TW201506091A - Black resin composition for touch panels - Google Patents

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 panel

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

In recent years, a protective glass-integrated touch panel in which a light-shielding film, a conductive film, and a sensor are directly formed on a protective glass has been proposed.

A smart phone or a tablet terminal having a protective glass-integrated touch panel is equipped with a proximity sensor for sensing the proximity of an object, for example, to give an approach to the user's face during a call. It can switch the ON/OFF function of the display.

As the proximity sensor, a light-emitting element that transmits infrared light and a light-receiving element that receives infrared rays and converts it into an electrical signal are widely used. In such a configuration, in order to make the appearance or the yield of the touch panel more excellent, it is preferable that the light shielding film that separates the proximity sensor and the object does not hinder the transmission and reception of infrared rays, and can penetrate the infrared rays. Although it is also considered to apply an infrared ray penetrating ink to the infrared ray penetrating portion to integrate the color tone with the peripheral light absorbing film, it is difficult to completely integrate the color tone, thereby increasing the troublesome step of ink coating in a narrow range.

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

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2012-68613

Patent Document 2: International Publication No. 2012/157222

However, conventionally, a light-shielding film which can penetrate infrared rays has a problem that the transmittance of infrared rays is insufficient, or fading occurs due to the influence of an etching liquid in the manufacturing process of a light-shielding film.

Further, in particular, in the light-shielding film containing a red pigment and a blue pigment, in addition to the deterioration of the reflection chromaticity, the visibility is deteriorated, and there is also a problem that the pigment is sublimated by heating in the production step.

Therefore, an object of the present invention is to provide a black resin composition for a touch panel for forming a light-shielding film for a touch panel, which has high chemical resistance and can achieve high transmittance of infrared rays under sufficient visible light.

(1) A black resin composition for a touch panel comprising a black pigment, a resin, and a solvent selected from the group consisting of the general formulas (I) to (III) below; [Chemical Formula 1]

(In the general formulae (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 and 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, and R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and a and b are independently represented by 0 to 4 The integer.)

(2) The black resin composition for a touch panel according to the above (1), further comprising a pigment selected from the group consisting of a blue pigment, a green pigment, a yellow pigment, and a violet pigment.

(3) The black resin composition for a touch panel according to the above (1) or (2), further comprising a photopolymerization initiator.

(4) A light-shielding film for a touch panel, which is formed of the black resin composition for a touch panel according to any one of the above (1) to (3).

(5) A touch panel front panel comprising the light-shielding film for a touch panel described in (4) above.

(6) A black resin composition for forming a light-shielding film for a touch panel, the black resin composition containing a general formula selected from the group consisting of the following general formulas (I) to (III) Black pigment, resin and solvent;

[Chemical 6]

(In the general formulae (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 and 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, and R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and a and b are independently represented by 0 to 4 The integer.)

(7) The black resin composition according to the above (6), which is used for forming a light-shielding film for a touch panel, wherein the black resin composition further contains a coloring matter selected from the group consisting of a blue pigment, a green pigment, a yellow pigment, and a purple pigment. The pigments that make up the group.

(8) The black resin composition according to the above (6) or (7), which is used for forming a light-shielding film for a touch panel, wherein the black resin composition further contains a photopolymerization initiator.

(9) A touch panel front panel comprising a light-shielding film for a touch panel formed using the black resin composition according to any one of the above (6) to (8).

According to the black resin composition for a touch panel of the present invention, it is possible to form a light-shielding film for a touch panel which is excellent in chemical resistance, can sufficiently shield visible light, and can efficiently penetrate infrared rays.

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

The black resin composition for a touch panel of the present invention is mainly characterized by containing a black pigment selected from the general formula selected from the group consisting of the above general formulas (I) to (III). Further, in the above general formulae (I) to (III), R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may further have other substituents. The general formulas represented by the above general formulas (I) to (III) each have a cis-trans isomer relationship, and for example, a black pigment represented by the general formula (I) or a black pigment represented by the general formula (II) may be used alone. Or a black pigment represented by the general formula (III), or a mixture of a plurality of black pigments may be used in combination with a mixture of a black pigment represented by the general formula (I) and a black pigment represented by the general formula (II).

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

Further, the black pigments represented by the above general formulas (I) to (III) are known per se (Japanese Patent Laid-Open Publication No. 2012-515233), and are also commercially available (for example, Irgaphor Black S0100CF; manufactured by BASF Co., Ltd.).

