WO2014208348A1 - Black resin composition for touch panels - Google Patents

Black resin composition for touch panels Download PDF

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Publication number
WO2014208348A1
WO2014208348A1 PCT/JP2014/065562 JP2014065562W WO2014208348A1 WO 2014208348 A1 WO2014208348 A1 WO 2014208348A1 JP 2014065562 W JP2014065562 W JP 2014065562W WO 2014208348 A1 WO2014208348 A1 WO 2014208348A1
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WO
WIPO (PCT)
Prior art keywords
pigment
resin composition
touch panel
black
group
Prior art date
Application number
PCT/JP2014/065562
Other languages
French (fr)
Japanese (ja)
Inventor
涼介 相原
欣彦 井上
Original Assignee
東レ株式会社
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Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2014530981A priority Critical patent/JP6569220B2/en
Publication of WO2014208348A1 publication Critical patent/WO2014208348A1/en

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Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • G02B5/223Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415Five-membered rings
    • C08K5/3417Five-membered rings condensed with carbocyclic rings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00Other synthetic dyes of known constitution
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007Filters, e.g. additive colour filters; Components for display devices
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a black resin composition for a touch panel.
  • 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.
  • 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.
  • 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
  • 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.
  • the reflection chromaticity is not neutral and visibility is deteriorated, and the pigment is sublimated by heating in the manufacturing process.
  • 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.
  • 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).
  • R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms
  • 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 (1) further containing a pigment selected from the group consisting of a blue pigment, a green pigment, a yellow pigment, and a purple pigment.
  • 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).
  • a touch panel front plate comprising the touch panel light-shielding film according to (4).
  • R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms
  • 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
  • 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.
  • the black resin composition for a touch panel of the present invention 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).
  • 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).
  • 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.
  • the black pigment represented by the general formula (I) and the general formula (II) 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.
  • 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). .
  • the black resin composition for a touch panel of the present invention may contain other light shielding materials.
  • 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.
  • blue pigments examples 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.
  • green pigments examples 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.
  • yellow pigments examples 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
  • 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.
  • 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.
  • red pigments examples 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, 185, 187, 188, 190, 193, 194, 200
  • 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.
  • orange pigments examples 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.
  • 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.
  • an acrylic resin having a carboxyl group is preferable.
  • the acrylic polymer having a carboxyl group a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferable.
  • 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.
  • 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.
  • an acrylic resin having an ethylenically unsaturated group in the side chain is preferable if the sensitivity during exposure and development is improved.
  • 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.
  • 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.
  • a monomer for example, a polyfunctional or monofunctional acrylic monomer or oligomer can be used.
  • 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.
  • 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.
  • 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.
  • a desired light-shielding film can be easily and precisely formed by photolithography, that is, exposure and development processes.
  • 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.
  • photopolymerization initiator examples include benzophenone compounds, acetophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, oxime ester compounds, carbazole compounds, triazine compounds, and phosphorus compounds.
  • inorganic type photoinitiators, such as titanate are mentioned.
  • benzophenone N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone
  • benzoin benzoin methyl ether
  • Benzoin isobutyl ether benzyldimethyl ketal
  • ⁇ -hydroxyisobutylphenone thioxanthone
  • 2-chlorothioxanthone 1-hydroxycyclohexyl phenyl ketone
  • 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane
  • Irgacure® 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone
  • Irgacure® 2- (dimethylamino)
  • 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.
  • an 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.
  • a polymer dispersant examples 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.
  • 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.
  • 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 / ⁇ m) 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.
  • a 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.
  • organic solvent include esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents, or lactone polar solvents.
  • organic solvent for dissolving the acrylic resin examples 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.
  • 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.
  • the surfactant examples 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
  • silicone-based interfaces mainly composed of polydimethylsiloxane An activator or a fluorosurfactant may be used.
  • 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.
  • 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.
  • 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.
  • the bead mill examples include a coball mill, a basket mill, a pin mill, and a dyno mill.
  • 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.
  • the bead size used for dispersion is preferably a fine dispersed bead of 0.03 to 0.10 mm.
  • 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.
  • the substrate on which the black resin composition for a touch panel of the present invention is applied examples 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.
  • substrate by processing the board
  • the coating film is heated and dried and cured by air drying, heat drying or vacuum drying to form a dry 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.
  • 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.
  • Gorilla registered trademark
  • 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).
  • 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
  • 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.
  • MPC-2200 spectroscopic clock
  • 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.
  • a light-shielding film having a film thickness of 1.0 ⁇ m 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
  • 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.
  • 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 mm ⁇ 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Adeka Arcles registered trademark
  • NCI-831 a photopolymerization initiator
  • the prepared photosensitive black resin composition 1 is filtered through a 2 ⁇ m 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 ⁇ m (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.
  • 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.
  • substrate was hold
  • substrate 1 was obtained by performing a post-baking.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a good light-shielding substrate could be obtained.
  • 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.
  • 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.
  • 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.

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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

タッチパネル用黒色樹脂組成物Black resin composition for touch panels
 本発明は、タッチパネル用黒色樹脂組成物に関する。 The present invention relates to a black resin composition for a touch panel.
 近年、カバーガラス上に遮光膜、導電膜及びセンサーが直接形成された、カバーガラス一体型タッチパネルが提案されている。 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.
 カバーガラス一体型タッチパネルを具備するスマートフォンやタブレット端末等の多くには、対象物の接近を感知するための近接センサーが搭載されており、例えば通話時に使用者の顔の接近を感知して、ディスプレイのON/OFFを切り替えるような機能が付与されている。 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.
 上記の近接センサーとしては、赤外線を送信する発光素子と、赤外線を受信して電気信号に変換する受光素子とで構成されたものが広く用いられている。このような構成においては、タッチパネルの外観や歩留まりをより優良なものとするためにも、近接センサーと対象物とを隔てる遮光膜が、赤外線の送受信を阻害しないこと、すなわち赤外線を透過することが好適である。赤外線透過部位に赤外線透過インクを塗布して、周辺の遮光膜との色調を整合させる方法も考えられるが、色調の完全な整合は困難であり、さらには狭い範囲へのインク塗布という、煩雑な工程が増加してしまうためである。 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.
