JP6699691B2 - Black composition, black coating film, and laminate - Google Patents

Description

  The present invention relates to a black composition used for decorating an operation panel that can be used in electronic devices such as smartphones and digital music players, and a black coating film formed using the black composition, particularly for decorating a touch panel. A coating film suitable for.

  In recent years, many electronic devices such as smartphones and digital music players are internally equipped with an input device called a capacitive touch panel. The capacitive touch panel is a switch that uses a phenomenon in which the capacitance of an electrode changes when a finger approaches the electrode.

  In the electrostatic capacity type touch panel, as described in Patent Document 1, decoration is performed when manufacturing the operation panel so that the light shielding section has sufficient concealing property and the electrostatic capacity switch does not malfunction or malfunction. Is applied. When looking at the liquid crystal display from the user's side in a mobile phone, etc., information and images are not displayed on the entire surface of the transparent glass, but there is a black-painted part on the outer peripheral part of the glass substrate to divide the display part. The display is made inside this. The frame portion (decorating portion) has a function of defining the display portion in a square shape and concealing a portion (wiring portion for a touch panel, etc.) that is inconvenient to see so as not to be visually recognized.

In addition, as the structure of the touch panel, a decorative portion is formed on the cover glass using a resin material for a black matrix used for manufacturing a color filter substrate, and then the degassing prevention and insulating properties are formed on the decorative portion. For the purpose of securing and improving flatness, a decorative cover glass-integrated touch panel sensor structure or the like is known in which an overcoat layer made of a transparent insulating material is provided, and a touch panel sensor is further formed thereon (for example, Patent Document 1). 2).
As described above, in order to produce a touch panel on which a decorative portion is formed on a glass substrate, an overcoat layer is provided for the purpose of preventing gas emission from the decorative portion and improving flatness as a coated surface. Although it is necessary to form the film, if the resin material for the black matrix used in the conventional color filter substrate production is simply diverted, the adhesiveness with the overcoat layer, which is the organic layer, is poor, and therefore peeling occurs at the interface. There is a problem that occurs.

JP, 2000-012345, A JP 2012-155644 A

  INDUSTRIAL APPLICABILITY The present invention provides a black composition having excellent adhesion, good adhesion to an organic layer, excellent aesthetics, and linearity of a pattern when used as a display device. The purpose is to do. Furthermore, it aims at providing the high quality black coating film suitable for decorating a touch panel using this black composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that at least two types of organic pigments (A), binder resins (B), specific silane coupling agents (C), and specific By using a black coloring composition containing a photopolymerizable monomer and having specific spectral characteristics, when used in a laminate having at least one side of an organic layer, the adhesion to the organic layer, and to the substrate It was found that a high-quality black coating film having excellent adhesiveness and a good pattern shape can be obtained, which is particularly suitable for touch panel decoration, and the present invention has been made based on this finding.

That is, the present invention is a black composition containing at least two kinds of organic pigments (A), a binder resin (B), a silane coupling agent (C), and a photopolymerizable monomer (D),
The organic pigment (A) contains at least a red pigment and a blue pigment,
The content of the red pigment is 45% by weight or more based on the total amount of the organic pigment (A), and the silane coupling agent (C) has an epoxy group or an isocyano group (C1). From the group consisting of the photopolymerizable monomer (D1) containing a urethane bond and the photopolymerizable monomer (D2) having a structure modified with caprolactone. Contains at least one selected,
When the coating film is formed on the black composition under the condition that the film thickness is 2.0 μm, the light transmittance in all wavelength ranges of 400 to 700 nm is 25% or less,
And, the adhesion of the organic layer to the black coating layer made of the black composition is less than 10 in the number of peeled out of 100 cross-cuts according to the cross-cut adhesion test method,
The black composition is characterized in that the organic layer is a layer obtained by heating an acrylic resin at a film thickness of 2.00 μm at 230° C. for 20 minutes.

  Further, in the present invention, the content of the silane coupling agent (C1) is 0.1% by weight or more and less than 5% by weight in 100% by weight of the total solid content of the black composition. Regarding things.

  Further, in the present invention, the ratio ([M]/[P]) of the content [P] of the binder resin (B) and the content [M] of the photopolymerizable monomer (D) is 0. 30 to 0.80 with respect to the black composition.

  The present invention also relates to the above black composition, which further comprises an oxime ester photopolymerization initiator.

  The present invention also relates to a black coating film formed by using the black composition.

  Further, the present invention relates to the black coating film having a film thickness of 1.0 μm or more.

  The present invention also relates to the black coating film, which is used for decorating a touch panel.

  Further, the present invention relates to a laminate having a black coating film layer formed of the black coating film and an organic layer in contact with at least one surface of the black coating film layer.

  The black composition of the present invention is excellent in stability, has good adhesion to an organic layer and good adhesion to a substrate, and can impart an aesthetically pleasing tint and pattern linearity. The black coating film using the black composition is particularly suitable for touch panel decoration.

The difference PW1-PW2 between the maximum value (PW1) and the minimum value (PW2) of the line width of the pattern is shown.

Hereinafter, the present invention will be described in detail.
In addition, in this application, when it describes with "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", it demonstrates especially. "Acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless otherwise specified. Shall be represented.
In addition, “CI” mentioned in the present specification means color index (CI).

First, the black composition in the present invention will be specifically described.
<<Black composition>>
The black composition of the present invention is a black composition containing at least two kinds of organic pigments (A), a binder resin (B), and a silane coupling agent (C). When a coating film is formed under the condition of 0.0 μm, the light transmittance in the entire wavelength range of 400 to 700 nm is 25% or less, and the adhesion of the black coating film layer comprising the black composition to the organic layer The property is that the number of peeled pieces in 100 cross-cuts according to the cross-cut adhesion test method is less than 10 pieces.

<Colorant>
(Organic pigment (A))
The black composition of the present invention contains at least two kinds of organic pigments (A). This makes it possible to obtain a black coating film excellent in light-shielding properties and aesthetics.
As the organic pigment that can be used, various pigments can be used as long as the effects of the present invention are not impaired, and examples thereof include the following.
Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81:2, 81:3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 266, 272, 276 and the like.
Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213 and the like.
Examples of orange pigments include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 81 and the like.
Examples of green pigments include C.I. I. Pigment Green 7, 10, 36, 58 and the like.
Examples of blue pigments include C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 80 and the like.
Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like.
As the black pigment, C.I. I. Pigment Black 1, 31, 32 and the like.

  Among these, combinations containing at least two pigments selected from the group consisting of red pigments, blue pigments, yellow pigments, and black pigments, or perylene blacks such as Pigment Black 31 and 32 and organic pigments other than perylene black Is preferred. More preferably, it contains at least a red pigment and a blue pigment from the viewpoint of light-shielding properties and aesthetics.

  More specifically, among others, as a red pigment, C.I. I. Pigment Red 177 or 254, a blue pigment such as C.I. I. Pigment Blue 15:6 or 15:3 is preferable. Other pigments include C.I. I. Pigment Yellow 138, 139, 150, or 185, a black pigment such as C.I. I. Pigment Black 31 or 32 is preferable.

Each content in the organic pigment (A) is based on the total of the organic pigment (A) (100% by weight), the red pigment is 20 to 60% by weight, the blue pigment is 20 to 60% by weight, and other pigments. Is preferably 0 to 40% by weight.
The content of the organic pigment (A) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total solid content of the black composition (100% by weight). % Can be used.

