JP2015028125A - Black composition and black coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black composition which excels in light-shielding property and stability and can impart a superior hue to an appearance when used for a display device, and to provide a high-quality black coating film using the black composition, which is suitable for decorating a touch panel.SOLUTION: The black composition comprises carbon black (A), at least two organic pigments (B), a dye derivative (C) expressed by general formula (1), and a binder resin (D). The black composition has such properties that when the composition is formed into a coating film having a film thickness of 1.0 μm, the film shows a maximum of light transmittance of 10% or less at a wavelength from 400 to 700 nm and a standard deviation of the light transmittance of less than 3% at a wavelength from 400 to 700 nm.

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. The 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.

  A black composition in which carbon black and an organic pigment are combined in order to achieve the light shielding properties required for the decorative portion is disclosed. However, in the conventional black composition, when mixing a dispersion containing carbon or an organic pigment, agglomerated foreign matter is generated, or the stability of the colored composition mixed due to the aggregation of the carbon and the organic pigment is deteriorated. was there.

JP 2009-295365 A Japanese Patent Laid-Open No. 21-295365 Japanese Laid-Open Patent Publication No. 04-63870 Japanese Patent Laid-Open No. 19-249046

  An object of this invention is to provide the black composition excellent in stability which can provide the color which was excellent in light-shielding property, and was excellent in the beauty | look in using it as a display device. 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 carbon black (A), at least two types of organic pigments (B), and a dye derivative represented by the following general formula (1) ( C), and a black colored composition containing the binder resin (D) and having specific spectral characteristics has been found to provide a black composition excellent in light-shielding properties and aesthetics. It was made.

That is, the present invention is a black composition containing carbon black (A), at least two kinds of organic pigments (B), a dye derivative (C) represented by the following general formula (1), and a binder resin (D). When the coating film is formed under the condition that the black composition has a film thickness of 1.0 μm, the maximum value of the light transmittance at a wavelength of 400 to 700 nm is 10% or less, and the light with a wavelength of 400 to 700 nm is used. It is related with the black composition characterized by the standard deviation of the transmittance | permeability being less than 3%.

[In General Formula (1), Q represents an organic dye residue, X represents a direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ — ( Y ₂ represents an alkylene group that may have a substituent or an arylene group that may have a substituent.), Y ₁ represents —NH— or —O—, and Z represents n When is 1, it represents a hydroxyl group, an alkoxy group, a substituent represented by the following general formula (2), or —NH—XQ (where Q and X are as defined above), and n is 2 In the case of -4, it represents a hydroxyl group, an alkoxy group, or a substituent represented by the following general formula (2), R ₁ and R ₂ each independently represents an alkyl group which may have a substituent, R may form a heterocyclic ring containing at least nitrogen atom ₁ and and R ₂ are bonded to each other m represents an integer of 1 to 6, n represents an integer of 1 to 4.

[In General Formula (2), Y ₃ represents —NH— or —O—. M, R ₁ and R ₂ are as described above. ]]

The present invention also includes an organic pigment (B) and / or a dye derivative (C), wherein the black composition satisfies the following formulas (T1), (T2), and (T3), respectively, and at least one of It is a pigment derivative (C), It is related with the said black composition characterized by the above-mentioned.

(T1): 400 nm ≦ λmin <500 nm
(T2): 500 nm ≦ λmin <600 nm
(T3): 600 nm ≦ λmin <700 nm

[In the formulas (T1), (T2), and (T3),
λmin is a wavelength at which the light transmittance at a wavelength of 400 nm to 700 nm is minimized. ]

  In the present invention, the carbon black (A) contains at least two types of carbon blacks having different particle diameters, and the average primary particle diameter of the carbon black (a1) having the smallest average primary particle diameter is D1 and the average primary particle diameter. The black composition is characterized in that 8 nm ≦ D1 ≦ 20 nm and 21 nm ≦ D2 ≦ 40 nm, where D2 is the average primary particle size of carbon black (a2) having the largest particle size.

  In addition, the present invention further includes a photopolymerization initiator (E) and an ethylenically unsaturated monomer (F), and the solid content in the black composition is based on the weight (1.0). When the weight ratio of the photopolymerization initiator (E), the ethylenically unsaturated monomer (F), and the binder resin (D) is W1, W2, and W3, respectively, 0.10 ≦ W1 + W2 ≦ 0. 45, 0.10 ≦ W2 / W3 ≦ 1.10.

  The present invention also relates to the black composition, wherein the photopolymerization initiator (E) contains an oxime ester-based initiator.