 赤外線を透過する遮光膜としては、例えばペリレン系黒色顔料とカーボンブラックとを含む遮光膜(特許文献1)や、青色顔料と赤色顔料とを含む遮光膜(特許文献2)が知られている。 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.
特開2012-68613号公報JP 2012-68613 A 国際公開第2012/157222号International Publication No. 2012/157222
 しかしながら、従来の赤外線を透過可能な遮光膜は、赤外線の透過率が十分でないか、あるいは遮光膜の製造の過程においてエッチング液の影響により褪色が生じるという問題点を抱えるものであった。 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.
 また、特に赤色顔料と青色顔料と含む遮光膜においては、反射色度がニュートラルにならず視認性が悪化することに加え、製造工程における加熱により顔料が昇華するという問題もあった。 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.
 そこで本発明は、耐薬品性が高く、可視光を申し分なく遮光しながら、かつ赤外線の高い透過率を達成可能な、タッチパネル用遮光膜を形成するためのタッチパネル用黒色樹脂組成物を提供することを目的とする。 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) 下記一般式(I)~(III)からなる群から選ばれる一般式で表される黒色顔料、樹脂及び溶媒を含有する、タッチパネル用黒色樹脂組成物。 (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).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
(一般式(I)~(III)中、R及びRは、それぞれ独立して、水素又は炭素数1~10のアルキル基を表し、R及びRは、それぞれ独立して、R11、OR11、SR11、COR11、CONR1213、NR12COR11、OCOR11、COOR11、SCOR11、OCSR11、COSR11、CSOR11、CN、ハロゲン原子又は水酸基を表し、R11、R12及びR13は、それぞれ独立して、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環基を表し、a及びbは、それぞれ独立して、0~4の整数を表す。)
(2) さらに青色顔料、緑色顔料、黄色顔料及び紫色顔料からなる群から選ばれる顔料を含有する、上記(1)に記載のタッチパネル用黒色樹脂組成物。
(3) さらに光重合開始剤を含有する、上記(1)又は(2)に記載のタッチパネル用黒色樹脂組成物。
(4) 上記(1)~(3)のいずれかに記載のタッチパネル用黒色樹脂組成物より形成される、タッチパネル用遮光膜。
(5) 上記(4)記載のタッチパネル用遮光膜を具備する、タッチパネル前面板。
(6) 下記一般式(I)~(III)からなる群から選ばれる一般式で表される黒色顔料、樹脂及び溶媒を含有する黒色樹脂組成物の、タッチパネル用遮光膜を形成するための使用。
(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 .
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
(一般式(I)~(III)中、R及びRは、それぞれ独立して、水素又は炭素数1~10のアルキル基を表し、R及びRは、それぞれ独立して、R11、OR11、SR11、COR11、CONR1213、NR12COR11、OCOR11、COOR11、SCOR11、OCSR11、COSR11、CSOR11、CN、ハロゲン原子又は水酸基を表し、R11、R12及びR13は、それぞれ独立して、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環基を表し、a及びbは、それぞれ独立して、0~4の整数を表す。)
(7) さらに青色顔料、緑色顔料、黄色顔料及び紫色顔料からなる群から選ばれる顔料を含有する上記(6)に記載の黒色樹脂組成物の、タッチパネル用遮光膜を形成するための使用。
(8) さらに光重合開始剤を含有する上記(6)又は(7)に記載の黒色樹脂組成物の、タッチパネル用遮光膜を形成するための使用。
(9) 上記(6)~(8)のいずれかに記載の黒色樹脂組成物を使用して形成されたタッチパネル用遮光膜を具備する、タッチパネル前面板。
(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.
 本発明のタッチパネル用黒色樹脂組成物によれば、耐薬品性に優れ、可視光を十分に遮光可能であり、さらには赤外線を高効率に透過することが可能な、タッチパネル用遮光膜を形成することができる。 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.
 本発明のタッチパネル用黒色樹脂組成物は、上記一般式(I)~(III)からなる群から選ばれる一般式で表される黒色顔料、樹脂及び溶媒を含有することを特徴とする。 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).
 本発明のタッチパネル用黒色樹脂組成物は、上記一般式(I)~(III)からなる群から選ばれる一般式で表される黒色顔料を含有することが肝要である。なお、上記一般式(I)~(III)においてRは、水素又は炭素数1~10のアルキル基を表すが、このアルキル基はさらに他の置換基を有していても構わない。上記一般式(I)~(III)で示される一般式は、それぞれシス-トランス異性体の関係にあるが、例えば一般式(I)で表される黒色顔料、一般式(II)で表される黒色顔料又は一般式(III)で表される黒色顔料を、それぞれ単独で用いても構わないし、一般式(I)で表される黒色顔料及び一般式(II)で表される黒色顔料を組み合わせた混合物のように、複数種の黒色顔料を混合して用いても構わない。 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.
 上記一般式(I)~(III)で表されるいずれかの黒色顔料を用いることで、可視光領域における高い遮光性と赤外光領域における高い透過性とを両立でき、かつ高い耐薬品性を有する遮光膜の形成が可能となる。 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
 なお、上記一般式(I)~(III)で表される黒色顔料自体は公知であり(特表2012-515233号公報)市販もされている(例えば、Irgaphor Black S0100CF;BASF(株)製)。 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). .
 上記一般式(I)~(III)で表される黒色顔料は遮光材としての役割を担うが、本発明のタッチパネル用黒色樹脂組成物は、その他の遮光材を含有しても構わない。その他の遮光材としては、例えば、カーボンブラック、チタンブラック、酸化クロム、酸化鉄、アニリンブラック、ペリレン系顔料又はC.I.ソルベントブラック123が挙げられる。 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.
 本発明のタッチパネル用黒色樹脂組成物は、さらに青色顔料、緑色顔料、黄色顔料及び紫色顔料からなる群から選ばれる顔料を含有することが好ましい。これら顔料を含有することにより、形成された遮光膜の色目や紫外領域の透過率をより向上させることができる。 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.
 青色顔料としては、例えば、C.I.ピグメントブルー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又は79が挙げられるが、C.I.ピグメントブルー15、15:1、15:2、15:3、15:4、15:6又は60が好ましく、C.I.ピグメントブルー15:6がより好ましい。 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.