(Carbon black)
The black composition of the present invention may contain carbon black for the purpose of imparting the light-shielding property necessary for concealing the wiring portion of the touch panel. The carbon black is not particularly limited, and any carbon black may be used, and the surface thereof may be treated with a resin or the like. The carbon black may be used alone or in combination of two or more kinds.

  Examples of carbon black include MONARCH manufactured by CABOT or BLACK PERLS (1400, 1300, 1100, 1000, 900, 880, 800, 700, L, 570, 520, 490, 480, 470, 460, 450, 430). , 420, 410), VULCAN (P, 9A32, XC72R, XC72), MOGULL, REGAL (660R, 660, 500R, 330R, 330, 300R, 250R, 250, 99R, 99I), ELFTEX (5, 8, 12,). PELLETS115), MA (77, 7, 8, 11, 100, 100R, 100S, 230, 200RB, 14), # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990) manufactured by Mitsubishi Chemical. 980, 970, 960, 950, 900, 850750B, 650B, 52, 50, 47, 45, 45L, 44, 40, 33, 32, 30, 95, 85, 260, 3230B, 3350B), CF9, MCF88, MA600. , Color Black (FW2000, FW2, FW2V, FW1, FW18, S170, S160), Special Black (4, 4A, 550, 350, 6, 5), Printex (95, 90, 85, 80, 75, manufactured by DEGUSSA). 40, 60, 150T, U, V, 140U, 140V, 55, 45, P, L6, L, 300, 30, ES23, 3, ES22, 35, XE2), NIPex35, Tokai Carbon Seast (9H SAF- HS, 9 SAF, [6 ISAF, 600 ISAF-LS, 5H-IISAF-HS, KH(N339), 3H HAF-HS, NH(N351), 3 HAF, 3M, NLI-HAF, 300 HAF-LS, 116 MAF]. ), Asahi #80, Asahi #75, Asahi #70 (-IH, -IN, -L), Asahi HS-500, Asahi F-200, Colombian Carbon ROYAL SPECTRA, NEO SPECTRA MARK ( I and II), NEO SPECTRA AG, SUPERBA (NEO MK III), NEO SPECTRA MARK IV, RAVEN (5000, 7000, 5750, 5250, 3500, 3200, 2000, 1500), CONDUCTEX (40-220, SC), RAVEN. C BEADS, RAVEN (1255, 125 0, 1200, 1170, 1040, 1035, 1030 BEADS, 1020, 1000, 890POWDWE, 890HPOWDER, 850, 825BEADS, CONDUCTEX (975BEADS, 900BEADS) and the like can be mentioned. Preferably CABOT MONARCH (1100, 800), BLACK PERLS (1100, 800), DEGUSSA made PRINTE X 95, Mitsubishi Chemical #850, CABOT made REGAL (300R, 250R, 250, 99R, 99I), Mitsubishi. Chemically manufactured MA (7, 11, 100R), # (47, 45, 45L), DEGUSSA's Printex55, NIPex35, particularly preferably CABOT's MONARCH1100, DEGUSSA's PrinteX 95, Mitsubishi Chemical's #47, CABOT. REGAL 250R manufactured by DEGUS, PRINTE X55 manufactured by DEGUSSA, and NIPex35 can be used. The carbon blacks may be used alone or in combination of two or more.

  When carbon black is used, its content is preferably 1 to 50% by weight, more preferably 1 to 50% by weight, based on the total solid content of the black composition (100% by weight), from the viewpoint of light shielding properties. It can be used in an amount of 30% by weight.

<Binder resin (B)>
The binder resin (B) contained in the resin composition of the present invention disperses the colorant (A), and examples thereof include a thermoplastic resin and a thermosetting resin. The binder resin (B) is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. When used in the form of an alkali-developable photosensitive coloring composition, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic substituent. Further, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used to further improve the photosensitivity.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin. , Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

  Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic substituent include resins having an acidic substituent such as a carboxyl group and a sulfone group. As the alkali-soluble resin, specifically, an acrylic resin having an acidic substituent, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, Or an isobutylene/(anhydrous) maleic acid copolymer etc. are mentioned. Above all, at least one resin selected from an acrylic resin having an acidic substituent and a styrene/styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent has high heat resistance and transparency, and thus is preferably used. Be done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an ethylenically unsaturated double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers , The carboxyl group of the unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction, and the generated hydroxyl group is reacted with a polybasic acid anhydride to remove the ethylenically unsaturated double bond and the carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, and 3,4-epoxybutyl (meth)acrylate. , And 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more kinds. From the viewpoint of reactivity with unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferable.

  Examples of the unsaturated monobasic acid include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted compounds. Examples thereof include monocarboxylic acids, and these may be used alone or in combination of two or more kinds.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. These may be used alone or in combination of two or more kinds. I don't care. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic acid anhydride such as trimellitic anhydride, or use a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to leave the remaining anhydride. It is also possible to hydrolyze the group. When tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers There is a method of adding an ethylenically unsaturated monomer having an epoxy group to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group is copolymerized with another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of the ethylenically unsaturated monomer having an isocyanate group.

As the ethylenically unsaturated monomer having a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol Examples thereof include (meth)acrylates and hydroxyalkylmethacrylates such as cyclohexanedimethanol mono(meth)acrylate, and these may be used alone or in combination of two or more kinds. Further, a polyether mono(meth)acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and/or butylene oxide to the hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or Polyester mono(meth)acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[methacryloyloxy]ethyl isocyanate, but are not limited thereto. Two or more types can be used together.

  In order to preferably disperse the organic pigment (A), the weight average molecular weight (Mw) of the binder resin (B) is preferably in the range of 10,000 to 100,000, more preferably 10,000 to 80,000. Is. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

  Further, from the viewpoints of dispersibility, stability, developability, and heat resistance of the colorant, a carboxyl group that functions as a colorant adsorbing group and an alkali-soluble group during development, a fat that functions as an affinity group for a colorant carrier and a solvent. The balance between the aromatic group and the aromatic group is important for the dispersibility of the pigment, the penetrability of the developer in the coating film, the solubility of the uncured portion in the developer, and the durability, and the resin having an acid value of 20 to 300 mgKOH/g. Is preferably used. When the acid value is less than 20 mgKOH/g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH/g, fine patterns may not remain.

  The content of the binder resin (B) is preferably 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film forming property and various resistances are good, and the colorant concentration is It is preferable to use it in an amount of 500 parts by weight or less because it is high and can express good color characteristics. More preferably 100 to 400 parts by weight. More preferably, it is 160 to 320 parts by weight. The chromaticity region can be expanded by such a composition ratio of the pigment.

<Silane coupling agent (C)>
The black composition of the present invention contains a silane coupling agent (C1) having an epoxy group or an isocyano group as the silane coupling agent (C) for the purpose of imparting good adhesion to the organic layer. .. Most preferably, it is a silane coupling agent having an epoxy group.

Specifically as the silane coupling agent (C1),
β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxy A silane coupling agent having an epoxy group such as propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane,
a silane coupling agent having a (meth)acryloxy group such as γ-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane,
Examples thereof include silane coupling agents having an isocyano group such as 3-isocyanatopropyltriethoxysilane.
These silane coupling agents (C1) can be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

  Further, a known silane coupling agent (C2) other than the silane coupling agent (C1) may be used in combination. Specific examples of the silane coupling agent (C2) include silane coupling agents having a vinyl group, a styryl group, an amino group, a ureido group, a mercapto group, a sulfide group and the like.