  Moreover, this invention relates to the said black composition characterized by containing antioxidant.

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

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

  By using the black composition of the present invention to form a decorative portion of an electronic device on which a capacitive touch panel is mounted, it is possible to impart a color with excellent light shielding properties and aesthetics.

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 contains carbon black (A), at least two types of organic pigments (B), a dye derivative (C) represented by the following general formula (1), and a black color containing a binder resin (D). When the coating film is formed under the condition that the black composition has a film thickness of 1.0 μm, the maximum value of the light transmittance at a wavelength of 400 to 700 nm is 10% or less, and the wavelength is 400 to The black composition is characterized in that the standard deviation of light transmittance at 700 nm is less than 3%.

  The black composition of the present invention has a maximum light transmittance of 10% or less at a wavelength of 400 to 700 nm and a light transmission of a wavelength of 400 to 700 nm when a coating film is formed under the condition of a film thickness of 1.0 μm. The standard deviation of the rate is less than 3%. The maximum value of the light transmittance is more preferably 8% or less, still more preferably 6% or less. The standard deviation of light transmittance is more preferably 2% or less.

The standard deviation (σ) of the light transmittance is, for example, when the light transmittance at a wavelength of 400 to 700 nm is measured in increments of 1 nm, a light transmittance of n = 301 points is obtained, and the transmittance at the i-th wavelength is T _i , When the average value of the light transmittance at 301 points is T _Ave , it can be calculated from the measured value of the light transmittance by the following method.

Here, n is an integer of 60 or more, and the measurement wavelength is selected so that the difference between an arbitrary i-th wavelength and the i-1th wavelength is 1 nm or more and 5 nm or less.
By using a black composition capable of forming a coating film having such spectral characteristics, it is possible to obtain a coating film having excellent light shielding properties and aesthetics.

<Carbon black (A)>
The black composition of the present invention contains 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.
When selecting the kind of carbon black (A) independently, the preferable range of an average primary particle diameter is 8 to 40 nm, More preferably, it is 10 to 35 nm, More preferably, it is 15 to 30 nm.

Among them, the carbon black (A) contains at least two types of carbon blacks having different particle diameters D, the average primary particle diameter of the carbon black (a1) having the smallest average primary particle diameter is D1, and the average primary particle diameter is the largest. When the average primary particle diameter of carbon black (a2) is D2, it is preferable that 8 nm ≦ D1 ≦ 20 nm and 21 nm ≦ D2 ≦ 40 nm because a coating film having excellent light-shielding properties can be formed.
In particular, a composition containing no carbon black having an average primary particle diameter D exceeding 40 nm is particularly preferable.
In the black composition using each carbon black, there exists a tendency as shown below.

  In a black composition in which carbon black (a1) having an average primary particle diameter D of 8 nm ≦ D ≦ 20 nm is used alone, a black composition in which carbon black having the same weight and larger average primary particle diameter D is used alone Compared to products, the number of carbon black particles per unit volume is large, which is advantageous from the viewpoint of light shielding properties. However, photocurability may be inferior due to high light shielding properties. Furthermore, it is difficult to stably disperse carbon black, and a problem of causing a phenomenon of a residue (or also referred to as background stain) in which a part of the black composition remains on a glass substrate after development is likely to occur.

  On the other hand, in a black composition in which carbon black (a2) having an average primary particle diameter D of 21 nm ≦ D ≦ 40 nm is used alone, black in which carbon black having the same weight and a smaller average primary particle diameter is used alone. Compared to the composition, the number of carbon black particles per unit volume is small and photocurability is advantageous, but light shielding properties may be inferior.

  In addition, in the black composition in which carbon black having an average primary particle diameter D exceeding 40 nm is used, the unit volume is larger than that in the black composition in which only carbon black having an average primary particle diameter D of less than 40 nm is used. Although the number of hitting carbon black particles is small, the photocuring property is advantageous, but the light shielding property and the pattern shape of the black matrix, in particular, the linearity tends to be inferior.

As the carbon black (a1), carbon black having an average primary particle diameter D of 10 nm ≦ D ≦ 18 nm is preferable, and carbon black having a specific surface area of 200 to 600 m ² / g can be suitably used. When carbon black with a specific surface area of less than 200 m ² / g is used, it tends to cause deterioration of the pattern shape and adhesion of the black matrix, and when carbon black of more than 600 m ² / g is used, carbon It tends to be difficult to stably disperse black. Moreover, it is preferable that an average primary particle diameter is 8 nm or more from the ease of acquisition of carbon black.