 緑色顔料としては、例えば、C.I.ピグメントグリーン1、2、4、7、8、10、13、14、15、17、18、19、26、36、45、48、50、51、54、55又は58が挙げられるが、C.I.ピグメントグリーン7、36又は58が好ましい。 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.
 黄色顔料としては、例えば、C.I.ピグメントイエロー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、173、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又は208が挙げられるが、C.I.ピグメントイエロー83、117、129、138、139、150、154、155、180又は185が好ましく、C.I.ピグメントイエロー83、138、139、150又は180がより好ましい。 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.
 紫色顔料としては、例えば、C.I.ピグメントバイオレット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又は50が挙げられるが、C.I.ピグメントバイオレット19又は23が好ましく、C.I.ピグメントバイオレット23がより好ましい。 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.
 なお、本発明のタッチパネル用黒色樹脂組成物は、さらに赤色顔料やオレンジ顔料等の、他色の顔料を含有しても構わない。 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.
 赤色顔料としては、例えば、C.I.ピグメントレッド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又は276が挙げられるが、C.I.ピグメントレッド48:1、122、168、177、202、206、207、209、224、242又は254が好ましく、C.I.ピグメントレッド177、209、224、242又は254がより好ましい。 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.
 オレンジ顔料としては、例えば、C.I.ピグメントオレンジ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又は79が挙げられるが、C.I.ピグメントオレンジ38又は71が好ましい。 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.
 本発明のタッチパネル用黒色樹脂組成物は、樹脂を含有する。樹脂としては、例えば、エポキシ樹脂、カルド樹脂、アクリル樹脂、シロキサン樹脂又はポリイミド樹脂が挙げられるが、塗膜の耐熱性や黒色樹脂組成物の貯蔵安定性等に優れる、アクリル樹脂又はポリイミド樹脂が好ましい。 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. .
 アクリル樹脂としては、カルボキシル基を有するアクリル樹脂が好ましい。カルボキシル基を有するアクリル系ポリマーとしては、不飽和カルボン酸とエチレン性不飽和化合物との共重合体が好ましい。不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸又はビニル酢酸が挙げられる。エチレン性不飽和化合物としては、例えば、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸n-プロピル、アクリル酸イソプロピル、メタクリル酸n-プロピル、メタクリル酸イソプロピル、アクリル酸n-ブチル、メタクリル酸n-ブチル、アクリル酸sec-ブチル、メタクリル酸sec-ブチル、アクリル酸イソ-ブチル、メタクリル酸イソ-ブチル、アクリル酸tert-ブチル、メタクリル酸tert-ブチル、アクリル酸n-ペンチル、メタクリル酸n-ペンチル、2-ヒドロキシエチルアクリレート、2-ヒドロキシエチルメタクリレート、ベンジルアクリレート若しくはベンジルメタクリレート等の不飽和カルボン酸アルキルエステル、スチレン、p-メチルスチレン、o-メチルスチレン、m-メチルスチレン若しくはα-メチルスチレン等の芳香族ビニル化合物、アミノエチルアクリレート等の不飽和カルボン酸アミノアルキルエステル、グリシジルアクリレート若しくはグリシジルメタクリレート等の不飽和カルボン酸グリシジルエステル、酢酸ビニル若しくはプロピオン酸ビニル等のカルボン酸ビニルエステル、アクリロニトリル、メタクリロニトリル若しくはα-クロルアクリロニトリル等のシアン化ビニル化合物、1,3-ブタジエン若しくはイソプレン等の脂肪族共役ジエン、それぞれ末端にアクリロイル基若しくはメタクリロイル基を有するポリスチレン、ポリメチルアクリレート、ポリメチルメタクリレート、ポリブチルアクリレート又はポリブチルメタクリレートが挙げられる。 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.
 中でも、メタクリル酸及び/又はアクリル酸と、メタクリル酸メチル、2-ヒドロキシエチルメタクリレート、ベンジルメタクリレート及びスチレンからなる群から選ばれたモノマーと、の2~4元共重合体で、重量平均分子量(Mw)が2千~10万(テトラヒドロフランをキャリヤーとしてゲルパーミェーションクロマトグラフィーで測定し、標準ポリスチレンによる検量線を用いて換算したもの)、酸価が70~150(mgKOH/g)の樹脂が、アルカリ現像液に対する適度な溶解性を有するため好ましい。 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.
 また、露光及び現像の際の感度を向上させるのであれば、側鎖にエチレン性不飽和基を有するアクリル樹脂が好ましい。この場合、側鎖が有するエチレン性不飽和基としては、アクリル基又はメタクリル基が好ましい。このようなアクリル樹脂は、カルボキシル基を有するアクリル樹脂のカルボキシル基に、グリシジル基又は脂環式エポキシ基を有するエチレン性不飽和化合物を付加反応させて得ることができる。 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.
 側鎖にエチレン性不飽和基を有するアクリル樹脂としては、公知文献(例えば、特許第3120476号公報又は特開平8-262221号公報)に記載のアクリル樹脂又は市販の“サイクロマー(登録商標)”P(ダイセル化学工業(株)製)若しくはアルカリ可溶性カルド樹脂が挙げられる。 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.