The black pigments represented by the above general formulas (I) to (III) are responsible for the role as a light-shielding material. However, the black resin composition for a touch panel of the present invention may contain other light-shielding materials. Examples of the other light shielding material include carbon black, titanium black, chromium oxide, iron oxide, aniline black, an anthraquinone pigment, or C.I. solvent black 123.

The black resin composition for a touch panel of the present invention preferably further comprises There are pigments selected from the group consisting of blue pigments, green pigments, yellow pigments, and purple pigments. By containing such pigments, the color tone or the transmittance of the ultraviolet region of the formed light-shielding film can be further enhanced.

As the blue pigment, for example, CI 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; preferably CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 or 60, more preferably CI Pigment Blue 15:6.

As the green pigment, for example, CI pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58; preferably CI pigment green 7, 36 or 58.

Examples of the yellow pigment include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, and 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, 170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196 199, 200, 202, 203, 204, 205, 206, 207 or 208; preferably CI pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185, more preferably CI pigment yellow 83, 138, 139, 150 or 180.

As the purple pigment, for example, C.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; Preferably, it is CI Pigment Violet 19 or 23, more preferably CI Pigment Violet 23.

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

Examples of the red pigment include CI 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, 179, 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; Preferably, CI pigment red 48:1, 122, 168, 177, 20 2. 206, 207, 209, 224, 242 or 254; more preferably C.I. Pigment Red 177, 209, 224, 242 or 254.

Examples of the orange pigment include CI 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, preferably CI Pigment Orange 38 or 71.

The black resin composition for a touch panel of the present invention contains a resin. The resin may, for example, be an epoxy resin, a cardo resin, an acrylic resin, a decane resin or a polyimide resin, and is preferably an acrylic resin which is excellent in heat resistance of a coating film or storage stability of a black resin composition. Or polyimine resin.

As the acrylic resin, an acrylic resin having a carboxyl group is preferred. As the acrylic resin having a carboxyl group, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferred. The unsaturated carboxylic acid may, for example, be acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid or 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, and methacrylic acid. Isopropyl ester, n-butyl acrylate, n-butyl methacrylate, second butyl acrylate, second butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, methyl An unsaturated carboxylic acid alkane such as tert-butyl acrylate, n-amyl acrylate, n-amyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate or benzyl methacrylate Alkyl ester, aromatic vinyl compound such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene or α -methylstyrene, unsaturated carboxylic acid amine such as amine acrylate An unsaturated carboxylic acid glycidyl ester such as a base ester, a glycidyl acrylate or a glycidyl methacrylate, a vinyl carboxylate such as vinyl acetate or vinyl propionate, acrylonitrile or methacrylonitrile or α - chloro acrylonitrile, the vinyl cyanide , an aliphatic conjugated diene such as 1,3-butadiene or isoprene, polystyrene, polymethyl acrylate or polymethyl group having an acryl fluorenyl group or a methacryl fluorenyl group at the terminal, respectively. Methyl acrylate, polybutyl acrylate or polybutyl methacrylate.

Wherein, methacrylic acid and/or acrylic acid is selected from the group consisting of methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate and styrene. a monomeric 2 to 4 membered copolymer having a weight average molecular weight (Mw) of 2,000 to 100,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier, and a standard curve obtained using standard polystyrene) The resin having an acid value of 70 to 150 (mgKOH/g) is preferred because it has moderate solubility to an alkali developer.

Further, in order to enhance the sensitivity at the time of exposure and development, an acrylic resin having an ethylenically unsaturated group in a side chain is preferred. In this case, as the ethylenically unsaturated group which the side chain has, an acryl group or a methacryl group is preferable. Such an acrylic resin can be obtained by subjecting an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to an addition reaction of a carboxyl group of an acrylic resin having a carboxyl group.

The acrylic resin having an ethylenic unsaturated group in the side chain, for example, an acrylic resin described in a publicly known document (for example, Japanese Patent No. 3120476 or JP-A No. 8-262221), or a commercially available "Cyclomer (registered trademark) ) "P (Daicel Chemical Industry Co., Ltd.) or alkali-soluble cardo resin.