Specifically as such a silane coupling agent (C2),
A silane coupling agent having a vinyl group such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane,
a silane coupling agent having a styryl group such as p-styryltrimethoxysilane,
N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-amino A silane coupling agent having an amino group such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane,
A silane coupling agent having a ureido group such as 3-ureidopropyltriethoxysilane,
A silane coupling agent having a mercapto group such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
Examples thereof include silane coupling agents having a sulfide group such as bis(triethoxysilylpropyl)tetrasulfite.

From the viewpoint of sensitivity and stability, the content of the silane coupling agent (C1) is preferably 0.1% by weight or more and less than 5% by weight based on the total solid content of the black composition (100% by weight). .. More preferably, it is 0.5% by weight or more and 4.5% by weight or less from the viewpoint of adhesion.
When the silane coupling agent (C2) is included, the content of (C2) is 0.1% by weight or more and 5% by weight based on the total solid content of the black composition (100% by weight) from the viewpoint of sensitivity and stability. It is preferably less than wt %. More preferably, it is 0.5% by weight or more and 4.5% by weight or less from the viewpoint of adhesion.

<Photopolymerizable monomer (D)>
The black composition of the present invention comprises, as the photopolymerizable monomer (D), a group consisting of a photopolymerizable monomer having a urethane bond (D1) and a photopolymerizable monomer having a caprolactone structure (D2). It contains at least one selected.

The photopolymerizable monomer (D1) and the photopolymerizable monomer (D2) improve the adhesiveness with the organic layer, and impart the adhesiveness to the substrate by imparting a good pattern shape. For that purpose, it is cured by ultraviolet rays or heat to produce a transparent resin. Since these photopolymerizable monomers have a longer distance between the crosslink groups crosslinked by photopolymerization than other photopolymerizable monomers, flexibility can be imparted to the black composition coating film. ..
As a result, it becomes possible to relieve the stress at the interface with the organic layer to be laminated, so that it is possible to obtain a black composition coating film having excellent adhesion to the organic layer. Further, it becomes possible to induce thermal sag in the heat treatment step when forming the pattern of the black composition and obtain a forward tapered shape.

(Photopolymerizable monomer having urethane bond (D1))
The photopolymerizable monomer (D1) having a urethane bond can be used without limitation as long as it has a urethane bond. For example, by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate. The polyfunctional urethane acrylate which has the obtained (meth)acryloyl group etc. is mentioned. The combination of the (meth)acrylate having a hydroxyl group and the polyfunctional isocyanate is arbitrary and is not particularly limited.

Examples of the photopolymerizable monomer (D1) include known urethane (meth)acrylates described in JP-A-2006-259351 and KUA-41, KUA-61, KUA-C21, KUA-PC21 manufactured by KSM Co., Ltd. , KUA-PEA21, KUA-PEB21, KUA-PEC21, KUA-10H, KUA-9N, KUA-15N, Kyoei Chemical Co., Ltd. AT-606, UA-306H, UA-306T, UA-306I, UA-510H, Urethane (meth)acrylates such as UA-8001G, DAUA-167, and Shin-Nakamura Chemical Co., Ltd. U-2PPA, U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, UA -33H, U-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P are mentioned.
These photopolymerizable monomers (D1) having a urethane bond can be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

(Photopolymerizable monomer having a caprolactone structure (D2))
The photopolymerizable monomer (D2) having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, and ditrimethylol. Ε-caprolactone modification obtained by esterifying (meth)acrylic acid and ε-caprolactone with a polyhydric alcohol such as propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol and trimethylolmelamine Mention may be made of polyfunctional (meth)acrylates. Among them, a polyfunctional monomer having a caprolactone structure represented by the following general formula (1) is preferable.

[一般式（１）中、６個のＲは全てが下記式（２）で表される基であるか、または６個のＲのうち１〜５個が下記式（２）で表される基であり、残余が下記式（３）で表される基である。] General formula (1)

[In the general formula (1), all six Rs are groups represented by the following formula (2), or 1 to 5 of the six Rs are represented by the following formula (2). And the rest is a group represented by the following formula (3). ]

[一般式（２）中、Ｒ¹は水素原子またはメチル基を示し、ｍは１または２の数を示し、「＊」は結合手であることを示す。] General formula (2)

[In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond. ]

[一般式（３）中、Ｒ¹は水素原子またはメチル基を示し、「＊」は結合手であることを示す。] General formula (3)

[In the general formula (3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond. ]

The photopolymerizable monomer (D2) having such a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and DPCA-20 (the above general formulas (1) to (3) ), m=1, the number of groups represented by the formula (2)=2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (the same formula, m=1, represented by the formula (2)) Number of groups=3, compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m=1, number of groups represented by formula (2)=6, R ¹ is all hydrogen atoms) Compound), DPCA-120 (m=2 in the formula, the number of groups represented by the formula (2)=6, and compounds in which R ¹ is all hydrogen atoms) and the like.
These photopolymerizable monomers (D2) having a caprolactone structure can be used singly or as a mixture of two or more kinds at an arbitrary ratio if necessary.

Examples of the photopolymerizable monomer (D) contained in the black composition of the present invention are other than the photopolymerizable monomer (D1) having a urethane bond and the photopolymerizable monomer (D2) having a caprolactone structure. It may contain other photopolymerizable monomers. Specific examples of other photopolymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane Tri(meth)acrylate, pentaerythritol tri(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth) Acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate and monoesters with succinic acid, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy ( Various acrylic and methacrylic acid esters such as (meth)acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth) ) Acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable monomers may be used alone or as a mixture of two or more at an arbitrary ratio, if necessary.

The content of the photopolymerizable monomer (D) is preferably 5 to 250 parts by weight, based on 100 parts by weight of the colorant in total, and 10 to 200 parts by weight from the viewpoint of photocurability and developability. It is more preferable to use, as the photopolymerizable monomer (D), when either the photopolymerizable monomer (D1) or (D2) is used alone, the total amount of the colorants is 100 in both cases. The amount is preferably 3 to 250 parts by weight, and more preferably 5 to 150 parts by weight from the viewpoint of photocurability and developability. When the photopolymerizable monomers (D1) and (D2) are used in combination, the content of the two types of (D1) and (D2) photopolymerizable monomers is 100 parts by weight of the total amount of the colorant. The amount is preferably 3 to 250 parts by weight, and more preferably 5 to 150 parts by weight from the viewpoint of photocurability and developability.

  The content of the photopolymerizable monomer (D) is the ratio of the content [P] of the binder resin (B) and the content [M] of the photopolymerizable monomer (D) ([M]/ [P]) is preferably 0.30 to 0.80, and more preferably 0.35 to 0.7. When ([M]/[P]) is in this range, the linearity and adhesiveness of the pattern shape are more excellent, which is preferable.

Further, the black composition of the present invention can form a coating film by a photolithography method, a printing method, or the like. When the coating film is formed by the photolithography method, the black composition preferably contains a photopolymerization initiator (E), a sensitizer, a chain transfer agent, a solvent and the like in addition to the above (A) to (D).
Hereinafter, these materials will be exemplified.