 本発明のタッチパネル用黒色樹脂組成物は、さらにモノマーを含有しても構わない。モノマーとしては、例えば、多官能若しくは単官能のアクリル系モノマー又はオリゴマーを用いることができる。多官能のアクリル系モノマーとしては、例えば、ビスフェノールAジグリシジルエーテル(メタ)アクリレート、ポリ(メタ)アクリレートカルバメート、変性ビスフェノールAエポキシ(メタ)アクリレート、アジピン酸1,6-ヘキサンジオール(メタ)アクリル酸エステル、無水フタル酸プロピレンオキサイド(メタ)アクリル酸エステル、トリメリット酸ジエチレングリコール(メタ)アクリル酸エステル、ロジン変性エポキシジ(メタ)アクリレート、アルキッド変性(メタ)アクリレート、公知文献(例えば、特許第3621533号公報又は特開平8-278630号公報)記載のフルオレンジアクリレート系オリゴマー、トリプロピレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ビスフェノールAジグリシジルエーテルジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリアクリルホルマール、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、2,2-ビス[4-(3-アクリロキシ-2-ヒドロキシプロポキシ)フェニル]プロパン、ビス[4-(3-アクリロキシ-2-ヒドロキシプロポキシ)フェニル]メタン、ビス[4-(3-アクリロキシ-2-ヒドロキシプロポキシ)フェニル]スルホン、ビス[4-(3-アクリロキシ-2-ヒドロキシプロポキシ)フェニル]エーテル、4,4’-ビス[4-(3-アクリロキシ-2-ヒドロキシプロポキシ)フェニル]シクロヘキサン、9,9-ビス[4-(3-アクリロキシ-2-ヒドロキシプロポキシ)フェニル]フルオレン、9,9-ビス[3-メチル-4-(3-アクリロキシ-2-ヒドロキシプロポキシ)フェニル]フルオレン、9,9-ビス[3-クロロ-4-(3-アクリロキシ-2-ヒドロキシプロポキシ)フェニル]フルオレン、ビスフェノキシエタノールフルオレンジアクリレート、ビスフェノキシエタノールフルオレンジメタアクリレート、ビスクレゾールフルオレンジアクリレート又はビスクレゾールフルオレンジメタアクリレートが挙げられるが、より感度を向上させるため、3以上の官能基を有するモノマーが好ましく、5以上の官能基を有するモノマーがより好ましく、ジペンタエリスリトールヘキサ(メタ)アクリレート又はジペンタエリスリトールペンタ(メタ)アクリレートがさらに好ましい。 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.
 本発明のタッチパネル用黒色樹脂組成物は、さらに光重合開始剤を含有することが好ましい。本発明のタッチパネル用黒色樹脂組成物が含有する樹脂として、アクリル樹脂に代表される感光性樹脂を用い、これに光重合開始剤を組み合わせることによって、本発明のタッチパネル用黒色樹脂組成物に感光性を付与することができる。そしてその結果として、フォトリソグラフィーすなわち露光及び現像工程により、所望の遮光膜を簡便かつ高精細に形成することが可能となる。なお、本発明のタッチパネル用黒色樹脂組成物が感光性であり、かつ青色顔料、緑色顔料、黄色顔料及び紫色顔料からなる群から選ばれる顔料を含有する場合には、露光及び現像の際の光硬化の感度をさらに向上させることが可能となる。 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.
 光重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、オキサントン系化合物、イミダゾール系化合物、ベンゾチアゾール系化合物、ベンゾオキサゾール系化合物、オキシムエステル化合物、カルバゾール系化合物、トリアジン系化合物、リン系化合物又はチタネート等の無機系光重合開始剤が挙げられる。 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.
 より具体的には、例えば、ベンゾフェノン、N,N’-テトラエチル-4,4’-ジアミノベンゾフェノン、4-メトキシ-4’-ジメチルアミノベンゾフェノン、2,2-ジエトキシアセトフェノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール、α-ヒドロキシイソブチルフェノン、チオキサントン、2-クロロチオキサントン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノ-1-プロパン、“イルガキュア(登録商標)”369である2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン、“イルガキュア(登録商標)”379である2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン、“イルガキュア(登録商標)”907である2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォルノプロパン-1-オン、CGI-113である2-[4-メチルベンジル]-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン、“イルガキュア(登録商標)”OXE01である1,2-オクタンジオン,1-[4-(フェニルチオ)-2-(O-ベンゾイルオキシム)]、“イルガキュア(登録商標)”OXE02であるエタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(0-アセチルオキシム)若しくはCGI-242であるエタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)(いずれもチバ・スペシャリティ・ケミカル(株)製)、t-ブチルアントラキノン、1-クロロアントラキノン、2,3-ジクロロアントラキノン、3-クロル-2-メチルアントラキノン、2-エチルアントラキノン、1,4-ナフトキノン、9,10-フェナントラキノン、1,2-ベンゾアントラキノン、1,4-ジメチルアントラキノン、2-フェニルアントラキノン、2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール2量体、2-メルカプトベンゾチアゾール、2-メルカプトベンゾオキサゾール、4-(p-メトキシフェニル)-2,6-ジ-(トリクロロメチル)-s-トリアジン、カルバゾール系化合物である“アデカ(登録商標)オプトマー”N-1818又はオキシムエステル系化合物である“アデカアークルズ”NCI-831若しくはNCI-930(いずれもADEKA(株)製)あるいはPBG304又はPBG305(いずれも常州強力電子新材料(有)製)が挙げられるが、より感度を向上させるため、“イルガキュア(登録商標)”379、“イルガキュア(登録商標)”OXE02、“アデカ(登録商標)オプトマー”N-1919、“アデカアークルズ”NCI-831及びPBG304からなる群から選ばれる2種類を併用することが好ましい。 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.
 本発明のタッチパネル用黒色樹脂組成物は、ガラス板又はシリコンウエハー等の無機物との接着性を向上させるため、密着改良剤を含有しても構わない。密着改良剤としては、例えば、シランカップリング剤又はチタンカップリング剤が挙げられる。密着改良剤の添加量は、通常、樹脂に対して0.2~20質量%程度である。 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.
 本発明のタッチパネル用黒色樹脂組成物は、遮光材及び顔料の分散安定性を向上させるため、高分子分散剤を含有しても構わない。高分子分散剤としては、例えば、ポリエステル系高分子分散剤、アクリル系高分子分散剤、カルボジイミド系分散剤、ポリエチレンイミン系高分子分散剤、ポリウレタン系高分子分散剤又はポリアリルアミン系高分子分散剤が挙げられる。これらの高分子分散剤は、分散する遮光材及び顔料の種類を考慮して、適宜選択すればよい。また高分子分散剤は、アミン価のみを有する分散剤、酸価のみを有する分散剤、アミン価及び酸価を有する分散剤又はアミン価及び酸価をいずれも有さない分散剤に区分されるが、本発明の効果をより顕著なものとするため、アミン価を有する分散剤が好ましく、アミン価のみを有する高分子分散剤がより好ましい。 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.
