JP6390143B2 - 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 for electronic devices such as smartphones and digital music players, and a black coating film formed using the black composition, particularly for touch panel decoration It is related with the coating film suitable for.

  In recent years, electronic devices such as smartphones and digital music players have been equipped with many input devices called capacitive touch panels. A capacitive touch panel is a switch that utilizes the phenomenon that the capacitance of an electrode changes as a finger approaches the electrode.

  In the capacitive touch panel, as described in Patent Document 1, decoration is provided when manufacturing the operation panel so that the capacitive switch has sufficient concealment and does not cause malfunction or malfunction of the capacitive switch. Is given. When looking at the liquid crystal display from the user side in mobile phones etc., information and images are not displayed on the entire transparent glass, but there are black parts on the outer periphery of the glass substrate to partition the display, The display is made inside this. This frame portion (decorating portion) has a function of concealing a portion that is inconvenient (such as a wiring portion for a touch panel) from being visually recognized while defining the display portion in a quadrangular shape.

In addition, as the structure of the touch panel, a decorative part is formed on the cover glass using a resin material for black matrix used for manufacturing a color filter substrate, and then, on the decorative part, degassing prevention and insulating properties are formed. For the purpose of securing and improving flatness, a decorative cover glass-integrated touch panel sensor structure 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 Documents) 2).
Thus, in order to produce a touch panel on which a decorative portion is formed on a glass substrate, an overcoat layer is formed for the purpose of preventing outgas from the decorative portion and improving flatness as a coated surface. Although it is necessary to form it, it is difficult to peel off at the interface because the adhesiveness with the overcoat layer, which is an organic layer, is poor only by diverting the resin material for the black matrix used in conventional color filter substrate manufacturing. There is a problem that occurs.

JP 2000-012345 A JP 2012-155644 A

  The present invention provides a black composition with excellent stability that can be used as a display device and has good adhesion to an organic layer, excellent aesthetics, and pattern linearity. The purpose is to do. Furthermore, it aims at providing the high quality black coating film suitable for touchscreen decoration use using this black composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that at least two kinds of organic pigments (A), a binder resin (B), a specific silane coupling agent (C), and a specific When used in a laminate that contains a photopolymerizable monomer and has a specific spectral characteristic and is used in a laminate in which at least one side is an organic layer, the adhesion to the organic layer, and the substrate It has been found that a high quality black coating film suitable for touch panel decoration can be obtained, 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 silane coupling agent (C) contains a silane coupling agent (C1) having an epoxy group, a (meth) acryloxy group, or an isocyano group, and the photopolymerizable monomer has a urethane bond. Containing at least one selected from the group consisting of a monomer (D1) and a photopolymerizable monomer (D2) having a caprolactone structure;
When the black composition is formed under the condition that the film thickness is 2.0 μm, the light transmittance in the entire wavelength range of wavelength 400 to 700 nm is 25% or less,
And the adhesiveness with respect to the organic layer of the black coating film layer which consists of this black composition is related with the black composition characterized by the number of peeling in 100 cross-cuts by a cross-cut adhesion test method being less than ten.

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

  In the present invention, the ratio ([M] / [P]) between the content [P] of the binder resin (B) and the content [M] of the photopolymerizable monomer (D) is 0. It is related with the said black composition characterized by being 30-0.80.

  The present invention further relates to the black composition, further comprising an oxime ester photopolymerization initiator.

  Moreover, this invention relates to the black coating film formed using the said black composition.

  Moreover, this invention relates to the said black coating film characterized by being 1.0 micrometer or more in film thickness.

  Moreover, this invention relates to the said black coating film characterized by being for touchscreen decoration.

  Moreover, this invention relates to the laminated body characterized by having the black coating film layer which consists of the said black coating film, and the organic layer which touches at least one side of the said black coating film layer.

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

It represents the difference PW1−PW2 between the maximum value (PW1) and the minimum value (PW2) of the line width of the pattern.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” mentioned in the present specification means a 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 types of organic pigments (A), a binder resin (B), and a silane coupling agent (C). When the 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 black coating layer made of the black composition is adhered to the organic layer. The number of peels per 100 grids according to the grid grid adhesion test method is less than 10.