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 the polyfunctional acrylic monomer include bisphenol A diepoxypropyl ether (meth) acrylate, poly (meth) acrylate urethane, and modified bisphenol A epoxy group (A). Acrylate, 1,6-hexanediol (meth) acrylate, phthalic anhydride propylene oxide (meth) acrylate, trimellitic acid diethylene glycol (meth) acrylate, rosin The modified bis(meth) acrylate, the alkyd modified (meth) acrylate, and the bismuth acrylate system described in the publication of Japanese Patent No. 3621533 or JP-A No. 8-278630 Oligomer, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, trimethylol Propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylaldehyde, pentaerythritol tetra(meth)acrylic acid Ester, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]propane, Bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]methane, bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]indole, bis[ 4-(3-propenyloxy-2-hydroxypropoxy)phenyl]ether, 4,4'-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl] ring Hexane, 9,9-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]anthracene, 9,9-bis[3-methyl-4-(3-propenyloxy) 2-hydroxypropoxy)phenyl]anthracene, 9,9-bis[3-chloro-4-(3-propenyloxy-2-hydroxypropoxy)phenyl]anthracene, bisphenoxy Ethyl alcohol diacrylate, bisphenoxyethanol hydrazine dimethacrylate, bisformyl hydrazine diacrylate or bisformyl hydrazine dimethacrylate; in order to further improve the sensitivity, it is preferred to have three or more functional groups. The monomer is more preferably a monomer having 5 or more functional groups, and still more preferably dipentaerythritol 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. By using a photosensitive resin represented by an acrylic resin as the resin contained in the black resin composition for a touch panel of the present invention, and combining a photopolymerization initiator therein, the black resin for the touch panel of the present invention can be used. The composition imparts photosensitivity. As a result, a desired light-shielding film can be formed easily and accurately by photolithography, that is, exposure and development steps. Further, 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, the photohardening during exposure and development can be further enhanced. Sensitivity.

Examples of the photopolymerization initiator include a diphenylketone compound, an acetophenone compound, and 9-oxosulfuric acid. Compound, imidazole compound, benzothiazole compound, benzo An azole compound, an oxime ester compound, an oxazole compound, and three An inorganic photopolymerization initiator such as a compound, a phosphorus compound or a titanate.

More specifically, for example, diphenyl ketone, N, N'-tetraethyl-4,4'-diaminodiphenyl ketone, 4-methoxy-4'-dimethylamino group Diphenyl ketone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutyl phenyl ketone, 9-oxygen sulfur 2-chloro 9-oxosulfur , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinyl-1-propane, "IRGACURE (registered trademark)" 369 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone, "IRGACURE (registered trademark)" 379 2-(dimethylamino)-2-[4-(methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, "IRGACURE (registered trademark)" 907 2-methyl-1-[4-(methylthio)phenyl]-2- L-phenylpropan-1-one, 2-[4-methylbenzyl]-2-dimethylamino-1-(4-) of CGI-113 Phenylphenyl)-butanone, "IRGACURE (registered trademark)" OXE01 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzamide)], "IRGACURE (registered trademark)" ketone of OXE02, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-B醯肟) or CGI-242 ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine肟) (all manufactured by Ciba Specialty Chemicals Co., Ltd.), tert-butyl hydrazine, 1-chloroindole, 2,3-dichloropurine, 3-chloro-2-methylindole, 2-B Base, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzopyrene, 1,4-dimethylhydrazine, 2-phenylindole, 2-(o-chlorobenzene -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoene Oxazole, 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-three "ADEKA (registered trademark) OPTMER" N-1818 which is an oxazole compound or "ADEKA CRUISE" NCI-831 or NCI-930 (made by ADEKA) or PBG304 or PBG305 which are oxime ester compounds ( All of them are made by Changzhou Powerful Electronic New Material (Y); in order to enhance the sensitivity, it is better to use IRG02 (registered trademark) 379, "IRGACURE (registered trademark)" OXE02, "ADEKA (registered trademark) OPTMER" N-1919, "ADEKA CRUISE" NCI-831 and PBG304 are two groups.

The black resin composition for the touch panel of the present invention is for lifting and glass The adhesion between inorganic materials such as glass sheets or tantalum wafers may also contain a dense adhesion improver. The viscous modifier may, for example, be a decane coupling agent or a titanium coupling agent. The amount of the adhesion improving agent added is usually about 0.2 to 20% by mass based on the resin.