 アミン価のみを有する分散剤としては、例えば、ディスパービック102、160、161、162、2163、2164、166、167、168、2000、2050、2150、2155、LPN6919、LPN21116、LPN21234、9075若しくは9077(以上、いずれもビックケミー社製)、EFKA 4015、4020、4046、4047、4050、4055、4060、4080、4300、4330、4340、4400、4401、4402、4403若しくは4800(以上、いずれもBASF社製)又はアジスパーPB711(味の素ファインテクノ社製)が挙げられるが、3級アミノ基を有する高分子分散剤である、ディスパービックLPN6919又はLPN21116等が好ましい。 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.
 アミン価及び酸価を有する高分子分散剤としては、例えば、ディスパービック142、145、2001、2010、2020、2025若しくは9076又はAnti-Terra-205(以上、いずれもビックケミー社製)、ソルスパース24000(ルーブリゾール(株)社製)あるいはアジスパーPB821、PB880若しくはPB881(以上、いずれも味の素ファインテクノ社製)が挙られる。
これらの高分子分散剤は密着性や感光性を低下させない程度に添加することが好ましく、高分子分散剤の添加量は、通常、遮光材及び顔料に対して1~40質量%程度である。
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.
 本発明のタッチパネル用黒色樹脂組成物においては、反射率、遮光性及び密着性のバランスを保つため、遮光材及び顔料/樹脂、モノマー及び高分子分散剤の質量比は、60/40~5/95の範囲であることが好ましく、50/50~10/90の範囲であることがより好ましい。樹脂、モノマー及び高分子分散剤の量が少なすぎると、反射率が高くなる。一方で、遮光材及び顔料の量が少なすぎると、厚み当たりの光学濃度(OD値/μm)が低くなり、膜厚を厚くする必要が生じる。 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.
 本発明のタッチパネル用黒色樹脂組成物は、溶媒を含有する。溶媒は、分散する顔料の分散安定性及び添加する樹脂等の溶解性等を考慮して、水又は有機溶媒を適宜選択すればよい。有機溶媒としては、例えば、エステル類、脂肪族アルコール類、(ポリ)アルキレングリコールエーテル系溶媒、ケトン類、アミド系極性溶媒又はラクトン系極性溶媒が挙げられる。 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.
 アクリル樹脂を溶解する有機溶媒としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ-n-プロピルエーテル、エチレングリコールモノ-n-ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ-n-プロピルエーテル、ジエチレングリコールモノ-n-ブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ-n-プロピルエーテル、プロピレングリコールモノ-n-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ-n-プロピルエーテル、ジプロピレングリコールモノ-n-ブチルエーテル、トリプロピレングリコールモノメチルエーテル若しくはトリプロピレングリコールモノエチルエーテル等の(ポリ)アルキレングリコールモノアルキルエーテル類、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、1,3-ブチレングリコールジアセテート、プロピレングリコールモノメチルエーテルアセテート(以下、「PMA」)、ジプロピレングリコールメチルエーテルアセテート若しくはプロピレングリコールモノエチルエーテルアセテート等の(ポリ)アルキレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル若しくはテトラヒドロフラン等の他のエーテル類、メチルエチルケトン、シクロヘキサノン、2-ヘプタノン若しくは3-ヘプタノン等のケトン類、2-ヒドロキシプロピオン酸メチル若しくは2-ヒドロキシプロピオン酸エチル等の乳酸アルキルエステル類、2-ヒドロキシ-2-メチルプロピオン酸エチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、2-ヒドロキシ-3-メチルブタン酸メチル、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、3-メチル-3-メトキシブチルプロピオネート、酢酸エチル、酢酸n-プロピル、酢酸i-プロピル、酢酸n-ブチル、酢酸i-ブチル、蟻酸n-ペンチル、酢酸i-ペンチル、プロピオン酸n-ブチル、酪酸エチル、酪酸n-プロピル、酪酸i-プロピル、酪酸n-ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸n-プロピル、アセト酢酸メチル、アセト酢酸エチル若しくは及び2-オキソブタン酸エチル等の他のエステル類、トルエン若しくはキシレン等の芳香族炭化水素類又はN-メチルピロリドン、N,N-ジメチルホルムアミド若しくはN,N-ジメチルアセトアミド等のアミド類等が挙げられる。 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.
 さらに、基板の大型化に伴いダイコーティング装置による塗布が主流になってきているところ、適度な揮発性及び乾燥性を実現するため、沸点が170℃以上の溶媒を30~75質量%含有することが好ましく、さらには、沸点が200℃以上の溶媒を1~20質量%含有することが、ダイコーティング装置での異物欠点や真空乾燥装置での乾燥起因欠点を低減するためにおいてより好ましい。このような場合、少なくとも2種以上からなる混合溶媒を用いることが好ましい。 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.
 本発明のタッチパネル用黒色樹脂組成物は、塗布性及び着色被膜の平滑性を確保しながらベナードセルするため、界面活性剤を含有しても構わない。界面活性剤の添加量は、遮光材及び顔料に対して0.001~10質量%が好ましく、0.01~1質量%がより好ましい。 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.
 界面活性剤としては、例えば、ラウリル硫酸アンモニウム若しくはポリオキシエチレンアルキルエーテル硫酸トリエタノールアミン等の陰イオン界面活性剤、ステアリルアミンアセテート若しくはラウリルトリメチルアンモニウムクロライド等の陽イオン界面活性剤、ラウリルジメチルアミンオキサイド若しくはラウリルカルボキシメチルヒドロキシエチルイミダゾリウムベタイン等の両性界面活性剤、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル若しくはソルビタンモノステアレート等の非イオン界面活性剤、ポリジメチルシロキサン等を主骨格とするシリコーン系界面活性剤又はフッ素系界面活性剤等が挙げられる。 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.
 本発明のタッチパネル用黒色樹脂組成物における樹脂成分(溶媒を除く、モノマー、オリゴマー及び光重合開始剤等の添加剤も含む成分)と、着色材とを合わせた固形分濃度としては、塗工性や乾燥性の観点から2~30質量%が好ましく、5~20質量%がより好ましい。 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.