<Colorant>
(Organic pigment (A))
The black composition of the present invention contains at least two organic pigments (A). Thereby, it can be set as the black coating film excellent in light-shielding property 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 yellow pigments 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, 17 , And the like 177,179,180,181,182,185,187,188,193,194,199,213.
Examples of the orange pigment 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.
Examples of black pigments include 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 organic pigments other than perylene black and perylene black such as pigment black 31 and 32 The combination of is preferable. 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 the red pigments, C.I. I. Pigment Red 177 or 254, C.I. I. Pigment Blue 15: 6 or 15: 3 is preferably included. As other pigments, C.I. I. Pigment yellow 138, 139, 150, or 185, as a black pigment, C.I. I. It is preferable that the pigment black 31 or 32 is included.

Each content in the organic pigment (A) is 20 to 60% by weight for the red pigment, 20 to 60% by weight for the blue pigment, and other pigments based on the total amount of the organic pigment (A) (100% by weight). 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% in total, based on the total solid weight of the black composition (100% by weight). % Can be used.

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

  As carbon black, for example, MONARCH made 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, PELLETS 115), Mitsubishi Chemical MA (77, 7, 8, 11, 100, 100R, 100S, 230, 200RB, 14), # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990) 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 made by DEGUSSA (FW2000, FW2, FW2V, FW1, FW18, S170, S160), Special Black (4, 4A, 550, 350, 6, 5), Printex (95, 90, 85, 80, 75) 40, 60, 150T, U, V, 140U, 140V, 55, 45, P, L6, L, 300, 30, ES23, 3, ES22, 35, XE2), NIPex35, Tokai Carbon's seast (9H SAF -HS, 9 SAF, [6ISAF, 600ISAF-LS, 5H-IISAF-HS, KH (N339), 3H HAF-HS, NH (N351), 3 HAF, 3M, NLI-HAF, 300 HAF-LS, 116 MAF]), Asahi Carbon's 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, 1250, 1200, 1170, 1 40,1035,1030 BEADS, 1020,1000,890POWDWE, 890HPOWDER, 850,825BEADS), CONDUCTEX (975BEADS, 900BEADS) and the like. Preferably, MONARCH (1100, 800) manufactured by CABOT, BLACK PERLS (1100, 800), PrintX 95 manufactured by DEGUSSA, # 850 manufactured by Mitsubishi Chemical, REGAL manufactured by CABOT (300R, 250R, 250, 99R, 99I), Mitsubishi Chemical MA (7, 11, 100R), # (47, 45, 45L), DEGUSSA Printex55, NIPex35, particularly preferably MONARCH1100 manufactured by CABOT, PrintX95 manufactured by DEGUSSA, # 47 manufactured by Mitsubishi Chemical, CABOT REGAL 250R, manufactured by DEGUSSA, PrintX55, NIPex35 manufactured by DEGUSSA can be used. The carbon black 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 thermoplastic resins and thermosetting resins. 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. Moreover, when using with the form of an alkali image development type photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  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, and 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 resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include 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. Among them, 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, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been 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 is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (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. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds 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 in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a 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 or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. It may be used in combination. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above 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 on 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 or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

  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 in the range of 10,000 to 80,000. It 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.

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

  The content of the binder resin (B) is preferably 30 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is It is preferably used in an amount of 500 parts by weight or less because it is high and can exhibit good color characteristics. More preferably, it is 100-400 weight part. More preferably, it is 160-320 weight part. 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 is a silane coupling agent having an epoxy group, a (meth) acryloxy group, or an isocyano group as the silane coupling agent (C) for the purpose of imparting good adhesion to the organic layer. (C1) is contained. Most preferred 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 Silane coupling agents having an epoxy group such as propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane,
Silane coupling agents 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 individually by 1 type or in mixture of 2 or more types by arbitrary ratios 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),
Silane coupling agents having a vinyl group such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, 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 Silane coupling agents 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;
Silane coupling agents having a mercapto group such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
Silane coupling agents having sulfide groups such as bis (triethoxysilylpropyl) tetrasulfide,
Etc.

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

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

The photopolymerizable monomer (D1) and the photopolymerizable monomer (D2) improve adhesion to the organic layer and impart adhesion to the substrate by imparting a good pattern shape. For this purpose, a transparent resin is produced by curing with ultraviolet rays or heat. Since these photopolymerizable monomers have a longer distance between cross-linked groups cross-linked by photopolymerization than other photopolymerizable monomers, they can impart flexibility to the black composition coating film. .
As a result, it is possible to relieve stress at the interface with the organic layer to be laminated, and thus it is possible to obtain a black composition coating film having excellent adhesion with the organic layer. In addition, in the heat treatment step when forming the pattern of the black composition, it is possible to induce thermal sagging and obtain a forward tapered shape.