The black resin composition for a touch panel of the present invention may contain a polymer dispersant in order to enhance 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, and a polyurethane system. A polymer dispersant or a polyallylamine-based polymer dispersant. These polymer dispersants may be appropriately selected in consideration of the type of the light-shielding material and the pigment to be dispersed. Further, the polymer dispersant can be classified into a dispersant having only an amine valence, a dispersant having only an acid value, a dispersant having an amine valence and an acid value, or a dispersant having neither an amine valence nor an acid valence, but The effect of the present invention is more remarkable, and it is preferably a dispersant having an amine value, more preferably a polymer dispersant having only an amine price.

As the dispersing agent having only an amine value, for example, DISPERBYK 102, 160, 161, 162, 2163, 2164, 166, 167, 168, 2000, 2050, 2150, 2155, LPN6919, LPN21116, LPN21234, 9075 or 9077 (above) All are BYK CHEMIE company, EFKA 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403 or 4800 (all of which are manufactured by BASF) or AJISPER PB711 (manufactured by Ajinomoto FINE TECHNO Co., Ltd.) is preferably DISPERBYK LPN6919 or LPN21116 which is a polymer dispersant having a tertiary amine group.

Examples of the polymer dispersant having an amine value and an acid value include DISPERBYK 142, 145, 2001, 2010, 2020, 2025, or 9076 or Anti-Terra-205 (all of which are manufactured by BYK CHEMIE Co., Ltd.) and SOLSPERS 24000 (Lubrizol ( Share) company system) or AJISPER PB821, PB880 or PB881 (all of which are manufactured by Ajinomoto FINE TECHO Co., Ltd.).

The polymer dispersant is preferably added in such a manner that the adhesion or the photosensitivity is not lowered, and the amount of the polymer dispersant is usually from about 1 to 40% by mass based on the light-shielding material and the pigment.

In the black resin composition for a touch panel of the present invention, in order to maintain a balance between reflectance, light blocking property, and adhesion, the mass ratio of the light shielding material and the pigment/resin, the monomer, and the polymer dispersant is preferably 60. The range of /40~5/95 is more preferably in the range of 50/50~10/90. When the amount of the resin, the monomer, and the polymer dispersant is too small, the reflectance becomes high. On the other hand, when the amount of the light-shielding material and the pigment is too small, the optical density (OD value/μm) per unit thickness 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. The solvent may be appropriately selected from water or an organic solvent in consideration of dispersion stability of the dispersed pigment, solubility of the resin to be added, and the like. The organic solvent may, for example, be an ester, an aliphatic alcohol, a (poly)alkylene glycol ether solvent, a ketone, a guanamine-based polar solvent or a lactone-based polar solvent.

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, and diethylene glycol single. Methyl ether, diethylene glycol monoethyl ether, 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 glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, two (poly)alkylene glycol monoalkyl ethers such as propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol single Ethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl Ethyl ether acetate, 1,3-butylene glycol diacetate, propylene glycol monomethyl ether acetate (hereinafter referred to as "PMA"), dipropylene glycol methyl ether acetate or propylene glycol monoethyl ether acetate ( Polyalkylene glycol monoalkyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or other ethers such as tetrahydrofuran, a ketone such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone, an alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate, 2-hydroxyl Ethyl 2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 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, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-Butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, C Other esters such as methyl ketone, ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoxyacetate or ethyl 2-oxobutyrate, toluene or xylene An aromatic hydrocarbon or an amide such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.

Further, as the size of the substrate increases, coating by the die coating apparatus becomes mainstream, and in order to achieve appropriate volatility and drying property, it is preferable to contain 30 to 75 mass% of the medium having a boiling point of 170 ° C or more. Further, in order to reduce the disadvantage of the foreign matter in the die coating apparatus or the drying cause in the vacuum drying apparatus, it is more preferable to contain 1 to 20% by mass of the solvent having a boiling point of 200 ° C or higher. In this case, it is preferred to use a mixed solvent composed of at least two or more kinds.

The black resin composition for a touch panel of the present invention may contain a surfactant in order to ensure smoothness of the coatability and coloring film and to prevent a benard cell. The amount of the surfactant to be added is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass based on the light-shielding material and the pigment.

The surfactant may, for example, be an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether triethanolamine, a cationic surfactant such as stearylamine acetate or lauryl trimethylammonium chloride, or a laurel. A nonionic interface such as an amphoteric surfactant such as dimethylamine or lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate An active agent, a polyfluorene-based surfactant or a fluorine-based surfactant having a polydimethylsiloxane or the like as a main skeleton.