As the carbon black (a2), carbon black having an average primary particle diameter of 22 nm ≦ D ≦ 37 nm is preferable, and carbon black having a specific surface area of 40 to 600 m ² / g can be suitably used. When carbon black having a specific surface area of less than 40 m ² / g is used, there is a tendency to cause deterioration of pattern shape and adhesion, and when carbon black greater than 600 m ² / g is used, the stability of carbon black is likely to be caused. Dispersion tends to be difficult.

The average primary particle diameter D of carbon black contained in the black composition can be obtained by the following method.
First, the black composition is diluted about 100 times using a solvent contained in the black composition to obtain a diluted product. Next, the diluted product is air-dried on a sample stage, and several tens of thousands of photographs are taken with an electron microscope for the obtained carbon black. The maximum particle diameter of carbon black is measured at about 2000 to 3000, and the average primary particle diameter D is obtained by simply averaging the measured values. For a black composition containing two or more types of carbon black, first, the number-based particle size distribution of the entire carbon black contained in the black composition is determined. Next, assuming that each particle size distribution of two or more types of carbon black follows a normal distribution, curve fitting is performed with the number of Gaussian functions expected from the shape of the particle size distribution and the number of peaks, and each distribution function is determined. . The average primary particle diameter D of each carbon black is determined from the parameters of the obtained distribution function. The average primary particle diameter D is usually expressed as a value (nm) obtained by rounding off the first decimal place.

When two or more types of carbon black are used in the black composition of the present invention, the carbon black (a1) having the smallest average primary particle diameter has the average primary particle diameter D1 and the carbon black having the largest average primary particle diameter. When the average primary particle diameter of (a2) is D2, it is preferable to use together carbon black of 8 nm ≦ D1 ≦ 20 nm and 21 nm ≦ D2 ≦ 40 nm. At this time, it is preferable not to mix carbon black having an average primary particle diameter D exceeding 40 nm because the light shielding property of the coating film of the black composition can be improved.
The average primary particle size of carbon black before mixing can also be measured by the same method using an electron microscope as described above. Commercially available carbon black can be used for both carbon black satisfying 8 nm ≦ D1 ≦ 20 nm and carbon black satisfying 21 nm ≦ D2 ≦ 40 nm.

  Examples of carbon black having an average primary particle diameter D of 8 nm ≦ D ≦ 20 nm include MONARCH made by CABOT, BLACK PERLS (1400, 1300, 1100, 1000, 900, 880, 800, 700), VULCAN (P 9A32), Mitsubishi Chemical # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990, 980, 970, 960, 950, 900, 850), MCF88, MA600, Color Black made by DEGUSSA (FW2000, FW2, FW2V, FW1, FW18, S170, S160), Special Black (6, 5), Printex (95, 90, 85, 80, 75, 40, 60), Tokai Carbon's seast (9 SAF-HS, 9 SAF), Asahi Carbon's Asahi # 80, Colombian Carbon's ROYAL SPECTRA, NEO SPECTRA MARK (I and II), NEO SPECTRA AG, SUPERBA (NEO MK III), NEO SPECTRA MARK IV, RA (5000, 7000, 5750, 5250, 3500, 3200, 2000, 1500), CONDUCTEX (40-220, SC), RAVEN C BEADS, and the like. Preferably, MONARCH (1100, 800) manufactured by CABOT, BLACK PERLS (1100, 800), PrintX 95 manufactured by DEGUSSA, # 850 manufactured by Mitsubishi Chemical, particularly preferably MONARCH1100 manufactured by CABOT, and PrintX 95 manufactured by DEGUSSA are used. it can. The carbon black may be used alone or in combination of two or more.