(Photopolymerizable monomer having a 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, a (meth) acrylate having a hydroxyl group is reacted with a polyfunctional isocyanate. The polyfunctional urethane acrylate which has the (meth) acryloyl group obtained 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, 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) acrylate U-2PPA, U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, UA, such as UA-8001G, DAUA-167, Shin-Nakamura Chemical Co., Ltd. -33H, U-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA -122P.
These photopolymerizable monomers (D1) having a urethane bond can be used singly or as a mixture of two or more at any ratio as necessary.

(Photopolymerizable monomer having 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. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylol Ε-caprolactone modification obtained by esterifying (meth) acrylic acid and ε-caprolactone with polyhydric alcohols such as propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylolmelamine Mention may be made of polyfunctional (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following general formula (1) is preferable.

General formula (1)
[In general formula (1), all six R are groups represented by the following formula (2), or 1 to 5 of the six Rs are represented by the following formula (2). It is group and the remainder is group represented by following formula (3). ]

General formula (2)
[In 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. ]

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

Examples of such photopolymerizable monomer (D2) having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (the above general formulas (1) to (3) ) M = 1, the number of groups represented by formula (2) = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (same formula, m = 1, represented by 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 (a compound in which m = 2 in the formula, the number of groups represented by formula (2) = 6, and R ¹ is all hydrogen atoms).
These photopolymerizable monomers (D2) having a caprolactone structure can be used singly or as a mixture of two or more at any ratio as required.

The photopolymerizable monomer (D) contained in the black composition of the present invention is other than the photopolymerizable monomer (D1) having a urethane bond and the photopolymerizable monomer (D2) having a caprolactone structure. Other photopolymerizable monomers may be included. 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 monoesterified with succinic acid, tricyclodecanyl (meth) acrylate, ester acrylate, methylolation (Meth) acrylic esters of melamine, various acrylic esters and methacrylic esters such as epoxy (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 can be mentioned.
These photopolymerizable monomers can be used singly or in combination of two or more at any ratio as required.

The content of the photopolymerizable monomer (D) is preferably 5 to 250 parts by weight with respect to a total of 100 parts by weight of the colorant, and 10 to 200 parts by weight from the viewpoint of photocurability and developability. More preferably, when either the photopolymerizable monomer (D1) or (D2) is used alone as the photopolymerizable monomer (D), the total amount of the colorant is 100 for any content. It is preferable that it is 3-250 weight part with respect to a weight part, and it is more preferable that it is 5-150 weight part from a viewpoint of photocurability and developability. When the photopolymerizable monomers (D1) and (D2) are used in combination, the contents of the two types of photopolymerizable monomers (D1) and (D2) are based on 100 parts by weight of the total colorant. 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) to 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. If ([M] / [P]) is within this range, it is preferable because the linearity and adhesion of the pattern shape are excellent.

Further, the black composition of the present invention can form a coating film by a photolithography method, a printing method, or the like. When forming a coating film by a photolitho system, it is preferable that a black composition contains a photoinitiator (E), a sensitizer, a chain transfer agent, a solvent, etc. other than said (A)-(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 an exposure apparatus used in a photolithography method and generates radicals or ions.
As photopolymerization initiator (E), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one Acetophenone compounds such as 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin compounds such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoy Benzophenone compounds such as -4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone compounds such as 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 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 (to Chloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl)- Triazines such as 4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine Compound, 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]-, 1- ( Oxime ester compounds such as -acetyloxime), phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 9,10-phenanthrene Examples include quinone compounds such as quinone, camphorquinone, and ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, and titanocene compounds.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

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

Furthermore, 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 ~R 4 is a hydrogen atom, an alkyl group or a phenyl group which may have a substituent, a C ₁ -C _6. ]

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

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

<Sensitizer>
Furthermore, the black composition of the present invention can contain a sensitizer.
Examples of the sensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) ) Amine compounds such as benzophenone can also be used in combination. These sensitizers can be used alone or in combination.
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 singly or in combination of two or more at any ratio as necessary.

  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. More preferably, it is 50 parts by weight.

<Chain transfer agent>
Furthermore, a chain transfer agent can 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. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis Thioglycolate, pentaerythritol tetrakisthiopropionate, dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionate tris (2-hydroxyethyl) ) Isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto -s- triazine, 2-(N, N-dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination.