The resin component of the black resin composition for a touch panel of the present invention (excluding a solvent, which also includes a component of an additive such as a monomer, an oligomer, and a photopolymerization initiator), and a solid concentration of the color component combined with the coloring material. From the viewpoint of coatability and drying property, it is preferably 2 to 30% by mass, and more preferably 5 to 20% by mass.

The method for producing the black resin composition for a touch panel of the present invention may be, for example, a method in which a pigment is directly dispersed in a resin solution using a disperser, or a pigment is dispersed in water or an organic solvent using a disperser to prepare a pigment. A dispersion, followed by a method of mixing the pigment dispersion with a resin solution. The dispersion method of the pigment may, for example, be a ball mill, a sand mill, a 3-roll mill or a high-speed impact mill, and is preferably a bead mill from the viewpoint of dispersion efficiency or micro-dispersion. As the bead mill, for example, a Co-ball mill, a basket mill, a pin mill, or a dyno mill can be mentioned. As the bead of the bead mill, for example, titanium oxide beads, zirconium dioxide beads or zircon beads can be mentioned. The bead diameter for dispersion is preferably 0.01 to 5.0 mm, more preferably 0.03 to 1.0 mm. When the primary particle diameter of the pigment and the secondary particles formed by the aggregation of the primary particles are small, the dispersed beads are preferably 0.03 to 0.10 mm as the bead diameter for dispersion. In this case, it is preferred to disperse it by a bead mill having a separator which can disperse the finely dispersed beads and the dispersion. On the other hand, when dispersing a pigment containing coarse particles having a submicron degree, in order to obtain a sufficient pulverization force, it is preferred to use a bead diameter of Dispersed beads of 0.10 mm or more.

The light-shielding film for a touch panel of the present invention is characterized in that it is formed of a black resin composition for a touch panel of the present invention. The method for producing the light-shielding film for a touch panel of the present invention is as follows, for example. As a method of applying the black resin composition for a touch panel of the present invention to a substrate, for example, a substrate is applied by a dip coating method, a roll coating method, a spin coating method, a die coating method, or a wire bar coating method. A method of immersing in a solution, or a method of spraying a solution onto a substrate. Examples of the substrate to which the black resin composition for a touch panel of the present invention is applied include quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass or chemically strengthened glass coated with cerium oxide on the surface. Such as inorganic glass, or organic plastic film or sheet. Further, when the black resin composition for a touch panel of the present invention is applied onto a substrate, the surface of the substrate can be treated by a bonding aid such as a decane coupling agent, an aluminum chelating agent or a titanium chelating agent. The adhesion between the coating film and the substrate is improved.

After the black resin composition for a touch panel of the present invention is applied onto a substrate, the coated film is dried by heating, dried by air drying, heat drying, vacuum drying, or the like to form a dried film. In order to suppress uneven drying or unevenness in the formation of the film, it is preferred to apply a substrate on which the black resin composition for a touch panel of the present invention is applied, and to dry-pressure under reduced pressure using a vacuum dryer equipped with a heating device. Heat hardened.

The obtained coating film is usually formed into an oxygen blocking film as needed, and then patterned by a method such as photolithography. Thereafter, after removing the oxygen blocking film as needed, the film is further dried by heating and hardened to obtain a light shielding film. The thermosetting conditions vary depending on the resin. When an acrylic resin is used, it is usually heated at 200 to 250 ° C for 1 to 60 minutes.

The touch panel front panel of the present invention is characterized by comprising the light shielding film for a touch panel of the present invention. The touch panel front panel may be composed of a transparent substrate and a light shielding film of the present invention formed on a partial region of the transparent substrate.

[Examples]

The present invention will now be described in further detail by way of examples and comparative examples, but the invention is not limited thereto.

<Evaluation method> [sublimation]

A light-shielding film of a desired film thickness was formed on a chemically strengthened glass (Gorilla (registered trademark); manufactured by Corning) having a thickness of 0.7 mm, and heated in a hot air oven at 280 ° C for 30 minutes, and then the surface of the coating film was wiped with a white cloth to visually observe Whether or not the sublimate from the pigment is attached. When the sublimate from the pigment adhered, the white cloth coloring person was judged as B, and the uncolored one was judged as A.

[penetration rate]

A light-shielding film having an OD value of 3 was formed on a chemically strengthened glass having a thickness of 0.7 mm, and a spectrophotometer (UV-2500PC; Shimadzu Corporation, measuring wavelength region: 280 to 1000 nm, sample pitch: 1.0 nm, scanning speed: Low speed, slit width: 2.0 nm) The transmittance was measured.