 本発明のタッチパネル用黒色樹脂組成物の製造方法としては、例えば、分散機を用いて樹脂溶液中に直接顔料を分散させる方法、又は、分散機を用いて水若しくは有機溶媒中に顔料を分散させて顔料分散液を作製し、その後顔料分散液と樹脂溶液と混合する方法が挙げられる。顔料の分散方法としては、例えば、ボールミル、サンドグラインダー、3本ロールミル又は高速度衝撃ミルが挙げられるが、分散効率や微分散化の観点から、ビーズミルが好ましい。ビーズミルとしては、例えば、コボールミル、バスケットミル、ピンミル又はダイノーミルが挙げられる。ビーズミルのビーズとしては、例えば、チタニアビーズ、ジルコニアビーズ又はジルコンビーズが好ましい。分散に用いるビーズ径としては、0.01~5.0mmが好ましく、0.03~1.0mmがより好ましい。顔料の一次粒子径及び一次粒子が凝集して形成された二次粒子の粒子径が小さい場合には、分散に用いるビーズ径としては、0.03~0.10mmといった微小な分散ビーズが好ましい。この場合、微小な分散ビーズと分散液とを分離することが可能な、遠心分離方式によるセパレーターを有するビーズミルを用いて分散することが好ましい。一方で、サブミクロン程度の粗大な粒子を含有する顔料を分散させる際には、十分な粉砕力を得るため、ビーズ径が0.10mm以上の分散ビーズが好ましい。 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.
 本発明のタッチパネル用遮光膜は、本発明のタッチパネル用黒色樹脂組成物より形成されることを特徴とする。本発明のタッチパネル用遮光膜の製法例を以下に示す。本発明のタッチパネル用黒色樹脂組成物を基板上に塗布する方法としては、例えば、ディップ法、ロールコータ法、スピナー法、ダイコーティング法若しくはワイヤーバーによる方法、基板を溶液中に浸漬する方法又は溶液を基板に噴霧する方法が挙げられる。本発明のタッチパネル用黒色樹脂組成物を塗布する基板としては、例えば、石英ガラス、ホウケイ酸ガラス、アルミノケイ酸塩ガラス、表面をシリカコートしたソーダライムガラス若しくは化学強化ガラス等の無機ガラス類又は有機プラスチックのフィルム若しくはシートが挙げられる。なお、本発明のタッチパネル用黒色樹脂組成物を基板上に塗布する場合、シランカップリング剤、アルミニウムキレート剤又はチタニウムキレート剤等の接着助剤で基板表面を処理しておくことで、塗布膜と基板との接着力を向上させることができる。 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.
 本発明のタッチパネル用黒色樹脂脂組成物を基板上に塗布した後、風乾、加熱乾燥又は真空乾燥等により塗布膜の加熱乾燥及び硬化をさせて、乾燥被膜を形成する。被膜を形成する際の乾燥ムラや搬送ムラを抑制するため、本発明のタッチパネル用黒色樹脂脂組成物を塗布した基板を、加熱装置を備えた減圧乾燥機で減圧乾燥した後、加熱硬化することが好ましい。 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.
 得られた塗布膜は、通常、必要に応じて酸素遮断膜を形成した上で、フォトリソグラフィー等の方法を用いてパターン加工される。その後、必要に応じて、酸素遮断膜を除去した後、さらに加熱乾燥及び硬化をさせることで、遮光膜が得られる。熱硬化条件は、樹脂により異なるが、アクリル系樹脂を用いる場合には、通常、200~250℃で1~60分加熱するのが一般的である。 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.
 本発明のタッチパネル前面板は、本発明のタッチパネル用遮光膜を具備することを特徴とする。該タッチパネル前面板は、透明基板と、該透明基板の一部領域上に形成された本発明の遮光膜と、から構成することができる。 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.
 以下、実施例及び比較例を挙げて、本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。 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.
 <評価方法>
 [昇華物]
 厚み0.7mmの化学強化ガラス(Gorilla(登録商標);コーニング製)の上に所望の膜厚の遮光膜を形成し、280℃の熱風オーブンで30分間加熱した後、塗膜表面を白い布で拭い、顔料由来の昇華物の付着がないかを目視で観察した。顔料由来の昇華物の付着により白い布が着色したものはB、着色のなかったものはAと判定した。
<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.
 [透過率]
 厚み0.7mmの化学強化ガラスの上にOD値が3となる膜厚の遮光膜を形成し、分光光度計(UV-2500PC;島津製作所 測定波長領域:280~1000nm、サンプリングピッチ:1.0nm、スキャン速度:低速、スリット幅:2.0nm)を用いて透過率を測定した。
[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).
 [反射色度]
 厚み0.7mmの化学強化ガラスの上に所望の膜厚の遮光膜を形成し、分光光時計(MPC-2200;島津製作所製)を用いて、ガラス面からの反射色度(反射率R、L*a*b表色系のa*及びb*)を測定した。(測定波長領域:380~780nm、サンプリングピッチ:1.0nm、スキャン速度:低速、スリット幅:2.0nm)。青みの指標(マイナスの方向になるほど青みが強くなる)であるb*の値が、-0.3以下の場合をA、-0.2~0.2の場合をB、0.3~0.7をC、0.8以上をDと判定した。
[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値]
 厚み0.7mmの化学強化ガラスの上に膜厚1.0μmの遮光膜を形成し、X-rite 361T(visual)densitometerを用いて入射光及び透過光それぞれの強度を測定し、以下の式(1)より算出した。
OD値 = log10(I/I) ・・・ 式(1)
:入射光強度
I:透過光強度
 [PAN耐性]
 厚み0.7mmの化学強化ガラスの上に所望の膜厚の遮光膜を形成し、50℃に加熱したPAN溶液(HNO/HPO/CHCOOH/HO=質量比5/68/12/15)に2分間浸漬し、PAN溶液処理前後のOD値変化を測定した。
[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.
 (アクリルポリマー(P-1)の合成)
 文献(特許第3120476号公報;実施例1)記載の方法により、メチルメタクリレート/メタクリル酸/スチレン共重合体(質量比30/40/30)を合成後、40質量部のグリシジルメタクリレートを付加させ、精製水で再沈、濾過、乾燥することにより、重量平均分子量(Mw)10,000、酸価110(mgKOH/g)のアクリルポリマー(P-1)粉末を得た。
(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.