The content of the chain transfer agent is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the total solid content of the black composition (100% by weight). If the amount is less than 0.1% by mass, the effect of adding a polyfunctional thiol is insufficient. If the amount exceeds 30% by mass, the sensitivity is too high and the resolution may be lowered.
<Antioxidant>
Furthermore, 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.

Antioxidants 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. Antioxidants can be used.
Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 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-tert-butyl-5-methylphenol), 2,2′-thio -Bis- (6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-tert-butyl-4-hydroxy Phenyl) -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-) Hydrocinnamamide) 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), 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 (or more, Manufactured by API Corporation), IRGANOX245, IRGANOX259, IRGANOX565, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX10 6, IRGANOX 1425WL, IRGANOX 1222, IRGANOX 1330 (manufactured by BASF Japan Ltd.), ADK STAB AO-70, ADK STAB AO-50, ADK STAB AO-330, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-80 (and above, ASAHI) (Manufactured by Denka Kogyo Co., Ltd.), Sumizer BM, Sumizer GM, Sumizer GP, Sumizer GS, Sumizer GA-80, Sumizer BP-101, Sumizer BP-76 and Sumizer BP-101 (supplied by Sumitomo Chemical Co., Ltd.).

  Examples of hindered amine-based antioxidants 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, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) 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- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type compounds.

  Specific examples of the hindered amine-based antioxidant include Sanol LS-770, Sanol LS-765, Sanol LS-622LD, Kimasorp 944 (Sankyo Co., Ltd.), CYASORB UV-3346 (San Chemical Co., Ltd.), Knock rack 224, knock rack CD, Uvasil 299-299LM (above, Ouchi Shinsei Chemical Industry Co., Ltd.), MARK LA-63, MARKLA-68 (above, Asahi Denka Kogyo Co., Ltd.), TINUVIN 144, TINUVIN 312 (above, BASF・ Made by Japan).

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di ( , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (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 (diphenoxyphosphonoxy)- Benzene, phosphorous acid ethyl bis (2,4-di-tert- butyl-6-methylphenyl), and the like. Other examples include oligomer-type and polymer-type compounds having a phosphite structure.

  Specific examples of phosphorus-based antioxidants include IRGAFOS168, IRGAFOS12, IRGAFOS38, IRGAFOSEPQ, (manufactured by BASF Japan Ltd.), Sumizer Z-16 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB PEP-4C, ADK STAB PEP-8F, ADK STAB PEP-8, ADK STAB PEP-45, ADK STAB PEP-11C, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB P, ADK STAB C, ADK STAB QL, ADK STAB 135A, ADK STAB 1178, ADK STAB 1500, ADK STAB 1500 ADK STAB 3010, ADK STAB 522A, ADK STAB TPP (above, manufactured by Asahi Denka Kogyo Co., Ltd.), GSY-202 (above, AP Aiko Ltd. poration), SANKOHCA (Sanko Co., Ltd.), JPH1200, JP302, JPM313, JP304, JP308, JPP100, JP333E, JP318E, JP312 (manufactured by API Corporation) and the like.

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

  Specific examples of sulfur-based antioxidants include IRGANOXPS800FD, IRGANOXPS802FD (above, manufactured by BASF Japan), Adekastab AO-503, Adekastab AO-412S (above, made by Asahi Denka Kogyo Co., Ltd.), Sumizer TPL-R, Sumizer TPM, TP Sumitizer TP-D, Sumitizer TL, Sumitizer MB (above, manufactured by Sumitomo Chemical Co., Ltd.), DLTP “Yoshitomi”, DSTP “Yoshitomi”, DMTP “Yoshitomi”, DTTP “Yoshitomi” (above, manufactured by API Corporation).

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

  Specific examples of the benzotriazole antioxidant include Tomisorp 600 (manufactured by Yoshitomi Fine Chemical), TINUVIN 326, TINUVIN 327, TINUVIN P, TINUVIN 328 (above, manufactured by BASF Japan Ltd.), VIOSORB583, VIOSORB590 (manufactured by Kyodo Yakuhin). .

  Examples of the benzophenone 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, 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 (manufactured by Asahi Denka Kogyo Co., Ltd.) and the like. Other examples include oligomer-type and polymer-type compounds having a benzophenone structure.

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

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

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

  Examples of the salicylate ester 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 in combination of two or more at any ratio as required.