  Examples of carbon black having an average primary particle diameter D of 21 nm ≦ D ≦ 40 nm include, for example, VULCAN (XC72R, XC72), MOGUL L, BLACK PEARLS (L, 570, 520, 490, 480, 470, 460, manufactured by CABOT, 450, 430, 420, 410), REGAL (660R, 660, 500R, 330R, 330, 300R, 250R, 250, 99R, 99I), ELFTEX (5, 8, 12, PELLETS115), Mitsubishi Chemical MA (77 , 7, 8, 11, 100, 100R, 100S, 230, 200RB, 14), # (750B, 650B, 52, 50, 47, 45, 45L, 44, 40, 33, 32, 30, 95, 85, 260, 3230B, 3350B), CF9, made by DEGUSSA specialBlack (4, 4A, 550, 350), PrintX (150T, U, V, 140U, 140V, 55, 45, P, L6, L, 300, 30, ES23, 3, ES22, 35, XE2), NIPex35, Tokai Carbon's seast [6ISAF, 600ISAF-LS, 5H-IISAF-HS, KH (N339), 3HHAF-HS, NH (N351), 3 HAF, 3M, NLI-HAF, 300HAF-LS, 116 MAF], Asahi Carbon's Asahi # 75, Asahi # 70 (-IH, -IN, -L), Asahi HS-500, Asahi F-200, Colombian Carbon Raven (1255, 1250, 1200, 1170, 1040, 1035) 1030BEADS, 1020, 1000, 890POWDWE, 890HP OWDER, 850, 825BEADS), CONDUCTEX (975BEADS, 900BEADS), and the like. Preferably, REGAL (300R, 250R, 250, 99R, 99I) manufactured by CABOT, MA (7, 11, 100R), # (47, 45, 45L) manufactured by Mitsubishi Chemical, Printex55, NIPex35 manufactured by DEGUSSA, particularly preferably # 47 manufactured by Mitsubishi Chemical, REGAL250R manufactured by CABOT, PrintX55 manufactured by DEGUSSA, and NIPex35 can be used. The carbon black may be used alone or in combination of two or more.

  The weight ratio of carbon black (a1) and carbon black (a2) contained in the black composition is preferably (a1) / (a2) = 1/3 to 1/30, more preferably 1/3 to 1/10. It is. When (a1) / (a2) = 1/3 is exceeded, that is, when (a1) is large, stable dispersion of carbon black tends to be difficult. On the other hand, when (a1) / (a2) is less than 1/30, that is, when (a1) is reduced, the high light-shielding property expressed when (a1) carbon black and (a2) carbon black are used in combination. There is a tendency that the stability effect of the black composition cannot be expected.

  Carbon black (a1) and carbon black (a2) are preferably 10 to 50% by weight in total, more preferably 10 in total, based on the total solid weight of the black composition (100% by weight). It can be used in an amount of ˜30% by weight.

<Organic pigment (B)>
The black composition of the present invention contains at least two organic pigments. 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, at least a red pigment and a blue pigment are included so that a coating film excellent in light shielding properties and aesthetics can be obtained.

  Among these, C.I. I. Pigment Red 177 or 254, C.I. I. Pigment Blue 15: 6 or 15: 3, as a yellow pigment, C.I. I. Pigment yellow 138, 139, 150, or 185, as a black pigment, C.I. I. Pigment black 31 or 32 is preferable.

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

<Dye derivative (C)>
The pigment derivative (C) is represented by the following general formula (1). Moreover, it becomes possible to obtain the decorative coating film excellent in light-shielding property and aesthetics by selecting the pigment derivative which has the optimal spectral transmittance so that it may mention later. A pigment derivative (C) may be used individually by 1 type, and may be used in mixture of 2 or more types by arbitrary ratios.

[In General Formula (1), Q represents an organic dye residue, X represents a direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ — ( Y ₂ represents an alkylene group which may have a substituent or an arylene group which may have a substituent.), Y ₁ represents —NH— or —O—, and Z represents n When is 1, it represents a hydroxyl group, an alkoxy group, a substituent represented by the following general formula (2), or —NH—XQ (where Q and X are as defined above), and n is 2 In the case of ~ 4, it represents a hydroxyl group, an alkoxy group, or a substituent represented by the following general formula (2), R ₁ and R ₂ each independently represents an alkyl group which may have a substituent, R ₁ and R ₂ may be bonded to each other to form a heterocycle containing at least a nitrogen atom, and m is an integer from 1 to 6. Represents a number, and n represents an integer of 1 to 4.

[In General Formula (2), Y ₃ represents —NH— or —O—. M, R ₁ and R ₂ are as described above. ]]

  Examples of the alkylene group include a methylene group and an ethylene group. Examples of the arylene group include a phenylene group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the substituent that these groups have include a methyl group and an ethyl group.

  Examples of the organic dye in the organic dye residue Q include, for example, phthalocyanine series, quinacridone series, quinacridone quinone series, isoindolinone series, quinophthalone series, diketopyrrolopyrrole series, perylene series, perinone series, indigo series, thioindigo series, dioxazine. , Anthraquinone, pyranthrone, anthanthrone, flavanthrone, indanthrone, metal complex complex polycyclic organic pigments, benzimidazolone, insoluble azo, condensed azo, soluble azo, etc. Organic pigments or dyes, and pale yellow aromatic polycyclic compounds such as naphthalene compounds. Among these, phthalocyanine-based, benzimidazolone-based, anthraquinone-based, diketopyrrolopyrrole-based, and perylene-based organic dye residues are preferable because they can improve the dispersibility of the organic pigment and carbon black.