<Photopolymerization initiator (E)>
The photopolymerization initiator (E) is not particularly limited as long as it is a compound that absorbs light generated from the exposure device used in the photolithography system to generate radicals or ions.
As the photopolymerization initiator (E), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and other acetophenone compounds, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin compounds such as ether and benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′, Benzophenone compounds such as 4,4′-tetra(t-butylperoxycarbonyl)benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. Thioxanthone compound, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis( Trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2, 4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1) -Yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine Compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), O-(acetyl)-N-(1-phenyl-2-oxo) -2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, Oxime ester compounds such as 1-(0-acetyloxime), phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10 -Phenanthrenequinone, camphorquinone, quinone compounds such as ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds and the like are used.
These photopolymerization initiators can be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

  Of these, oxime ester photopolymerization initiators are preferable because they generally have high sensitivity and can form a pattern with excellent linearity. Examples of the oxime ester-based photopolymerization initiator include phenol-based and carbazole-based photopolymerization initiators, and carbazole-based photopolymerization initiators are preferred in the present invention.

[一般式（４）中、Ｒ₁〜Ｒ₄は、水素原子、Ｃ₁〜Ｃ₆のアルキル基、または置換基を有しても良いフェニル基を示す。] Further, an oxime ester photopolymerization initiator represented by the following general formula (4) is preferable, and a compound represented by the following chemical formula (5) is particularly preferable.

[In the general formula (4), R _{1 to} R ₄ represent a hydrogen atom, a C _{1 to} C ₆ alkyl group, or a phenyl group which may have a substituent. ]

  Examples of the substituent include a hydroxyl group, a mercapto group, a cyano group, a nitro group, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkoxyl group, an aryloxy group, an acyloxy group, an alkylthio group and an arylthio group.

  From the viewpoint of sensitivity, the content of the photopolymerization initiator (E) is preferably 0.5 to 50% by weight, and more preferably 3 to 30% by weight based on the total solid content of the photosensitive black composition (100% by weight). % By weight.

<Sensitizer>
Further, the black composition of the present invention may contain a sensitizer.
Examples of the sensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4 -2-ethylhexyl dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino) ) It is also possible to use an amine compound such as benzophenone together. These sensitizers may be used either individually or in combination of two or more.
Among the sensitizers, 4,4′-bis(dimethylamino)benzophenone and 4,4′-bis(diethylamino)benzophenone are preferable, and 4,4′-bis(diethylamino)benzophenone is more preferable.
These sensitizers can be used alone or in a mixture of two or more kinds at an arbitrary ratio as needed.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (E) contained in the black composition, and is 5 to 5 from the viewpoint of photocurability and developability. It is more preferably 50 parts by weight.

<Chain transfer agent>
Further, a chain transfer agent may be added to the photosensitive black composition of the present invention for the purpose of adjusting sensitivity. A polyfunctional thiol is preferable as the chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups, and examples thereof include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, and ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis Thioglycolate, pentaerythritol tetrakis thiopropionate, dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionate tris(2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2, 4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and the like can be mentioned. These polyfunctional thiols can be used alone or in combination of two or more.

The content of the chain transfer agent is preferably 0.1 to 30% by weight, and more preferably 1 to 20% by weight, based on the total solid content of the black composition (100% by weight). If it is less than 0.1% by mass, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by mass, the sensitivity may be too high and the resolution may be lowered.
<Antioxidant>
Further, the photosensitive black composition of the present invention may contain an antioxidant in order to suppress deterioration of the coating film due to light or heat.

Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers. , An antioxidant, etc. can be used.
Among these antioxidants, from the viewpoint of compatibility of the transmittance and the sensitivity of the coating film, preferred are hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants or sulfur antioxidants. Agents. Further, more preferably, it is a hindered phenol antioxidant, a hindered amine antioxidant, or a phosphorus antioxidant.

  Examples of the hindered phenol antioxidant include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di -T-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 2,2'-thio- Bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl) )-Propionate, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl -Cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro) Cinnamamide) and the like. Other examples include oligomer type and polymer type compounds having a hindered phenol structure.

  Specific examples of the hindered phenol antioxidant include Yoshinox BHT (=2,6-di-t-butyl-4-methylphenol) and Tominox TT (=tetrakis-[methylene-3-(3,5′). -Di-t-butyl-4'-hydroxyphenyl)propionate]methane), Yoshinox SR, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Tominox SS, Tominox 917, GSY-314 (above, manufactured by API Corporation), IRGANOX245, IRGANOX259, IRGANOX565, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1076, IRGANOX1425WL, IRGANOX1222, IRGANOX1330 (manufactured by BASF · Japan Co., Ltd.), ADK STAB AO-70, ADK STAB AO-50, STAB AO-330, Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stub AO-80 (above, Asahi Denka Kogyo Co., Ltd.), SummerizerBBM, SumilizerGM, SumilizerGP, SumilizerGS, SumilizerGA-80ilZurPirSum, SumilizerGA-80, SumilizerPummer, SumilizerGA-80ilSumerPummer. 101 (above, Sumitomo Chemical Co., Ltd. make).

  Examples of the hindered amine antioxidant include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4) -Piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,3) 4-butanetetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6 -Tetramethyl-4-piperidyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4 -Diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethine{(2,2,6,6-tetramethyl-4-piperidyl)imino}], dimethyl succinate and 1- Polycondensate with (2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N Examples include -(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine. Other examples include oligomer type and polymer type compounds having a hindered amine structure.

  Specific examples of the hindered amine antioxidant include Sanol LS-770, Sanol LS-765, Sanol LS-622LD, Chimasorp 944 (above, Sankyo Co., Ltd.), CYASORB UV-3346 (above, Sun Chemical Co., Ltd.), Knock Rack 224, Knock Rack CD, Uvasil 299-299LM (above, Ouchi Shinko Chemical Industry Co., Ltd.), MARK LA-63, MARKLA-68 (above Asahi Denka Kogyo KK), TINUVIN 144, TINUVIN 312 (above, BASF)・Made in Japan).

  Examples of phosphorus antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecyl. Phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, 4,4' isopropylidene diphenol alkyl phosphite, tris nonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris (2 ,4-Di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonyl) Phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidene bis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) Phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, phosphite ethylbis(2,2 4-ditert-butyl-6-methylphenyl) and the like. Other examples include oligomer type and polymer type compounds having a phosphite structure.

  Specific examples of the phosphorus-based antioxidant include IRGAFOS 168, IRGAFOS 12, IRGAFOS 38, IRGAFOSEPQ, (above, manufactured by BASF Japan Co., Ltd.), Sumilizer P-16 (manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stab PEP-4C, Adeka Stab PEP-8F, Adeka Stub. PEP-8, Adeka Stab PEP-45, Adeka Stab PEP-11C, Adeka Stab PEP-24G, Adeka Stub PEP-36, Adeka Stab HP-10, Adeka Stub P, Adeka Stub C, Adeka Stab QL, Adeka Stub 135A, Adeka Stub 1500, Adeka Stab 1500, Adeka Stab 2500, Adeka Stab 2500. ADEKA STAB 3010, ADEKA STAB 522A, ADEKA STAB TPP (all manufactured by Asahi Denka Kogyo KK), GSY-202 (all manufactured by AP Corporation), SANKOHCA (manufactured by Sanko Co., Ltd.), JPH1200, JP302, JPM313, JP304, JP308, JPP100, JP333E, JP318E, JP312 (above, made by API Corporation) are mentioned.