Further, 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 cured with ultraviolet rays, and light / heat It is preferable because it is possible to suppress the deterioration of the coating film.

<Solvent>
In the black composition, the dye is sufficiently dispersed in the dye carrier, and is 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. In order to facilitate the process, a solvent can be contained. 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.

  The solvent is preferably used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the black composition can be adjusted to an appropriate viscosity to form a desired colored film having a uniform film thickness. .

<The manufacturing method of a black composition>
In the black composition, each organic pigment is dispersed in various forms such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor in a dye carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid. It can be produced by finely dispersing using means.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the colored 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 a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more.

  The content of the pigment 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 improving dispersibility. Further, 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 part that has the property of adsorbing to the pigment and a part that is compatible with the resin or solvent, and adsorbs to the pigment to disperse the pigment into the resin or solvent. It works to stabilize. Specific examples of resin-type pigment dispersants 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 group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

  When a resin-type dispersant and a 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 colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

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

<Black coating film>
The black coating film of the present invention has a light transmittance of 25% or less in the entire wavelength range from 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 adhesion of the black coating layer made of the black composition to the organic layer is less than 10 in the number of peels per 100 grids according to the grid grid adhesion test method.

  If 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 the touch panel, and the wiring of the touch panel It is not preferable because it cannot be sufficiently concealed.

Moreover, it is preferable to use for the laminated body characterized by the black coating film layer which consists of a black coating film having an organic layer which touches at least one side of the said black coating film layer. The black coating film of this invention is excellent in adhesiveness with respect 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 side of which is an organic layer, and is formed into a frame shape on the outer periphery of the cover glass or protective film substrate of the touch panel, thereby decorating the touch panel with excellent light shielding properties and aesthetics. Can be used for
The number of cross-cuts peeled by the cross-cut adhesion test method is the cross-cut adhesion test method according to JIS K5400 using an organic substrate such as an acrylic resin coated on a black coating film. Thus, it is obtained by counting the number of peels in 100 grids.
When this number of peels is less than 10, it is suitable for decorating touch panels with excellent light shielding properties and aesthetics, especially by forming a frame shape on the outer periphery of the cover glass or protective film substrate of the touch panel. can do. More preferably, the number is less than 3, most preferably 0.

  As the overcoat agent, for example, organic resins such as acrylic, urethane, and epoxy are generally used, and other photo-curing, thermosetting, or thermoplastic transparent resin materials can be used.

Moreover, it is preferable that the pattern shape of the black coating film layer which consists of a black coating film is a forward taper shape. By making the pattern shape into a forward tapered shape, the substrate and the black coating film can be brought into contact with each other at the edge of the pattern, and a coating film having excellent adhesion to the substrate 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 the thickness is 1.0 μm or more, the concealability 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 removes coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, more preferably 0.5 μm or larger and mixed dust by means of centrifugation, sintered filter, membrane filter, etc. It is preferable to carry out.

  The black coating film formed from the black composition of the present invention can be formed on a base material 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.

  Formation of the black coating film by the photolithography method can be performed, for example, by the following method. That is, the photosensitive black composition prepared as a solvent developing type or alkali developing type colored resist material has a dry film thickness of 0. 0 on a substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that it may become 2-10 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the film can be immersed in a solvent or an alkaline developer or sprayed with a developer by spraying or the like to remove uncured portions and form a desired pattern. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a black coating film with higher alignment accuracy than the printing method can be formed.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, 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. “PGMAC” means methoxypropyl acetate.

  Moreover, the measuring method of the weight average molecular weight (Mw) of resin is as follows.

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

  Subsequently, the production method of the binder resin solution, the production method of the photopolymerizable monomer, the production method of the fine pigment, the structure of the dye derivative, and the production method of the pigment dispersion used in Examples and Comparative Examples will be described. .

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 20.0 parts of benzyl methacrylate, 17.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. Aronix M110 ") 20.7 parts and a mixture of 2,2'-azobisisobutyronitrile 1.1 parts were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution.
After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add PGMAC to the previously synthesized resin solution so that the nonvolatile content is 20 wt% Thus, 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 vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 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 completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Method for producing photopolymerizable monomer>
(Photopolymerizable monomer (D1-1))
Into a five-necked reaction vessel with 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 and reacted at 60 ° C. for 8 hours, and (meth) acryloyl A product (photopolymerizable monomer (D1-1)) containing a polyfunctional urethane acrylate (UA) having a group was obtained. In the product, the proportion of polyfunctional urethane acrylate (UA) is 70% by weight, and the remainder is occupied by other photopolymerizable monomers other than urethane acrylate. It was confirmed by the IR analysis that no isocyanate group was present in the reaction product.

