obtained in the same manner as in Example 1.

(Example 3)
The mass ratio of the pigment used as the colorant is black pigment 1 / blue pigment PB15: 6 = 50/50 (5.23 g of the above dispersion BK-1 and 5.23 g of pigment dispersion DB-1 are added to the photosensitive resist. Except for the above, a photosensitive black resin composition A-3 was obtained in the same manner as in Example 1. Using the obtained photosensitive resin composition A-3, a light-shielding substrate 3 was obtained in the same manner as in Example 1.

Example 4
The mass ratio of the pigment used as the colorant is black pigment 1 / green pigment PG58 = 80/20 (8.37 g of the above dispersion BK-1 and 2.09 g of pigment dispersion DG-1 are added to the photosensitive resist). A photosensitive black resin composition A-4 was obtained in the same manner as in Example 1 except that. Using the obtained photosensitive resin composition A-4, a light shielding substrate 4 was obtained in the same manner as in Example 1.

(Example 5)
The mass ratio of the pigment used as the colorant is black pigment 1 / yellow pigment PY150 = 80/20 (8.37 g of the above dispersion BK-1 and 2.09 g of pigment dispersion DY-1 are added to the photosensitive resist). A photosensitive black resin composition A-5 was obtained in the same manner as in Example 1 except that. A light-shielding substrate 5 was obtained in the same manner as in Example 1 using the obtained photosensitive resin composition A-5.

(Example 6)
The mass ratio of the pigment used as the colorant is black pigment 1 / purple pigment PV23 = 80/20 (adding 8.37 g of the above dispersion BK-1 and 2.09 g of pigment dispersion DV-1 to the photosensitive resist). A photosensitive black resin composition A-6 was obtained in the same manner as in Example 1 except that. Using the obtained photosensitive resin composition A-6, a light-shielding substrate 6 was obtained in the same manner as in Example 1.

(Example 7)
The mass ratio of the pigment used as the colorant is black pigment 1 / red pigment PR254 = 80/20 (8.37 g of the above dispersion BK-1 and 2.09 g of pigment dispersion DR-1 are added to the photosensitive resist). A photosensitive black resin composition A-7 was obtained in the same manner as in Example 1 except that. Using the obtained photosensitive resin composition A-7, a light-shielding substrate 7 was obtained in the same manner as in Example 1.

(Example 8)
The mass ratio of the pigment used as the colorant is black pigment 1 / red pigment PR177 = 80/20 (8.37 g of the above dispersion BK-1 and 2.09 g of pigment dispersion DR-2 are added to the photosensitive resist). A photosensitive black resin composition A-8 was obtained in the same manner as in Example 1 except that. Using the obtained photosensitive resin composition A-8, a light-shielding substrate 8 was obtained in the same manner as in Example 1.

(Comparative Example 1)
The mass ratio of the pigment used as the colorant is blue pigment PB15: 6 / red pigment PR254 = 50/50 (5.23 g of the above dispersion DB-1 and 5.23 g of the pigment dispersion DR-1 are added to the photosensitive resist. Except for the above, a photosensitive black resin composition A-9 was obtained in the same manner as in Example 1. Using the obtained photosensitive resin composition A-9, a light-shielding substrate 9 was obtained in the same manner as in Example 1.

(Comparative Example 2)
The mass ratio of the pigment used as the colorant is blue pigment PB15: 6 / red pigment PR177 = 50/50 (5.23 g of the above dispersion DB-1 and 5.23 g of pigment dispersion DR-2 are added to the photosensitive resist. Except for the above, a photosensitive black resin composition A-10 was obtained in the same manner as in Example 1. Using the obtained photosensitive resin composition A-10, a light-shielding substrate 10 was obtained in the same manner as in Example 1.

(Comparative Example 3)
Photosensitive black resin composition A in the same manner as in Example 1 except that the mass ratio of the pigment used as the colorant was titanium nitride = 100 (10.46 g of the dispersion Bk-2 was added to the photosensitive resist). -11 was obtained. Using the obtained photosensitive resin composition A-11, a light-shielding substrate 11 was obtained in the same manner as in Example 1.