  Sulfur-based antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and 2,4-bis[(octylthio)methyl]- Examples thereof include o-cresol and 2,4-bis[(laurylthio)methyl]-o-cresol. Other examples include oligomer type and polymer type compounds having a thioether structure.

  Specific examples of the sulfur-based antioxidant include IRGANOXPS800FD, IRGANOXPS802FD (above, manufactured by BASF Japan Ltd.), ADEKA STAB AO-503, ADEKA STAB AO-412S (above manufactured by Asahi Denka Kogyo KK), SumilizerTPL-R, SumilizerTPM, Sumilizer. , SumilizerTP-D, SumilizerTL, SumilizerMB (all manufactured by Sumitomo Chemical Co., Ltd.), DLTP “Yoshitomi”, DSTP “Yoshitomi”, DMTP “Yoshitomi”, and DTTP “Yoshitomi” (all manufactured by API Corporation).

  Examples of the benzotriazole-based antioxidant include oligomer type and polymer type compounds having a benzotriazole structure.

  Specific examples of the benzotriazole-based antioxidant include Tomisorp 600 (manufactured by Yoshitomi Fine Chemicals), TINUVIN326, TINUVIN327, TINUVIN P, TINUVIN328 (above, manufactured by BASF Japan Ltd.), VIOSORB583, VIOSORB590 (manufactured by Kyodo Chemical Co., Ltd.). ..

  Examples of the benzophenone-based antioxidant include oligomer type and polymer type compounds having a benzophenone structure.

  Examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone and 2-hydroxy-4. -Octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 -Methoxy-5 sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone, LA-51 (all manufactured by Asahi Denka Kogyo Co., Ltd.) and the like can be mentioned. Other examples include oligomer type and polymer type compounds having a benzophenone structure.

  Specific examples of the benzophenone-based antioxidant include Tomisorp 800 (manufactured by AP Corporation) and LA-51 (manufactured by Asahi Denka Kogyo Co., Ltd.).

  Examples of the triazine-based antioxidant include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine. Other examples include oligomer type and polymer type compounds having a triazine structure.

  Specific examples of the triazine-based antioxidant include CYASORB UV-1164 (manufactured by Sun Chemical Co., Ltd.).

  Specific examples of the hydroxylamine antioxidant include compounds such as IRGASTABFS042 (above, manufactured by BASF Japan Ltd.).

  Examples of the salicylate type antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate and the like. Other examples include oligomer type and polymer type compounds having a salicylate structure.

  These antioxidants can be used singly or as a mixture of two or more kinds at an arbitrary ratio according to need.

  When the content of the antioxidant is 0.001 to 5.0% by weight based on the solid content weight of the black composition, sufficient sensitivity can be obtained when the composition is cured by ultraviolet light, and It is preferable because it is possible to suppress the deterioration of the coating film due to.

<Solvent>
In the black composition, a dye is sufficiently dispersed in a dye carrier and applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 10 μm to form a filter segment or a black matrix. A solvent may be included to facilitate the process. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like, and these can be used alone or in combination.

  It is preferable to use the solvent in an amount of 500 to 4000 parts by weight based on 100 parts by weight of the colorant, because the solvent can adjust the viscosity of the black composition to an appropriate level and form a colored film having a desired uniform thickness. ..

<Method for producing black composition>
The black composition has various organic pigments dispersed in a dye carrier such as a binder resin and/or a solvent, preferably together with a dispersion aid, such as a three-roll mill, a two-roll mill, a sand mill, a kneader or an attritor. It can be finely dispersed and manufactured using a means.

(Dispersion aid)
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a resin type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing re-aggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has good viscosity stability and the like. Become.

  Examples of the dye derivative include organic pigments, anthraquinones, acridones, or triazines having a basic substituent, an acidic substituent, or a compound having a phthalimidomethyl group which may have a substituent introduced therein. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, JP 2001-335717, and JP 2003-2003. 128669, JP-A 2004-091497, JP-A 2007-156395, JP-A 2008-094873, JP-A 2008-094986, JP-A 2008-095007, and JP-A 2008-195916. Those described in Japanese Patent Publication No. 4585781 and the like can be used, and these can be used alone or in combination of two or more kinds.

  From the viewpoint of improving dispersibility, the content of the dye derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant. From the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin-type pigment dispersant has a pigment-affinity portion having a property of adsorbing to the pigment and a portion having compatibility with the resin or the solvent, and is adsorbed to the pigment to disperse the pigment in the resin or the solvent. It acts to stabilize. Specific examples of the resin-type pigment dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyester having a free carboxyl group, and the like Oily dispersants such as salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble polyvinylpyrrolidone, etc. Resins, water-soluble polymer compounds, polyester systems, modified polyacrylate systems, ethylene oxide/propylene oxide addition compounds, phosphoric acid ester systems and the like are used, and these can be used alone or in combination of two or more.

  As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer monoethanolamine, polyoxyethylene alkyl ether phosphate ester Anionic surfactants such as; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc. Nonionic surfactants; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline. Can be used alone or in admixture of two or more.

  When the resin-type dispersant and the surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the total amount of the colorant. When the content of the resin type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the effect of addition, and when the content is more than 55 parts by weight, the dispersion is affected by the excess dispersant. May be affected.

The black composition may contain a storage stabilizer in order to stabilize the viscosity of the composition over time.
Examples of storage stabilizers include organic acids such as benzyl trimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, lactic acid, oxalic acid and its methyl ether, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples include phosphine and phosphite.
The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the colorant.

<Black coating>
The black coating film of the present invention has a light transmittance of 25% or less in all wavelength ranges of 400 to 700 nm, when the coating film is formed under the condition that the black composition has a film thickness of 2.0 μm, and The adhesiveness of the black coating film layer made of the black composition to the organic layer is characterized in that the number of peeled pieces in 100 cross-cuts according to the cross-cut adhesion test method is less than 10.

  When the maximum value of the light transmittance of 400 to 700 nm exceeds 25% under the condition that the film thickness is 2.0 μm, the light shielding property is insufficient when used as a decorative coating film of a touch panel, and the wiring of the touch panel is It is not preferable because it cannot be sufficiently hidden.

Further, it is preferable to use the black coating film layer formed of a black coating film in a laminate characterized by having an organic layer in contact with at least one surface of the black coating film layer. The black coating film of the present invention has excellent adhesion to organic layers such as a peeling layer, an adhesive layer and an overcoat layer. Therefore, it is used as a laminate having a black coating film, at least one surface of which is an organic layer, and by forming it in a frame shape on the outer periphery of the cover glass of the touch panel or the protective film substrate, decoration of the touch panel excellent in light-shielding properties and aesthetics Can be used for
The number of cross-cuts removed by the cross-cut adhesion test method is a cross-cut adhesion test method according to JIS K5400, which is obtained by applying an organic layer such as an acrylic resin on a black coating film and using the obtained coated substrate. It can be obtained by counting the number of peeled pieces in 100 squares.
When the number of peeled pieces is less than 10, it is particularly suitable for decorating a touch panel excellent in light-shielding property and aesthetics by forming the cover glass of the touch panel or the outer periphery of the protective film substrate in a frame shape. can do. It is more preferably less than 3, and most preferably 0.