<Production method of fine pigment>
(Red fine pigment (R1))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of 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 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a diketopyrrolopyrrole-based red micronized pigment (R1) were obtained.

(Red fine pigment (R2))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (PR177, “chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of an anthraquinone red micronized pigment (R2).

(Blue refined pigment (B1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (PB15: 6, “LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) at 80 ° C. Kneaded for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A blue refined pigment (B1) was obtained.

(Blue refined pigment (B2))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 3 (PB15: 3, 200 parts of “LIONOL BLUE FG-7351” manufactured by Toyocolor Co., Ltd., 600 parts of sodium chloride, and 600 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. Next, the kneaded product was put into 8000 parts of warm water, stirred for 8 hours while heating to 120 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, It dried at 85 degreeC all day and night, and obtained 190 parts of blue refinement | purification pigments (B2).

(Yellow fine pigment (Y1))
Isoindolinone yellow pigment 3C. I. 100 parts of 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 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 4 hours. The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 96 parts of yellow refinement | purification pigment (Y1).

(Yellow fine pigment (Y2))
Isoindoline yellow pigment C.I. I. 100 parts of Pigment Yellow 185 (PY185, “Pariogen 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. . The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 96 parts of yellow refinement | purification pigment (Y2).

(Yellow fine pigment (Y3))
Azo-based yellow pigments C.I. I. 100 parts of Pigment Yellow 150 (PY150, “E-4GN” manufactured by LANXESS), 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. The mixture was poured into 5000 parts of warm water, stirred at a high-speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 490 parts of yellow fine pigment (Y3).

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

(Green refined pigment (G1))
Phthalocyanine green pigment C.I. I. 500 parts of Pigment Green 36 (PG36, “Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. for 8 hours. Kneaded. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green fine pigment (G1) was obtained.

(Green refined pigment (G2))
Phthalocyanine green pigment C.I. I. 500 parts of Pigment Green 7 (PG7, “Lionol Green YS-07” manufactured by Toyocolor Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. Kneaded for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green fine pigment (G2) was obtained.

(Black refined pigment (K1))
Perylene black pigment C.I. I. 500 parts of CI Pigment Black 31 ("PalIogen Black S0084" manufactured by BASF)), 250 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 5 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a black fine pigment (K1) was obtained.

<Structure of dye derivative>
Table 1 shows the structural formulas of the dye derivatives used for preparing 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 with 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, followed by filtration with a 5 μm filter to obtain a pigment dispersion (RP-1).

Red fine 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))
Except having changed into the composition of Table 2, and the compounding quantity (part by weight), it carried out similarly to the pigment dispersion (RP-1), and carried out the pigment dispersion (RP-2, BP-1 -2, YP-1-). 4, GP-1 and 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) for 5 hours using zirconia beads having a diameter of 1 mm. Thereafter, 30.0 parts of methoxypropyl acetate was added, followed by filtration with a 5 μm filter to obtain a pigment dispersion (CP-1).

Carbon black (CB-1): 12.6 parts “Regal 250R” 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 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 part "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 "FZ-2122" manufactured by Toray Dow Corning
(A solution obtained by diluting 1 part of (nonvolatile content 100% by weight) with 99 parts of cyclohexanone)
Solvent: 14.01 parts methoxypropyl acetate

[Examples 2 to 35, Comparative Example 1]
(Production of photosensitive black composition (BLK-2 to 36))
A photosensitive black composition (BLK-2 to 36) was obtained in the same manner as the photosensitive black composition (BLK-1) except that the composition and the blending amount (parts by weight) shown in Tables 3 to 6 were changed. It was.