 (黒色顔料分散液Bk-1の製造)
 黒色顔料1(BASF社製“Irgaphor Black S0100CF”:600.0g)にアクリル樹脂(P-1)のプロピレングリコールモノメチルエーテルアセテート35質量%溶液(321.4g)、高分子分散剤(BYK21116;ビックケミー社製;93.8g)及びプロピレングリコールモノエチルエーテルアセテート(1984.8g)をタンクに仕込み、ホモミキサー(特殊機化製)で1時間撹拌し、予備分散液1を得た。その後、0.10mmφジルコニアビーズ(東レ製)を70%充填した遠心分離セパレーターを具備した、ウルトラアペックスミル(寿工業製)に予備分散液1を供給し、回転速度8m/sで2時間分散を行い、固形分濃度25質量%、顔料/樹脂(質量比)=80/20の黒色顔料分散液Bk-1を得た。
(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.
 (有機顔料分散液DB-1の製造)
 黒色顔料1の代わりに有機顔料PB15:6(東洋インキ(株)製)を用いた以外は、黒色顔料分散液Bk-1と同様にして、有機顔料分散液DB-1を得た。
(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.
 (有機顔料分散液DG-1の製造)
 黒色顔料1の代わりに有機顔料PG58(DIC(株)製)を用いた以外は、黒色顔料分散液Bk-1と同様にして、有機顔料分散液DG-1を得た。
(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.
 (有機顔料分散液DY-1の製造)
 黒色顔料1の代わりに有機顔料PY150(ランクセス製)を用いた以外は、黒色顔料分散液Bk-1と同様にして、有機顔料分散液DY-1を得た。
(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.
 (有機顔料分散液DV-1の製造)
 黒色顔料1の代わりに有機顔料PV23(クラリアント(株)製)を用いた以外は、黒色顔料分散液Bk-1と同様にして、有機顔料分散液DV-1を得た。
(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.
 (有機顔料分散液DR-1の製造)
 黒色顔料1の代わりに有機顔料PR254(BASF製)を用いた以外は、黒色顔料分散液Bk-1と同様にして、有機顔料分散液DR-1を得た。
(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.
 (有機顔料分散液DR-2の製造)
 黒色顔料1の代わりに有機顔料PR177(BASF製)を用いた以外は、黒色顔料分散液Bk-1と同様にして、有機顔料分散液DR-2を得た。
(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.
 (黒色顔料分散液Bk-2の製造)
 黒色顔料1の代わりに窒化チタン(日清エンジニアリング(株)製)を用いた以外は、黒色顔料分散液Bk-1と同様にして、黒色顔料分散液Bk-2を得た。
(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.
 (黒色顔料分散液Bk-3の製造)
 黒色顔料1の代わりにカーボンブラック(TPX1291;CABOT製)を用いた以外は、黒色顔料分散液Bk-1と同様にして、黒色顔料分散液Bk-3を得た。
(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.
 (実施例1)
 PMAを29.52gに、光重合開始剤としてアデカアークルズ(登録商標)NCI-831を0.38g添加し、固形分が溶解するまで撹拌した。
(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.
 さらに、アクリルポリマー(P-1)のPMA35質量%溶液を16.03g、多官能モノマーとしてジペンタエリスリトールヘキサアクリレート(日本化薬(株)製)を3.38g、界面活性剤としてシリコーン系界面活性剤BYK333のPMA10質量%溶液を0.24g添加し、室温にて1時間撹拌し、感光性レジストを得た。この感光性レジストに黒色顔料分散液Bk-1を10.46g添加することで全固形分濃度20質量%、顔料/樹脂(質量比)=18/82、黒色顔料=100の感光性黒色樹脂組成物A-1を調製した。 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.
 調製した感光性黒色樹脂組成物1を2μmのテフロン(登録商標)製フィルターで濾過後、膜厚が1μm(ポストベーク後)になるように基板上にミカサ(株)製スピンコーティング装置1H-DSで塗布し、塗布した基板を90℃のホットプレート上のピン状突起物で2分加熱処理し、さらに2分間ホットプレート上に直接基板を静置してプリベイクを行った。この塗布膜にユニオン光学(株)製マスクアライナーPEM-6Mを用い、解像度テスト用マスクを介して紫外線を200mJ/cmの露光量で露光した。 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.
 次に、0.1質量%水酸化テトラメチルアンモニウム水溶液のアルカリ現像液で現像し、続いて純水洗浄することにより、パターンニング基板を得た。得られたパターンニング基板を熱風オーブン中230℃で30分保持し、ポストベイクを行なうことで遮光基板1を得た。 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.
 (実施例2)
 着色材として使用する顔料の質量比を黒色顔料1/青色顔料PB15:6=80/20(感光性レジストに上記分散液BK-1を8.37g、顔料分散液DB-1を2.09g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-2を得た。得られた感光性樹脂組成物A-2を用いて、実施例1と同様にして遮光基板2を得た。
(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.
 (実施例3)
 着色材として使用する顔料の質量比を黒色顔料1/青色顔料PB15:6=50/50(感光性レジストに上記分散液BK-1を5.23g、顔料分散液DB-1を5.23g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-3を得た。得られた感光性樹脂組成物A-3を用いて、実施例1と同様にして遮光基板3を得た。
(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.
 (実施例4)
 着色材として使用する顔料の質量比を黒色顔料1/緑色顔料PG58=80/20(感光性レジストに上記分散液BK-1を8.37g、顔料分散液DG-1を2.09g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-4を得た。得られた感光性樹脂組成物A-4を用いて、実施例1と同様にして遮光基板4を得た。
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.
 (実施例5)
 着色材として使用する顔料の質量比を黒色顔料1/黄色顔料PY150=80/20(感光性レジストに上記分散液BK-1を8.37g、顔料分散液DY-1を2.09g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-5を得た。得られた感光性樹脂組成物A-5を用いて、実施例1と同様にして遮光基板5を得た。
(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.
 (実施例6)
 着色材として使用する顔料の質量比を黒色顔料1/紫色顔料PV23=80/20(感光性レジストに上記分散液BK-1を8.37g、顔料分散液DV-1を2.09g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-6を得た。得られた感光性樹脂組成物A-6を用いて、実施例1と同様にして遮光基板6を得た。
(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.