  As the overcoating agent, for example, an organic resin such as an acrylic resin, a urethane resin, or an epoxy resin is generally used, and other photocurable, thermosetting, or thermoplastic transparent resin materials can be used.

  The pattern shape of the black coating film layer formed of a black coating film is preferably a forward taper shape. By making the pattern shape a forward taper shape, the base material and the black coating film can be brought into contact with each other at the end portion of the pattern, and a coating film having excellent adhesion to the base material can be obtained.

The dry film thickness of the black coating film is preferably 1.0 to 10 μm, and more preferably 1.0 μm or more. When it is 1.0 μm or more, the concealing property of the light shielding part can be further improved.
When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate or the like may be used.

  The black composition is subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and mixed dust by means of centrifugal separation, sintering filter, membrane filter or the like. Is preferably performed.

  The black coating film formed from the black composition of the present invention can be formed on a substrate such as a glass substrate or a plastic substrate by a printing method such as screen printing or a photolithography method and used as a light shielding film.

  The black coating film can be formed by the photolithography method, for example, by the following method. That is, a photosensitive black composition prepared as a solvent-developing or alkali-developing colored resist material is applied onto a substrate by spray coating, spin coating, slit coating, roll coating or the like to give a dry film thickness of 0. It is applied to have a thickness of 2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern that is provided in contact with or not in contact with the film. After that, the desired pattern can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be carried out as necessary. According to the photolithography method, it is possible to form a black coating film having higher alignment accuracy than the printing method.

Upon development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid pour) developing method and the like can be applied.
In order to increase the UV exposure sensitivity, after coating and drying the above colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively. Further, “PGMAC” means methoxypropyl acetate.

  The method for measuring the weight average molecular weight (Mw) of the resin is as follows.

(Weight average molecular weight (Mw) of resin)
The weight average molecular weight (Mw) of the resin is a polystyrene equivalent measured using a TPC gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw).

  Subsequently, a method for producing a binder resin solution used in Examples and Comparative Examples, a method for producing a photopolymerizable monomer, a method for producing a finely divided pigment, a structure of a dye derivative, and a method for producing a pigment dispersion will be described. .

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device in a separable 4-necked flask, heated to 80° C., and the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, benzyl methacrylate 20.0 parts, n-butyl methacrylate 17.2 parts, 2-hydroxyethyl methacrylate 12.9 parts, methacrylic acid 12.0 parts, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. 20.7 parts of Aronix M110″) and 1.1 parts of 2,2′-azobisisobutyronitrile were added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and PGMAC was added to the resin solution synthesized above so that the non-volatile content was 20% by weight. Then, an acrylic resin solution 1 was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction container equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device in a separable four-necked flask, heated to 80° C., and the inside of the reaction container was replaced with nitrogen, and then added dropwise. From the tube, 20 parts of methacrylic acid, 20 parts of benzyl methacrylate, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 25 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2, A mixture of 1.33 parts of 2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped, and after stirring while injecting dry air for 1 hour, after cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karenzu manufactured by Showa Denko KK) A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropping was completed, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution synthesized above so that the non-volatile content was 20% by mass. Then, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18,000.

<Method for producing photopolymerizable monomer>
(Photopolymerizable monomer (D1-1))
Into a 5-neck reaction vessel having an internal volume of 1 liter, 432 parts of pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 84 parts of hexamethylene diisocyanate were charged, reacted at 60° C. for 8 hours, and (meth)acryloyl. A product (a photopolymerizable monomer (D1-1)) containing a polyfunctional urethane acrylate (UA) having a group was obtained. The ratio of polyfunctional urethane acrylate (UA) in the product is 70% by weight, and the balance is occupied by other photopolymerizable monomers other than urethane acrylate. It was confirmed by IR analysis that there were no isocyanate groups in the reaction product.

<Method for producing finely divided pigment>
(Red micronized pigment (R1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 (PR254, "IRGAZIN RED 2030" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. Next, this kneaded product was poured into 8000 parts of warm water, stirred for 2 hours while heating at 80° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. , 190 parts of diketopyrrolopyrrole red finely divided pigment (R1) was obtained.

(Red micronized pigment (R2))
Anthraquinone red pigment C.I. I. Pigment Red 177 (PR177, "Chromophtal Red A2B" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. Next, this kneaded product was poured into 8000 parts of warm water, stirred for 2 hours while heating at 80° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. , 190 parts of anthraquinone red finely divided pigment (R2) was obtained.

(Blue micronized pigment (B1))
Phthalocyanine-based blue pigment C.I. I. Pigment Blue 15:6 (PB15:6, "LIONOL BLUE ES" manufactured by Toyo Color Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 80°C. Kneaded for 6 hours. Next, this kneaded product was poured into 8000 parts of warm water, stirred for 2 hours while heating at 80° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. , Blue finely divided pigment (B1) was obtained.

(Blue micronized pigment (B2))
Phthalocyanine-based blue pigment C.I. I. Pigment Blue 15:3 (PB15:3, 200 parts of "LIONOL BLUE FG-7351" manufactured by Toyo Color Co., Ltd., 600 parts of sodium chloride, and 600 parts of diethylene glycol are charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and the temperature is 80°C. Next, the kneaded product was poured into 8000 parts of warm water, stirred for 8 hours while heating at 120° C. to form a slurry, and filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, It was dried overnight at 85° C. to obtain 190 parts of a blue finely divided pigment (B2).

(Yellow micronized pigment (Y1))
Isoindolinone yellow pigment 3C. I. Pigment Yellow 139 (PY139, "PALIOTOL YELLOW D1819" manufactured by BASF), 800 parts of crushed salt, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 4 hours. This mixture was poured into 3000 parts of warm water and stirred at a high speed mixer for about 1 hour while heating at about 80°C to form a slurry, which was repeatedly filtered and washed to remove salt and solvent, and then at 80°C for 24 hours. After drying, 96 parts of yellow finely divided pigment (Y1) were obtained.

(Yellow micronized pigment (Y2))
Isoindoline yellow pigment C.I. I. Pigment Yellow 185 (PY185, "Paliogen Yellow D1155" manufactured by BASF), 800 parts of crushed salt, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 4 hours. .. This mixture was poured into 3000 parts of warm water and stirred at a high speed mixer for about 1 hour while heating at about 80°C to form a slurry, which was repeatedly filtered and washed to remove salt and solvent, and then at 80°C for 24 hours. After drying, 96 parts of yellow finely divided pigment (Y2) was obtained.

(Yellow micronized pigment (Y3))
Azo yellow pigment C.I. I. Pigment Yellow 150 (PY150, "E-4GN" manufactured by LANXESS Co., Ltd.), 500 parts of ground salt, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 4 hours. This mixture was poured into 5000 parts of warm water and stirred at a high speed mixer for about 1 hour while heating to about 80°C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent, and then at 80°C for 24 hours. After drying, 490 parts of yellow finely divided pigment (Y3) was obtained.

(Yellow micronized pigment (Y4))
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (PY138, "Pariotor Yellow K0960-HD" manufactured by BASF): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 120°C. Kneaded for 2 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70° C. to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. overnight. Then, 490 parts of a yellow finely divided pigment (Y4) was obtained.

(Green micronized pigment (G1))
Phthalocyanine green pigment C.I. I. Pigment Green 36 (PG36, "Rionol Green 6YK" manufactured by Toyo Color Co., Ltd.) 500 parts, sodium chloride 1500 parts, and diethylene glycol 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) at 80°C for 8 hours. Kneaded Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70° C. to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. overnight. Then, a green finely divided pigment (G1) was obtained.