Examples of the dye derivative (C) represented by the general formula (1) include dye derivatives represented by the following general formulas (2) to (11).

A dye derivative different from the dye derivative (C) can also be used.
Examples of the dye derivatives that can be used in combination include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, and JP-B-5-9469. What is described in the gazette etc. can be used.

  The content of all the pigment derivatives including the pigment derivative (C) is preferably 0.05 to 20% by weight, more preferably 0.5 to 0.5% based on the total solid weight of the black composition (100% by weight). It can be used in an amount of 10% by weight. When the content of the pigment derivative is less than 0.05% by weight, the effect of dispersing the organic pigment and carbon black tends not to be sufficiently exerted. There is a tendency to become unstable.

  The total content of carbon black (A), organic pigment (B), and dye derivative (C) is preferably 20% by weight or more, based on the total solid weight of the black composition (100% by weight), More preferably, it contains an amount of 30-60% by weight. Among these, when carbon black (A) is contained in an amount of 10% by weight or more, when the coating film is formed under the condition that the black composition has a film thickness of 1.0 μm, the maximum value of the light transmittance at a wavelength of 400 to 700 nm is 10. %, The standard deviation of the light transmittance at a wavelength of 400 to 700 nm can be easily set to less than 3%, and the light shielding property and aesthetic appearance can be improved. Preferably, it can be used in an amount of 10 to 50% by weight, more preferably 10 to 30% by weight in total.

<Light transmittance of organic pigment and pigment derivative>
The black composition of the present invention includes an organic pigment (B) and / or a dye derivative (C) that satisfy the following formulas (T1), (T2), and (T3), respectively, and at least one is a dye derivative (C) is preferable because light in a specific wavelength region can be prevented from being polarized and transmitted, and as a result, light-shielding properties and aesthetics can be improved.
(T1): 400 nm ≦ λmin <500 nm
(T2): 500 nm ≦ λmin <600 nm
(T3): 600 nm ≦ λmin <700 nm

[In the formulas (T1), (T2), and (T3),
λmin is a wavelength at which the light transmittance at a wavelength of 400 nm to 700 nm is minimized. ]

The λmin of the organic pigment and the dye derivative can be obtained by the following method, for example.
A dispersion of 10% by weight of organic pigment or pigment derivative, highly transparent pigment dispersant (such as BYK-167 manufactured by BYK-Chemie) or acrylic resin (solid content) of 10% by weight, and solvent of 80% by weight has a wavelength of 400 to 400%. It can obtain | require from the transmission spectrum measured about the coating film apply | coated so that the minimum value of the transmittance | permeability in 700 nm might become higher than 1% using the microspectrophotometer ("OSP-SP100" by Olympus Optical Co., Ltd.).

As the organic pigment (B) and the dye derivative (C) satisfying the formulas (T1), (T2), and (T3), there are differences depending on the matrix skeleton of each dye, the type of substituents, and the like. In general, those having the following parent skeleton can be mentioned.
Examples of the organic pigment (B) and the dye derivative (C) satisfying the formula (T1) include organic pigments (B) such as azo, quinophthalone, isondoline, and isoindolinone yellow pigments, or organic pigments thereof. And a pigment derivative (C) having a parent skeleton as a base skeleton.

  Examples of the organic pigment (B) and the dye derivative (C) that satisfy the formula (T2) include red organic pigments such as anthraquinone, diketopyrrolopyrrole, perylene, and azo, and purple organic pigments such as dioxazine ( B) or a pigment derivative (C) having these organic pigments as a base skeleton.

  Examples of the organic pigment (B) and the dye derivative (C) satisfying the formula (T3) include a phthalocyanine blue / green organic pigment (B) or a dye derivative (C) having these organic pigments as a base skeleton. It is done.

<Binder resin (D)>
The binder resin (D) contained in the resin composition of the present invention is a dispersion of a colorant, that is, carbon black (A) and an organic pigment (B). For example, a thermoplastic resin, a thermosetting resin, or the like is used. Can be mentioned. 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. Further, polyether mono (meth) acrylate obtained by addition polymerization of 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 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 carbon black (A) and the organic pigment (B), the weight average molecular weight (Mw) of the binder resin (D) is preferably in the range of 10,000 to 100,000, more preferably 10,000. It is in the range of ~ 80,000. 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, and 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.