 (実施例7)
 着色材として使用する顔料の質量比を黒色顔料1/赤色顔料PR254=80/20(感光性レジストに上記分散液BK-1を8.37g、顔料分散液DR-1を2.09g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-7を得た。得られた感光性樹脂組成物A-7を用いて、実施例1と同様にして遮光基板7を得た。
(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.
 (実施例8)
 着色材として使用する顔料の質量比を黒色顔料1/赤色顔料PR177=80/20(感光性レジストに上記分散液BK-1を8.37g、顔料分散液DR-2を2.09g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-8を得た。得られた感光性樹脂組成物A-8を用いて、実施例1と同様にして遮光基板8を得た。
(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.
 (比較例1)
 着色材として使用する顔料の質量比を青色顔料PB15:6/赤色顔料PR254=50/50(感光性レジストに上記分散液DB-1を5.23g、顔料分散液DR-1を5.23g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-9を得た。得られた感光性樹脂組成物A-9を用いて、実施例1と同様にして遮光基板9を得た。
(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.
 (比較例2)
 着色材として使用する顔料の質量比を青色顔料PB15:6/赤色顔料PR177=50/50(感光性レジストに上記分散液DB-1を5.23g、顔料分散液DR-2を5.23g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-10を得た。得られた感光性樹脂組成物A-10を用いて、実施例1と同様にして遮光基板10を得た。
(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.
 (比較例3)
 着色材として使用する顔料の質量比を窒化チタン=100(感光性レジストに上記分散液Bk-2を10.46g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-11を得た。得られた感光性樹脂組成物A-11を用いて、実施例1と同様にして遮光基板11を得た。
(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.
 (比較例4)
 着色材として使用する顔料の質量比をカーボンブラック=100(感光性レジストに上記分散液Bk-3を10.46g添加)とした以外は実施例1と同様にして、感光性黒色樹脂組成物A-12を得た。得られた感光性樹脂組成物A-12を用いて、実施例1と同様にして遮光基板12を得た。
(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.
 <評価結果>
 実施例1~8及び比較例1~4で作製した黒色樹脂組成物の組成及び作製した遮光基板の評価結果を、表1及び表2に示す。
<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.
 実施例1~8ではいずれも850~1000nmの赤外線領域における透過率が60%以上と高く、近接センサーの動作のために必要となる赤外領域の光すなわち赤外線を十分に透過し、反射色度も良好な遮光基板を得ることができた。 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.
 また、実施例2~6のようにさらに青色顔料、緑色顔料、黄色顔料又は紫色顔料を添加することで、280~480nmにおける透過率が向上した。この結果は、低露光量でも効率的な光硬化が可能であり、パターン加工性に優れた感光性遮光膜を提供可能であることを示唆するものである。 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.
 一方、比較例1及び2のように赤色顔料と青色顔料とを混合した系の遮光膜は、昇華物の発生やPAN耐性の面において劣り、耐薬品性等において優れる遮光膜を得ることができなかった。 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.
 また、比較例3及び4のように無機黒色顔料である窒化チタンやカーボンブラックを使用した系の遮光膜は、赤外線を透過せず、光学特性に優れた遮光膜を得ることができなかった。 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.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
 本発明のタッチパネル用黒色樹脂組成物は、近接センサー用の赤外線を透過するタッチパネル用前面板が具備する遮光膜の形成に利用することができる。 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 (9)

  1.  下記一般式(I)~(III)からなる群から選ばれる一般式で表される黒色顔料、樹脂及び溶媒を含有する、タッチパネル用黒色樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    (一般式(I)~(III)中、R及びRは、それぞれ独立して、水素又は炭素数1~10のアルキル基を表し、R及びRは、それぞれ独立して、R11、OR11、SR11、COR11、CONR1213、NR12COR11、OCOR11、COOR11、SCOR11、OCSR11、COSR11、CSOR11、CN、ハロゲン原子又は水酸基を表し、R11、R12及びR13は、それぞれ独立して、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環基を表し、a及びbは、それぞれ独立して、0~4の整数を表す。)
    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.
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    (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.  さらに青色顔料、緑色顔料、黄色顔料及び紫色顔料からなる群から選ばれる顔料を含有する、請求項1記載のタッチパネル用黒色樹脂組成物。 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.
  3.  さらに光重合開始剤を含有する、請求項1又は2記載のタッチパネル用黒色樹脂組成物。 The black resin composition for a touch panel according to claim 1 or 2, further comprising a photopolymerization initiator.
  4.  請求項1~3のいずれか一項記載のタッチパネル用黒色樹脂組成物より形成される、タッチパネル用遮光膜。 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.
  5.  請求項4記載のタッチパネル用遮光膜を具備する、タッチパネル前面板。 A touch panel front plate comprising the light shielding film for a touch panel according to claim 4.
  6.  下記一般式(I)~(III)からなる群から選ばれる一般式で表される黒色顔料、樹脂及び溶媒を含有する黒色樹脂組成物の、タッチパネル用遮光膜を形成するための使用。
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
    (一般式(I)~(III)中、R及びRは、それぞれ独立して、水素又は炭素数1~10のアルキル基を表し、R及びRは、それぞれ独立して、R11、OR11、SR11、COR11、CONR1213、NR12COR11、OCOR11、COOR11、SCOR11、OCSR11、COSR11、CSOR11、CN、ハロゲン原子又は水酸基を表し、R11、R12及びR13は、それぞれ独立して、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環基を表し、a及びbは、それぞれ独立して、0~4の整数を表す。)
    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.
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
    (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.  さらに青色顔料、緑色顔料、黄色顔料及び紫色顔料からなる群から選ばれる顔料を含有する請求項6記載の黒色樹脂組成物の、タッチパネル用遮光膜を形成するための使用。 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.
  8.  さらに光重合開始剤を含有する請求項6又は7記載の黒色樹脂組成物の、タッチパネル用遮光膜を形成するための使用。 Furthermore, the use for forming the light shielding film for touchscreens of the black resin composition of Claim 6 or 7 containing a photoinitiator.
  9.  請求項6~8のいずれか一項記載の黒色樹脂組成物を使用して形成されたタッチパネル用遮光膜を具備する、タッチパネル前面板。
     
    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.
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