(Comparative Example 4)
Photosensitive black resin composition A in the same manner as in Example 1 except that the mass ratio of the pigment used as the colorant was carbon black = 100 (10.46 g of the above dispersion Bk-3 was added to the photosensitive resist). -12 was obtained. Using the obtained photosensitive resin composition A-12, a light shielding substrate 12 was obtained in the same manner as in Example 1.

<Evaluation results>
Tables 1 and 2 show the compositions of the black resin compositions produced in Examples 1 to 8 and Comparative Examples 1 to 4 and the evaluation results of the produced light shielding substrates.

In each of Examples 1 to 8, the transmittance in the infrared region of 850 to 1000 nm is as high as 60% or more, sufficiently transmits the infrared region light necessary for the operation of the proximity sensor, that is, the infrared ray, and reflects chromaticity. In addition, a good light-shielding substrate could be obtained.

Further, as in Examples 2 to 6, the transmittance at 280 to 480 nm was improved by further adding a blue pigment, a green pigment, a yellow pigment or a purple pigment. This result suggests that efficient photocuring is possible even with a low exposure amount, and that a photosensitive light-shielding film having excellent pattern processability can be provided.

On the other hand, as in Comparative Examples 1 and 2, the light-shielding film in which a red pigment and a blue pigment are mixed is inferior in terms of generation of sublimates and PAN resistance, and can provide a light-shielding film excellent in chemical resistance. There wasn't.

Further, as in Comparative Examples 3 and 4, the light shielding film of the system using titanium nitride or carbon black, which is an inorganic black pigment, did not transmit infrared rays, and a light shielding film having excellent optical characteristics could not be obtained.

The black resin composition for a touch panel of the present invention can be used for forming a light shielding film provided on a front panel for a touch panel that transmits infrared rays for a proximity sensor.

Claims

A black resin composition for a touch panel, comprising a black pigment represented by a general formula selected from the group consisting of the following general formulas (I) to (III), a resin and a solvent.

(In the general formulas (I) to (III), R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 each independently represent R 11, oR 11, SR 11, COR 11, CONR 12 R 13, NR 12 COR 11, OCOR 11, COOR 11, SCOR 11, OCSR 11, COSR 11, CSOR 11, CN, a halogen atom or a hydroxyl group, R 11 , R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or the number of carbon atoms 2 to 20 heterocyclic groups, a and b each independently represent an integer of 0 to 4)
The black resin composition for a touch panel according to claim 1, further comprising a pigment selected from the group consisting of a blue pigment, a green pigment, a yellow pigment, and a purple pigment.
The black resin composition for a touch panel according to claim 1 or 2, further comprising a photopolymerization initiator.
A light shielding film for a touch panel, which is formed from the black resin composition for a touch panel according to any one of claims 1 to 3.
A touch panel front plate comprising the light shielding film for a touch panel according to claim 4.
Use of a black resin composition containing a black pigment, a resin and a solvent represented by the general formula selected from the group consisting of the following general formulas (I) to (III) for forming a light-shielding film for a touch panel.

(In the general formulas (I) to (III), R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 each independently represent R 11, oR 11, SR 11, COR 11, CONR 12 R 13, NR 12 COR 11, OCOR 11, COOR 11, SCOR 11, OCSR 11, COSR 11, CSOR 11, CN, a halogen atom or a hydroxyl group, R 11 , R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or the number of carbon atoms 2 to 20 heterocyclic groups, a and b each independently represent an integer of 0 to 4)
Furthermore, the use for forming the light shielding film for touchscreens of the black resin composition of Claim 6 containing the pigment chosen from the group which consists of a blue pigment, a green pigment, a yellow pigment, and a purple pigment.
Furthermore, the use for forming the light shielding film for touchscreens of the black resin composition of Claim 6 or 7 containing a photoinitiator.
A touch panel front plate comprising a touch panel light-shielding film formed using the black resin composition according to any one of claims 6 to 8.