Abbreviations in Tables 3 to 6 are described below.
《Chain transfer agent》
・ Showa Denko "Karenz MTPE1" (pentaerythritol tetrakis (3-mercaptobutyrate))
Photopolymerization initiator “Irgacure OXE-02” (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) manufactured by BASF ))
"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 all R 1 are hydrogen atoms)
“DPCA60” manufactured by Nippon Kayaku Co., Ltd. (formula, m = 1, number of groups represented by formula (2) = 6, R ¹ is all hydrogen atoms)
・ Kyoei Chemical Co., Ltd. “DAUA167” (53% carbitol acetate solution of urethane acrylate having carboxyl group)
・ "Aronix M402" manufactured by Toagosei Co., Ltd.
(Dipentaerythritol hexaacrylate / pentaacrylate mixture)

《Leveling agent solution》
・ "FZ-2122" manufactured by Toray Dow Corning
(A solution obtained by diluting 1 part of (non-volatile content: 100% by weight) 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 isocyano group 3-Isocyanatopropyltriethoxysilane / silane coupling agent (C-4); Vinyl group Silane coupling agent Vinyltrimethoxysilane / silane coupling agent (C-5); Silane coupling agent having an amino group
3-aminopropyltrimethoxysilane

<Light transmittance measurement evaluation>
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 film thickness of the obtained black composition was 2.0 μm.

[Preparation of coating film]
The black compositions of Examples and Comparative Examples were applied on a 100 mm × 100 mm, 0.7 mm thick glass substrate using a spin coater, and then dried in an oven at 70 ° C. for 20 minutes. Used, exposed to ultraviolet light at an integrated exposure of 150 mJ / cm ² , developed with an alkaline developer at 23 ° C., washed with ion-exchanged water, then heated at 220 ° C. for 30 minutes, allowed to cool, and film thickness 2. A 0 μm coated substrate was obtained.
[Light transmittance measurement]
About the obtained coating-film board | substrate, the light transmittance of wavelength 400-700 nm was measured using the microspectrophotometer (Olympus Optical company make "OSP-SP100"), and the maximum value (Tmax) of the light transmittance was calculated | required.

<Evaluation of photosensitive coloring composition>
About the black composition obtained by the Example and the comparative example, stability, linearity, pattern shape, and the adhesiveness with respect to an organic layer were evaluated as follows. Table 7 shows the evaluation results.

[Evaluation of stability]
About the black composition obtained by the Example and the comparative example, using the E type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.), the viscosity (V1) 24 hours after preparation and the condition of 23 degrees The viscosity (V2) after storage for 30 days was evaluated, and the viscosity change rate (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 acceptable (△)
Viscosity change rate 0.20 or more Stability failure (×)

[Evaluation of adhesion to organic layer]
The black compositions of Examples and Comparative Examples were applied on a 100 mm × 100 mm, 0.7 mm thick glass substrate using a spin coater, and then dried in an oven at 70 ° C. for 20 minutes. Used, exposed to ultraviolet light at an integrated exposure of 130 mJ / cm ² , developed with an alkaline developer at 23 ° C., washed with ion-exchanged water, then heated at 230 ° C. for 30 minutes, allowed to cool, A 5 μm coated substrate was obtained. On the black substrate thus prepared, “Optomer SS6699G” manufactured by JSR was applied so that the film thickness was 2.00 μm, and then heated at 230 ° C. for 20 minutes. Thereafter, the adhesion of the coating film was evaluated on the obtained coated substrate by a cross-cut adhesion test method according to JIS K5400, and the number of peels in 100 cross-cuts was counted.

Adhesion evaluation:
◎: Number of cross-cuts peeled off 0: Number of cross-cuts peeled from 1 to less than 3 Δ; Number of cross-cuts peeled from 3 to less than 10 ×; Number of cross-cuts peeled off: 10 or more

[Linearity evaluation (PW1-PW2)]
The black film composition obtained in Examples and Comparative Examples is applied to a 100 mm × 100 mm, 0.7 mm thick glass substrate, and the film thickness after drying at 70 ° C. for 20 minutes is 2.5 μm. Was made.
Using an ultra-high pressure mercury lamp, UV exposure was performed with a cumulative light quantity of 130 mJ / cm ² through a photomask, and then the unexposed part was developed with an alkaline developer at 23 ° C. and washed with ion-exchanged water. The linearity of the produced black pattern formation part was confirmed with a microscope, and the quality of linearity was evaluated. The quality of the linearity was determined 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. Linearity was evaluated according to the following criteria based on PW1-PW2.
In the case of PW1-PW2 ≦ 2 μm, it can be said that the electrode wiring pattern of the precision processed touch panel can be coated with high accuracy, and it can be said that the composition is more excellent.