[reflective chromaticity]

A light-shielding film having a desired film thickness was formed on a chemically strengthened glass having a thickness of 0.7 mm, and a reflection chromaticity (reflectance R, L*a*b) measured by a glass surface was measured using a spectrophotometer (MPC-2200; manufactured by Shimadzu Corporation). The color of the table is a* and b*). (Measurement wavelength region: 380 to 780 nm, sample pitch: 1.0 nm, scanning speed: low speed, slit width: 2.0 nm). The case where the b* value of the blue sensation index (the more the negative direction and the blue sensation is stronger) is determined to be A, the case where -0.2 to 0.2 is determined as B, and the case where it is 0.3 to 0.7 is judged as C. When it is 0.8 or more, it is judged as D.

[OD value]

A light-shielding film having a film thickness of 1.0 μm was formed on a chemically strengthened glass having a thickness of 0.7 mm, and the intensity of incident light and transmitted light was measured using an X-rite 361T (visual) densitometer, and was calculated by the following formula (1).

OD value = log ₁₀ (I ₀ /I)... Equation (1)

I ₀ : incident light intensity

I: transmitted light intensity

[PAN tolerance]

A light-shielding film of a desired film thickness is formed on a chemically strengthened glass having a thickness of 0.7 mm, and immersed in a PAN solution heated at 50 ° C (HNO ₃ /H ₃ PO ₄ /CH ₃ COOH/H ₂ O = mass ratio 5/68/ 12/15) 2 minutes, the change in OD value before and after treatment of the PAN solution was measured.

(Synthesis of Acrylic Polymer (P-1))

The methyl methacrylate/methacrylic acid/styrene copolymer (mass ratio: 30/40/30) was synthesized by the method described in the literature (Japanese Patent No. 3120476; Example 1), and 40 parts by mass was added. The glycidyl methacrylate was reprecipitated with purified water, filtered, and dried to obtain an acrylic polymer (P-1) powder having a weight average molecular weight (Mw) of 10,000 and an acid value of 110 (mgKOH/g).

(Manufacture of black pigment dispersion Bk-1)

Black pigment 1 ("Irgaphor Black S0100CF" manufactured by BASF Corporation: 600.0 g), propylene glycol monomethyl ether acetate solution of acrylic resin (P-1), 35 mass% solution (321.4 g), polymer dispersant (BYK 21116; BYK Corporation) 93.8g) and propylene glycol monoethyl ether acetate (1984.8 g) was placed in a tank, and stirred by a homogenizer (special machine) for 1 hour to obtain a preliminary dispersion 1. Then, the preliminary dispersion 1 was supplied to a nano-grinder (ultra apex mill, manufactured by Shojo Co., Ltd.) having a centrifugal separator of 70% filled with 0.10 mm φ zirconia beads (manufactured by Toray Industries, Inc.) at a rotation speed. The dispersion was carried out for 8 hours at 8 m/s to obtain a black pigment dispersion Bk-1 having a solid content concentration of 25% by mass and a pigment/resin (mass ratio) = 80/20.

(Manufacture of organic pigment dispersion DB-1)

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

(Manufacture of organic pigment dispersion DG-1)

The organic pigment dispersion DG-1 was obtained in the same manner as in the black pigment dispersion Bk-1 except that the organic pigment PG58 (manufactured by DIC) was used instead of the black pigment 1.

(Manufacture of organic pigment dispersion DY-1)

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

(Manufacture of organic pigment dispersion DV-1)

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

(Manufacture of organic pigment dispersion DR-1)

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

(Manufacture of organic pigment dispersion DR-2)

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

(Manufacture of black pigment dispersion Bk-2)

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

(Manufacture of black pigment dispersion Bk-3)

The black pigment dispersion liquid Bk-3 was obtained in the same manner as the black pigment dispersion liquid 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 CRUISE (registered trademark) NCI-831 as a photopolymerization initiator was added to PMA 29.53 g, and stirred until the solid content was dissolved.

Further, 16.03 g of a PMA 35 mass% solution of an acrylic polymer (P-1), 3.38 g of a dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, and a polybenzazole as a surfactant were added. Oxygen surfactant BYK333 PMA10 0.24 g of a mass % solution was stirred at room temperature for 1 hour, whereby a photosensitive resist was obtained. 10.46 g of a black pigment dispersion Bk-1 was added to the photosensitive resist, thereby preparing a photosensitive black resin having a total solid concentration of 20%, a pigment/resin (mass ratio) of 18/82, and a black pigment of 100. A-1.