(Green fine pigment (G2))
Phthalocyanine green pigment C.I. I. Pigment Green 7 (PG7, "Ryonor Green YS-07" manufactured by Toyo Color Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 80°C. Kneaded for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70° C. to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. overnight. Then, a green finely divided pigment (G2) was obtained.

(Black micronized pigment (K1))
Perylene black pigment C.I. I. Pigment Black 31 (“PalIogen Black S0084” manufactured by BASF), 500 parts, sodium chloride 2500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 5 hours. did. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70° C. to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. overnight. Then, a black micronized pigment (K1) was obtained.

<Structure of dye derivative>
Table 1 shows the structural formulas of the dye derivatives used to prepare the pigment dispersion.

<Method for producing pigment dispersion>
(Preparation of Pigment Dispersion (RP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm. Thereafter, 30.0 parts of methoxypropyl acetate was added, and the mixture was filtered through a 5 μm filter to obtain a pigment dispersion (RP-1).

Red finely divided pigment (R1): 10.8 parts C.I. I. Pigment Red 254
Dye derivative (A-1): 1.2 parts Acrylic resin solution 1: 40.0 parts Methoxypropyl acetate: 18.0 parts

(Preparation of Pigment Dispersion (RP-2, BP-1 to 2, YP1 to 4, GP-1 to 2, KP-1))
The pigment dispersions (RP-2, BP-1 to 2, and YP-1 to 1) are the same as the pigment dispersion (RP-1) except that the composition and the blending amount (parts by weight) shown in Table 2 are changed. 4, GP-1 to 2, KP-1) were obtained.

<Method for producing carbon black dispersion>
(Preparation of carbon black dispersion (CP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours using zirconia beads having a diameter of 1 mm. Thereafter, 30.0 parts of methoxypropyl acetate was added, and the mixture was filtered with a 5 μm filter to obtain a pigment dispersion (CP-1).

Carbon black (CB-1): 12.6 parts "Regal250R" manufactured by CABOT
Dye derivative (A-4): 1.4 parts Acrylic resin solution 1: 30.0 parts Methoxypropyl acetate: 26.0 parts

[Example 1]
(Production of Photosensitive Black Composition (BLK-1))
The following mixture (100 parts in total) was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive black composition (BLK-1).

Pigment dispersion (RP-1): 25.21 parts C.I. I. Pigment Red 254
Pigment dispersion (BP-1): 25.21 parts C.I. I. Pigment Blue PB15:6
Silane coupling agent (C-1): 0.66 part 3-glycidoxypropylmethyldiethoxysilane acrylic resin solution 2: 27.10 parts Photopolymerizable monomer (D1-1): 5.16 parts light Polymerization initiator: 0.66 parts "Irgacure OXE-02" manufactured by BASF
(Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H
-Carbazol-3-yl]-, 1-(0-acetyloxime))
Leveling agent solution: 2.00 parts Toray Dow Corning "FZ-2122" ((nonvolatile content 100% by weight) 1 part diluted with 99 parts cyclohexanone)
Solvent: 14.01 parts Methoxypropyl acetate

[Examples 2-35, Comparative Example 1]
(Production of photosensitive black composition (BLK-2 to 36))
Photosensitive black compositions (BLK-2 to 36) were obtained in the same manner as the photosensitive black composition (BLK-1) except that the compositions and the amounts (parts by weight) shown in Tables 3 to 6 were changed. It was In addition, Examples 11 and 12 in the present specification are reference examples.

The abbreviations in Tables 3 to 6 are described below.
《Chain transfer agent》
・Showa Denko's "Karenzu MTPE1" (pentaerythritol tetrakis (3-mercaptobutyrate))
Photopolymerization Initiator BASF Corporation "Irgacure OXE-02" (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime ))
-"Irgacure 379" manufactured by BASF (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone)

<Polymerizable monomer>
・Shin Nakamura Chemical Co., Ltd. “U-6LPA” (urethane acrylate compound)
-"DPCA30" manufactured by Nippon Kayaku Co., Ltd. (a compound in which m=1 in the general formulas (1) to (3), the number of groups represented by the formula (2)=3, and R1 are all hydrogen atoms)
* Nippon Kayaku Co., Ltd. "DPCA60" (the same formula, m=1, the number of groups represented by the formula (2)=6, R ¹
Compounds in which all are hydrogen atoms)
・Kyoei Chemical Co., Ltd. “DAUA167” (53% carbitol acetate solution of urethane acrylate having a carboxyl group)
・"Aronix M402" manufactured by Toagosei Co., Ltd.
(Dipentaerythritol hexaacrylate/pentaacrylate mixture)

<Leveling agent solution>
・Toray Dow Corning "FZ-2122"
(A solution obtained by diluting 1 part (100% by weight of nonvolatile content) with 99 parts of cyclohexanone.)

"Silane coupling agent"
-Silane coupling agent (C-1); Silane coupling agent having an epoxy group 3-glycidoxypropylmethyldiethoxysilane-Silane coupling agent (C-2); Silane coupling having a (meth)acryloxy group Agent 3-methacryloxypropylmethyldimethoxysilane/silane coupling agent (C-3); silane coupling agent having an isocyano group 3-isocyanatopropyltriethoxysilane/silane coupling agent (C-4); having a vinyl group Silane coupling agent Vinyltrimethoxysilane/silane coupling agent (C-5); Silane coupling agent having amino group
3-aminopropyltrimethoxysilane

<Evaluation of light transmittance measurement>
Table 6 shows the maximum value (Tmax) of the light transmittance at a wavelength of 400 to 700 nm when the coating film was formed under the condition that the thickness of the obtained black composition was 2.0 μm.

[Coating film preparation]
The black compositions of Examples and Comparative Examples were applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 0.7 mm by using a spin coater, and then dried in an oven at 70° C. for 20 minutes, and an ultrahigh pressure mercury lamp was used. Ultraviolet light exposure was performed at an integrated exposure amount of 150 mJ/cm ² , developed with an alkaline developer at 23° C., washed with ion-exchanged water, heated at 220° C. for 30 minutes, allowed to cool, and then a film thickness of 2. A coated substrate of 0 μm was obtained.
[Measurement of light transmittance]
The maximum transmittance (Tmax) of the obtained coated substrate was measured by measuring the light transmittance at a wavelength of 400 to 700 nm using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).

<Evaluation of photosensitive coloring composition>
The black compositions obtained in Examples and Comparative Examples were evaluated for stability, linearity, pattern shape and adhesion to an organic layer as follows. The evaluation results are shown in Table 7.

[Evaluation of stability]
With respect to the black compositions obtained in Examples and Comparative Examples, using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.), a viscosity (V1) 24 hours after production and a condition of 23 degrees The viscosity (V2) after storage for 30 days was evaluated, and the rate of change in viscosity (V2-V1)/V1 was evaluated.