  Since the binder resin (D), film formability and various resistances are good, it is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant (A), and the colorant concentration is high. From the viewpoint that good color characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less. 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.

  When the black composition of the present invention is formed under the condition that the black composition has a thickness of 1.0 μm, the maximum value of the light transmittance at a wavelength of 400 to 700 nm is 10% or less, and the light transmittance at a wavelength of 400 to 700 nm. The standard deviation is less than 3%. If the maximum value of the light transmittance at 400 to 700 nm exceeds 10%, the light shielding property is insufficient when used as a decorative coating film of a touch panel, and the wiring of the touch panel cannot be sufficiently concealed, which is not preferable. In addition, when the standard deviation of the light transmittance at a wavelength of 400 to 700 nm exceeds 3%, when used in combination with a liquid crystal display, there is a strong tendency to selectively pass light of a specific wavelength in the light source of the liquid crystal display. Since the portions appear to be colored, the aesthetics are impaired, which is not preferable.

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 the photolitho method, the black composition contains a photopolymerization initiator (E), an ethylenically unsaturated monomer (F), a sensitizer, and a chain transfer agent in addition to the above (A) to (D). In addition, a solvent may be included.
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.

Among them, a photopolymerization initiator of an oxime ester compound is generally preferable because it has a high sensitivity and can form a pattern having excellent linearity. Examples of the oxime ester photopolymerization initiator include phenols and carbazoles. In the present invention, carbazoles are preferable.
Furthermore, a photopolymerization initiator of an oxime ester compound represented by the following general formula (12) is preferable, and a compound represented by the following chemical formula (13) is particularly preferable.

[In General Formula (12), R _{51 to} R ₅₄ 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, 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 contained in the black composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Ethylenically unsaturated monomer (F)>
The photopolymerizable monomer (F) includes a monomer or an oligomer that is cured by ultraviolet rays or heat to generate a transparent resin.
Examples of the ethylenically unsaturated monomer (F) 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 product with succinic acid, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meth) acrylic esters, epoxy (meth) acrylates, urethane acrylates and other acrylic esters and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tris Vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile And the like.
These ethylenically unsaturated monomers can be used singly or as a mixture of two or more at any ratio as required.

  The (F) content of the ethylenically unsaturated monomer is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the total of the organic pigment and carbon black, and is 10 to 10 from the viewpoint of photocurability and developability. More preferably, it is 200 parts by weight.

  In the case where the black composition is a photosensitive black composition containing a photopolymerization initiator (E) and an ethylenically unsaturated monomer (F), the weight (based on the solid content in the black composition is 1.0). ), When the weight ratios of the photopolymerization initiator (E), the ethylenically unsaturated monomer (F), and the binder resin (D) are W1, W2, and W3, respectively, 0.10 ≦ W1 + W2 ≦ 0.45, 0.10 ≦ W2 / W3 ≦ 1.10, it is preferable because practical ultraviolet sensitivity can be obtained, and a straight line defect after developing a black pattern hardly occurs. .

Further, W1 + W2 is more preferably 0.15 ≦ W1 + W2 ≦ 0.35, and more preferably 0.15 ≦ W2 / W3 ≦ 0.80.
If W1 + W2 is 0.10 or more, practical ultraviolet sensitivity can be obtained, and if W1 + W2 is 0.45 or less, pattern-shaped linearity defects are unlikely to occur.
If W2 / W3 is 0.10 or more, practical ultraviolet sensitivity can be obtained.
When the photosensitive black composition contains a sensitizer, the weight ratio of the sensitizer is also included in W1, and the weight of the resin-type dispersant is not included in W2.

<Antioxidant>
It is preferable to add an antioxidant to the black composition for the purpose of imparting heat resistance and light resistance to the coating film.

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

<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-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. 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 photosensitive black composition. 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.

<Solvent>
For the black composition, sufficiently disperse the dye in the dye carrier and apply it on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 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 manufacturing method of a black composition>
The black composition comprises each of the organic pigment or carbon black and the dye derivative (C) in a three-roll mill, two-roll mill, sand mill, preferably 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 various dispersing means such as a kneader and an attritor. Moreover, each organic pigment and carbon black may be simultaneously dispersed on the dye carrier, or may be mixed separately on the dye carrier. Dispersing aids such as resin-type pigment dispersants and surfactants are excellent in dispersing organic pigments and carbon black, and have a great effect of preventing reaggregation of the pigment after dispersion.