The prepared photosensitive black resin composition 1 was filtered through a filter of Teflon (registered trademark) of 2 μm, and the Mikasa was used on the substrate so that the film thickness became 1 μm (post-bake). The spin coating apparatus 1H-DS was applied, and the coated substrate was heat-treated by columnar projections on a hot plate at 90 ° C for 2 minutes, and further allowed to stand on the hot plate for 2 minutes to perform prebaking. The coating film was exposed to an exposure machine PEM-6M using a UNION optical (manufacturing) mask, and exposed to an exposure amount of ultraviolet rays of 200 mJ/cm ² through a mask for a resolution test.

Subsequently, development was carried out using an alkali developing solution of a 0.1% by mass aqueous solution of tetramethylammonium hydroxide, followed by washing with pure water to obtain a patterned substrate. The obtained patterned substrate was held at 230 ° C for 30 minutes in a hot air oven and post-baked, whereby a light-shielding substrate 1 was obtained.

(Example 2)

The mass ratio of the pigment used as the coloring material was set to black pigment 1 / blue pigment PB15: 6 = 80 / 20 (8.37 g of the above dispersion Bk-1 was added to the photosensitive resist, and the pigment dispersion DB was added. The same procedure as in Example 1 was carried out except that -1 to 2.09 g), and a photosensitive black resin composition A-2 was obtained. The light-shielding substrate 2 was obtained in the same manner as in Example 1 using the obtained photosensitive black resin composition A-2.

(Example 3)

The mass ratio of the pigment used as the coloring material was set to black pigment 1 / blue pigment PB15: 6 = 50 / 50 (the above dispersion Bk-1 5.23 g was added to the photosensitive resist, and the pigment dispersion DB was added. The same procedure as in Example 1 was carried out except that -1 5.23 g), and a photosensitive black resin composition A-3 was obtained. The light-shielding substrate 3 was obtained in the same manner as in Example 1 except that the obtained photosensitive black resin composition A-3 was used.

(Example 4)

The mass ratio of the pigment used as the coloring material was set to black pigment 1/green pigment PG58=80/20 (the above dispersion Bk-1 8.37 g was added to the photosensitive resist, and the pigment dispersion DG-1 2.09 was added. The same procedure as in Example 1 was carried out except for g), to obtain a photosensitive black resin composition A-4. The light-shielding substrate 4 was obtained in the same manner as in Example 1 except that the obtained photosensitive black resin composition A-4 was used.

(Example 5)

The mass ratio of the pigment used as the coloring material was set to black pigment 1/yellow pigment PY150=80/20 (the above dispersion Bk-1 8.37 g was added to the photosensitive resist, and the pigment dispersion DY-1 2.09 was added. Other than g), the same procedure as in Example 1 was carried out to obtain a photosensitive black resin composition A-5. The light-shielding substrate 5 was obtained in the same manner as in Example 1 except that the obtained photosensitive black resin composition A-5 was used.

(Example 6)

The mass ratio of the pigment used as the coloring material was set to black pigment 1/purple pigment PV23=80/20 (the above dispersion Bk-1 8.37 g was added to the photosensitive resist, and the pigment dispersion DV-1 2.09 was added. Other than g), the same procedure as in Example 1 was carried out to obtain photosensitivity. Black resin composition A-6. The light-shielding substrate 6 was obtained in the same manner as in Example 1 except that the obtained photosensitive black resin composition A-6 was used.

(Example 7)

The mass ratio of the pigment used as the coloring material was set to black pigment 1/red pigment PR254=80/20 (the above dispersion Bk-1 8.37 g was added to the photosensitive resist, and the pigment dispersion DR-1 2.09 was added. Other than g), the photosensitive black resin composition A-7 was obtained in the same manner as in Example 1. The light-shielding substrate 7 was obtained in the same manner as in Example 1 except that the obtained photosensitive black resin composition A-7 was used.

(Example 8)

The mass ratio of the pigment used as the coloring material was set to black pigment 1/red pigment PR177=80/20 (the above dispersion Bk-1 8.37 g was added to the photosensitive resist, and the pigment dispersion DR-2 2.09 was added. Other than g), the same procedure as in Example 1 was carried out to obtain a photosensitive black resin composition A-8. The light-shielding substrate 8 was obtained in the same manner as in Example 1 except that the obtained photosensitive black resin composition A-8 was used.