Excellent linearity if it is 1μm or less (◎)
Good linearity when larger than 1 μm and 2 μm or less (○)
If it is larger than 2 μm, poor linearity (×)

[Pattern shape evaluation]
About the black pattern formation part produced in the said linearity evaluation, the cross section of the linear pattern was observed with the scanning electron microscope (SEM), and the taper shape was evaluated.
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:
A: The taper angle is less than 70 °; the taper angle is 70 ° or more and less than 80 ° Δ; the taper angle is 80 ° or more and 90 ° or less x;

  As shown in Table 7, the black composition of the present invention contains at least two types of organic pigments (A) and has a maximum light transmittance of 400 to 700 nm when the film thickness is 2.0 μm. Is 25% or less, it is excellent in light-shielding properties and aesthetics, has high light-shielding properties even when used as a decorative coating film for touch panels, and can sufficiently conceal wiring of touch panels. And it contains this black composition by containing the specific silane coupling agent (C1) and the photopolymerizable monomer (D1) which has a urethane bond, or the photopolymerizable monomer (D2) which has a caprolactone structure. The adhesion of the black coating layer made of a product to the organic layer is less than 10 in the number of peels per 100 grids according to the grid adhesion test method, and not only has excellent adhesion and pattern shape, The viscosity increase rate was low, the stability was good, and the linearity was good.

  In particular, when compositions having different photopolymerizable monomers are compared, the composition contains a large amount of photopolymerizable monomer (D1) having a urethane bond or photopolymerizable monomer (D2) having a caprolactone structure. As a result, the result was excellent in pattern shape.

  Moreover, when the compositions (Examples 1, 11, 12, 18, 19) differing only in the type of the silane coupling agent are compared, the silane coupling agent containing an epoxy group or the silane coupling agent containing a (meth) acryloxy group The black compositions (Examples 1, 11, and 12) containing a large amount of the silane coupling agent containing an isocyano group were more favorable in 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 the photosensitive composition of 100% by weight is 0.1% by weight or more and less than 5% by weight, the implementation is less than 0.1% by weight. It was excellent in adhesion to Example 20, and the black composition showed good stability as compared with Example 21 of 5% by weight or more.

  The linearity of the black composition in which the ratio (M / P) of the weight (P) of the transparent resin to the weight (M) of the precursor of the transparent resin is 0.30 to 0.80 is 0.3. It was a favorable result compared with the following Example 22 and Example 17 of 0.80 or more.

  Further, when Examples 1 and 23 are compared, the black composition using the oxime ester compound as the photopolymerization initiator has less photopolymerization initiator content than the black composition using the acetophenone compound. Also, the adhesion was good and the shape was excellent.

  On the other hand, in the black composition of Comparative Example 1 that did not contain the silane coupling agent (C), the number of peeled grids was more than 10, and the adhesion with the organic layer was poor in the adhesion evaluation.

  From the above results, when used as a display device by the black composition of the present invention, the adhesion with the organic layer is particularly good, and it is excellent in stability capable of imparting a color with excellent aesthetics, particularly the touch panel. It was confirmed that it was a high-quality black coating film suitable for decoration.

Claims (7)

A black composition for decorating a touch panel 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) is an silane having an epoxy group, a (meth) acryloxy group, or an isocyano group. A photopolymerizable monomer (D1) containing a coupling agent (C1) and having a structure in which the photopolymerizable monomer (D1) has a urethane bond and caprolactone has been modified ( Containing at least one selected from the group consisting of D2),
When the coating film is formed under the condition that the black composition for decorating the touch panel has a film thickness of 2.0 μm, the light transmittance in the entire wavelength range of wavelength 400 to 700 nm is 25% or less,
And the adhesiveness of the organic layer with respect to the black coating film layer which consists of this black composition for touchscreen decoration is less than 10 in the number of peeling in 100 grids by a grid pattern adhesion test method,
The black composition for decorating a touch panel , 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 content of the silane coupling agent (C1) is 0.1 wt% or more and less than 5 wt% in a total solid content of 100 wt% of the black composition for decorating a touch panel . Black composition for touch panel decoration . 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 for decorating a touch panel according to claim 1 , wherein the black composition is provided. Furthermore, an oxime ester photoinitiator is contained , The black composition for touchscreen decoration of any one of Claims 1-3 characterized by the above-mentioned. It forms using the black composition for touchscreen decoration of any one of Claims 1-4, The black coating film characterized by the above-mentioned.   The black coating film according to claim 5, which has a thickness of 1.0 μm or more. And claim 5 or 6 black coating layer made of a black coating film, wherein the laminated body characterized by comprising at least a contact with the one surface organic layer of the black coating layer.