  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 and the 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 with respect to 100 parts by weight of the total of the organic pigment and carbon black. . 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 of the composition over time, and contains an adhesion improver such as a silane coupling agent in order to improve the adhesion to the transparent substrate. It can also be made.

  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.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

  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.

<Black coating film>
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.
In particular, it can be used as a decorative coating film for a touch panel that is excellent in light-shielding properties and aesthetics by being formed in a frame shape on the outer periphery of a cover glass of a touch panel or a protective film substrate.

  It is preferable that the dry film thickness of a black coating film is 0.2-10 micrometers, More preferably, it is 0.2-5 micrometers. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of the black coating film by the photolithography method is performed 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.

  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, methods for producing binder resin solutions used in Examples and Comparative Examples, methods for refining organic pigments, structures of dye derivatives, methods for measuring light transmittance of organic pigments and dye derivatives, pigment dispersions, and carbon black dispersions A method for manufacturing the body 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% by mass Thus, an acrylic resin solution 1 was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
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, 7.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 22.0 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% by mass Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 25000.

(Preparation of acrylic resin solution 3)
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 further continued for 1 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 3 was prepared. The weight average molecular weight (Mw) was 18000.

<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 diketopyrrolopyrrole-based fine 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 anthraquinone-based fine pigment (R2) were obtained.

(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 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 refined 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 refined 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. And 490 parts of a refined pigment (Y4) was 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. Pigment Green 7 (PG7, “Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.) 500 parts, 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. 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 (G2) was obtained.

(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, “LIONOL BLUE FG-7351” manufactured by Toyocolor Co., Ltd.) 200 parts, sodium chloride 600 parts, and diethylene glycol 600 parts were charged in 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).

<Method for Measuring Light Transmittance of Fine Pigment and Dye Derivative>
After mixing 10 parts of the fine pigment or the pigment derivative shown in Table 1 with 50 parts of the acrylic resin solution 1 and uniformly stirring and mixing 20 parts of methoxypropyl acetate, the Eiger mill (Eiger Mill) was used with zirconia beads having a diameter of 1 mm. It was dispersed for 5 hours with “Mini Model M-250 MKII” manufactured by Japan. A dispersion obtained by filtering the obtained composition through a 5 μm filter was applied to a glass substrate with a bar coater, and the transmittance at 400 to 700 nm was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The wavelength (λmin) at which the transmittance is minimized was determined. The value of λmin is shown in Table 2.

<Method for producing pigment dispersion>
(Preparation of pigment dispersion GP-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 pigment dispersion GP-1.

Green refined pigment (G1): 12.6 parts C.I. I. Pigment Green 36
Dye derivative C2: 1.4 parts Acrylic resin solution 1: 30.0 parts Methoxypropyl acetate: 26.0 parts

(Preparation of pigment dispersions GP-2, YP1-5, BP-1 to 3, KP-1, and RP-1 to 2)
Pigment dispersions GP-2, YP1-5, BP-1 to 3, and KP-1 are the same as pigment dispersion GP-1 except that the composition is changed to the composition shown in Table 3 and the amount (parts by weight). , RP-1 and 2 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 pigment dispersion CP-1.

Carbon black (CB-2): 12.6 parts “Regal 250R” manufactured by CABOT
Dye derivative C2: 1.4 parts Acrylic resin solution 1: 30.0 parts Methoxypropyl acetate: 26.0 parts

(Preparation of carbon black dispersion CP-2 to 8)
Carbon black dispersions CP-2 to CP-8 were obtained in the same manner as pigment dispersion CP-1, except that the composition was changed to the composition shown in Table 5 and the blending amount (parts by weight). The details of the carbon black used are summarized in Table 4.

[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 (PR254): 16.32 parts Pigment dispersion BP-1 (PB15: 6): 16.32 parts Carbon dispersion CP-9: 15.74 parts Acrylic resin solution 2: 20.85 parts Ethylenically unsaturated monomer: 3.24 parts “Aronix M402” manufactured by Toagosei Co., Ltd.
(Dipentaerythritol hexaacrylate / pentaacrylate mixture)
Photopolymerization initiator: 0.90 part "Irgacure OXE-02" manufactured by BASF
(Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H
-Carbazol-3-yl]-, 1- (0-acetyloxime))
Leveling agent solution: 1.50 parts “FZ-2122” manufactured by Toray Dow Corning
((Non-volatile content: 100% by weight)) 1 part diluted with 99 parts cyclohexanone Methoxypropyl acetate: 25.14 parts

[Examples 2 to 26, Comparative Examples 1 to 7]
(Production of photosensitive black composition BLK-2 to 33)
Photosensitive black compositions BLK-2 to 33 were obtained in the same manner as the photosensitive black composition BLK-1, except that the compositions and amounts (parts by weight) described in Tables 6 and 7 were changed.