(Comparative Example 1)

The mass ratio of the pigment used as the coloring material was set to blue pigment PB15:6/red pigment PR254=50/50 (the above dispersion DB-1 5.23 g, pigment dispersion DR was added to the photosensitive resist) The same procedure as in Example 1 was carried out except that -1 5.23 g), and a photosensitive black resin composition A-9 was obtained. The light-shielding substrate 9 was obtained in the same manner as in Example 1 except that the obtained photosensitive black resin composition A-9 was used.

(Comparative Example 2)

The mass ratio of the pigment used as the coloring material was set to blue pigment PB15:6/red pigment PR177=50/50 (the above dispersion DB-1 was added to the photosensitive resist, 5.23 g, pigment dispersion DR The same procedure as in Example 1 was carried out except that -2 5.23 g), and a photosensitive black resin composition A-10 was obtained. The light-shielding substrate 10 was obtained in the same manner as in Example 1 except that the obtained photosensitive black resin composition A-10 was used.

(Comparative Example 3)

In the same manner as in Example 1, except that the mass ratio of the pigment used as the coloring material was set to titanium nitride = 100 (the dispersion liquid Bk-2 was added to the photosensitive resist, 10.46 g). Photosensitive black resin composition A-11. The light-shielding substrate 11 was obtained in the same manner as in Example 1 except that the obtained photosensitive black resin composition A-11 was used.

(Comparative Example 4)

The photosensitive film was obtained in the same manner as in Example 1 except that the mass ratio of the pigment used as the coloring material was set to carbon black = 100 (the dispersion liquid Bk-3 was added to the photosensitive resist). Aromatic black resin composition A-12. The light-shielding substrate 12 was obtained in the same manner as in Example 1 using the obtained photosensitive black resin composition A-12.

<evaluation result>

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 are shown in Tables 1 and 2.

In Examples 1 to 8, the transmittance in the infrared region of 850 to 1000 nm can be as high as 60% or more, and the light in the infrared region required for the action of the proximity sensor can be obtained. That is, a light-shielding substrate in which infrared rays are sufficiently penetrated and reflection chromaticity is also good.

Further, by adding blue pigment, green pigment, yellow pigment or violet pigment as in Examples 2 to 6, the transmittance in 280 to 480 nm was improved. As a result, it has been shown that it is possible to provide a photosensitive light-shielding film which is excellent in pattern processability even if it is light-cured efficiently even at a low exposure amount.

On the other hand, the light-shielding film of the system in which the red pigment and the blue pigment are mixed as in Comparative Examples 1 and 2 is deteriorated in the occurrence of sublimation or PAN resistance, and an excellent light-shielding film such as chemical resistance cannot be obtained.

Further, as in Comparative Examples 3 and 4, a light-shielding film of a system of titanium nitride or carbon black belonging to an inorganic black pigment was used, and the infrared rays were not penetrated, and a light-shielding film excellent in optical characteristics could not be obtained.

(industrial availability)

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 penetrates infrared rays for a proximity sensor.

Claims (9)

A black resin composition for a touch panel, comprising a black pigment, a resin, and a solvent selected from the group consisting of the general formulas (I) to (III) below; (In the general formulae (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 and 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, and R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and a and b are independently represented by 0 to 4 The integer). The black resin composition for a touch panel according to the first aspect of the invention, further comprising a pigment selected from the group consisting of a blue pigment, a green pigment, a yellow pigment, and a violet 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 is formed by a black resin composition for a touch panel according to any one of claims 1 to 3. A front panel of a touch panel is provided with a light shielding film for a touch panel of the fourth application patent. A black resin composition for forming a light-shielding film for a touch panel, the black resin composition containing a black pigment selected from a general formula selected from the group consisting of the following general formulas (I) to (III), Resin and solvent; [Chemical 5] (In the general formulae (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 and 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, and R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and a and b are independently represented by 0 to 4 The integer). The black resin composition of claim 6 is for use in forming a light-shielding film for a touch panel, wherein the black resin composition further comprises a group selected from the group consisting of a blue pigment, a green pigment, a yellow pigment, and a purple pigment. Set of pigments. The black resin composition of claim 6 or 7 is used for forming a light-shielding film for a touch panel, wherein the black resin composition further contains a photopolymerization initiator. A touch panel front panel having any one of the sixth to eighth patent applications A light-shielding film for a touch panel formed using a black resin composition.