Viscosity change rate less than 0.05 Excellent stability (◎)
Viscosity change rate 0.05 or more, less than 0.10 Good stability (○)
Viscosity change rate 0.10 or more, less than 0.20 Stability possible (△)
Viscosity change rate 0.20 or more Poor stability (x)

[Evaluation of adhesion to organic layer]
The black compositions of Examples and Comparative Examples were applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 0.7 mm by using a spin coater, and then dried in an oven at 70° C. for 20 minutes, and an ultrahigh pressure mercury lamp was used. UV exposure was performed at an integrated exposure amount of 130 mJ/cm ² , and development was performed with an alkali developing solution at 23° C., followed by washing with ion-exchanged water, followed by heating at 230° C. for 30 minutes and allowing to cool, and a film thickness of 2. A coated substrate of 5 μm was obtained. "Optomer SS6699G" manufactured by JSR Co. was applied onto the manufactured black substrate so that the film thickness was 2.00 μm, and then heated at 230° C. for 20 minutes. After that, the obtained coated substrate was evaluated for the adhesiveness of the coating film by a cross-cut adhesion test method according to JIS K5400, and the number of peeled pieces was counted in 100 cross-cuts.

Adhesion evaluation:
◎: Number of peeled crosses 0: ○: Number of peeled crosses 1 to less than 3 △: Number of peeled crosses 3 to less than 10 ×: Number of peeled crosses 10 or more

[Linearity evaluation (PW1-PW2)]
A coating film in which the black compositions obtained in Examples and Comparative Examples are coated on a glass substrate having a thickness of 100 mm×100 mm and 0.7 mm and dried at 70° C. for 20 minutes to have a film thickness of 2.5 μm. Was produced.
Ultraviolet light was exposed through a photomask at an integrated light amount of 130 mJ/cm ² using an ultrahigh pressure mercury lamp, and then the unexposed portion was developed with an alkaline developer at 23° C. and washed with ion-exchanged water. The linearity of the produced black pattern forming portion was confirmed with a microscope and the quality of the linearity was evaluated. Whether the linearity was good or bad was judged by evaluating the difference PW1-PW2 between the maximum value (PW1) and the minimum value (PW2) of the line width of the pattern shown in FIG. 1 with a microscope. The linearity was evaluated according to the following criteria based on the superiority or inferiority of PW1-PW2.
When PW1−PW2≦2 μm, it is determined that the electrode wiring pattern of the precision-processed touch panel can be accurately covered, and it can be said that the composition is more excellent.

Excellent linearity (◎) if it is 1 μm or less
Greater than 1 μm and 2 μm or less, good linearity (○)
Poor linearity (X) when larger than 2 μm

[Pattern shape evaluation]
With respect to the black pattern forming portion produced in the above linearity evaluation, the cross section of the linear pattern was observed by a scanning electron microscope (SEM) to evaluate the taper shape.
If the taper shape is a forward taper, it can be said that the coating film has excellent adhesion to the substrate.

Pattern shape evaluation:
⊚: taper angle is less than 70° ◯: taper angle is 70° or more and less than 80° Δ: taper angle is 80° or more and 90° or less ×; taper angle is greater than 90°

  As shown in Table 7, the black composition of the present invention contains at least two kinds of organic pigments (A) and has a maximum light transmittance of 400 to 700 nm under the condition that the film thickness is 2.0 μm. Since it is 25% or less, it has excellent light-shielding properties and aesthetics, and has high light-shielding properties even when it is used as a decorative coating film for a touch panel, and the wiring of the touch panel can be sufficiently hidden. In addition, by containing a specific silane coupling agent (C1) and a photopolymerizable monomer (D1) having a urethane bond, or a photopolymerizable monomer (D2) having a caprolactone structure, the black composition The adhesion of the black coating layer made of a material to the organic layer is less than 10 in the number of peeled out of 100 cross-cuts according to the cross-cut adhesion test method, and not only is the adhesion and pattern shape excellent, The viscosity was low, the stability was good, and the linearity was good.

  In particular, comparing compositions having different photopolymerizable monomer compositions, the composition containing a large amount of the photopolymerizable monomer (D1) having a urethane bond or the photopolymerizable monomer (D2) having a caprolactone structure. As a result, the better the pattern shape, the better.

  Also, comparing compositions (Examples 1, 11, 12, 18, 19) that differ only in the type of silane coupling agent, a silane coupling agent containing an epoxy group or a silane coupling agent containing a (meth)acryloxy group. The black compositions containing a large amount of the silane coupling agent containing an isocyano group (Examples 1, 11, and 12) had a better adhesion to the organic layer.

  Further, in the black composition in which the content of the silane compound (C1) in the total solid content of 100% by weight of the photosensitive composition is 0.1% by weight or more and less than 5% by weight, an amount of less than 0.1% by weight is used. The adhesiveness was excellent with respect to Example 20, and the stability of the black composition was good as compared with Example 21 containing 5% by weight or more.

  Further, the linearity of the black composition having a ratio (M/P) of the weight (P) of the transparent resin and the weight (M) of the precursor of the transparent resin is 0.30 to 0.80 is 0.3. The results were good as compared with the following Example 22 and Example 17 of 0.80 or more.

  In addition, comparing Examples 1 and 23, the black composition using the oxime ester compound as the photopolymerization initiator contained less photopolymerization initiator than the black composition using the acetophenone compound. The adhesiveness was good and the shape was also excellent.

  On the other hand, in the black composition of Comparative Example 1 containing no silane coupling agent (C), the number of cross-cuts was more than 10, and the adhesion to the organic layer was poor in the evaluation of adhesion.

  From the above results, by using the black composition of the present invention, when used as a display device, the adhesiveness with the organic layer is particularly good, and the stability that can impart an aesthetically pleasing tint is excellent, especially the touch panel. It was confirmed that it was a high-quality black coating film suitable for decoration.

Claims (8)

A black composition containing at least two kinds of organic pigments (A), a binder resin (B), a silane coupling agent (C), and a photopolymerizable monomer (D),
The organic pigment (A) contains at least a red pigment and a blue pigment,
The content of the red pigment is 45 wt% or more based on the total amount of the organic pigment (A), the silane coupling agent (C) is a silane coupling agent having an epoxy group (C1), The photopolymerizable monomer (D) is at least one selected from the group consisting of a photopolymerizable monomer having a urethane bond (D1) and a photopolymerizable monomer having a structure modified with caprolactone (D2). Containing seeds,
When a coating film is formed on the black composition under the condition that the film thickness is 2.0 μm, the light transmittance is 25% or less in all wavelength ranges of 400 to 700 nm,
And, the adhesion of the organic layer to the black coating layer formed of the black composition is less than 10 in the number of peeled out of 100 cross-cuts according to the cross-cut adhesion test method,
The black composition, wherein the organic layer is a layer obtained by heating an acrylic resin at a film thickness of 2.00 μm at 230° C. for 20 minutes.   The black composition according to claim 1, wherein the content of the silane coupling agent (C1) is 0.1% by weight or more and less than 5% by weight in 100% by weight of the total solid content of the black composition.   The ratio ([M]/[P]) of the content [P] of the binder resin (B) and the content [M] of the photopolymerizable monomer (D) is 0.30 to 0.80. The black composition according to claim 1 or 2, wherein the black composition is present.   The black composition according to any one of claims 1 to 3, further comprising an oxime ester-based photopolymerization initiator.   A black coating film formed by using the black composition according to claim 1.   The black coating film according to claim 5, which has a film thickness of 1.0 µm or more.   The black coating film according to claim 5 or 6, which is for decorating a touch panel.   A laminate comprising a black coating film layer comprising the black coating film according to any one of claims 5 to 7, and an organic layer in contact with at least one surface of the black coating film layer.

Images