Abbreviations in Table 6 and Table 7 are described below.
As the photopolymerization initiator, “Irgacure OXE-02” (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0- Acetyloxime)) or “Irgacure 369” (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one) manufactured by BASF, As the polymer, “Aronics M402” (dipentaerythritol hexaacrylate / pentaacrylate mixture) manufactured by Toagosei Co., Ltd., “TO-1382” (dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd., and Dipentaerythritol pentaacrylate and monoester with succinic acid Mixtures of goods), examples of the leveling agent solution, manufactured by Dow Corning Toray Co., Ltd., "FZ-2122" (non-volatile content: 100% by weight)) is a solution obtained by diluting 1 part cyclohexanone 99 parts.

  In Tables 6 and 7, W1 + W2 and W2 / W3 are the photopolymerization initiator (E) and ethylenic content when the weight of the solid content in the black composition is based on (1.0). It is a value when the weight ratios of the unsaturated monomer (F) and the binder resin (D) are W1, W2, and W3, respectively.

<Light transmittance measurement evaluation>
When the coating film was formed under the condition that the film thickness of the obtained black composition was 1.0 μm, the maximum value (Tmax) of the light transmittance at a wavelength of 400 to 700 nm and the standard deviation (σ (T Table 8 shows the light transmittances of the organic pigments and dye derivatives used.

[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. Using, except for Examples 18 and 21 to 23, UV exposure was performed at an integrated exposure of 150 mJ / cm ² (Examples 18 and 23 to 300 mJ / cm ² ), and development was performed with an alkaline developer at 23 ° C. The film was washed with exchanged water, then heated at 220 ° C. for 30 minutes and allowed to cool to obtain a coated substrate having a thickness of 1.0 μm.

[Light transmittance measurement]
About the obtained coating-film board | substrate, the light transmittance of wavelength 400-700nm was measured using a microspectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"), the maximum value (Tmax) of light transmittance, and standard deviation (sigma) (T) was determined.

[Evaluation of heat resistance]
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. Using, except for Examples 18 and 21 to 23, UV exposure was performed at an integrated exposure of 150 mJ / cm ² (Examples 18 and 23 to 300 mJ / cm ² ), and development was performed with an alkaline developer at 23 ° C. The film was washed with exchanged water, then heated at 220 ° C. for 30 minutes and allowed to cool to obtain a coated substrate having a thickness of 1.0 μm. About the obtained coating-film board | substrate, after heating for 60 minutes in 260 degreeC oven, the light transmittance of wavelength 400-700 nm was measured using the microspectrophotometer ("OSP-SP100" by Olympus Optical Co., Ltd.), and light The maximum transmittance (Tmax2) was determined. This (Tmax2) and (Tmax) were compared to determine the value of X = | (Tmax2) − (Tmax) | / (Tmax). It can be said that the smaller the value of X, the better the heat resistance. Table 8 shows the value of X.

[(T1) to (T3)]
(T1) to (T3) are a collection of finer pigments or dye derivatives having a wavelength that minimizes the light transmittance at wavelengths of 400 nm to 700 nm.

<Evaluation of photosensitive coloring composition>
About the photosensitive black composition obtained by the Example and the comparative example, stability, residual film sensitivity, and linearity were evaluated as follows. Table 9 shows the evaluation results.

[Evaluation of stability]
About the black composition obtained by the Example and the comparative example, the viscosity (V2) 24 hours after preparation and the viscosity (V2) after 30-day storage on conditions of 23 degree | times were evaluated, and a viscosity change rate (V2-V1) ) / V1 was evaluated. When the viscosity change rate ≦ 0.10, the stability was good (◯), and when the viscosity change rate> 0.10, the stability was poor (x).

[Ultraviolet sensitivity (remaining film ratio) / 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 two exposure doses of 150 mJ / cm ² and 300 mJ / cm ² through a photomask, and the unexposed area was developed with an alkaline developer at 23 ° C. And washed with ion-exchanged water. A value (remaining film ratio) obtained by dividing the film thickness (t1) of the pattern formation portion of the produced pattern formation substrate by the coating film thickness (2.5 μm) was obtained. When the remaining film ratio is 0.90 or more, it can be said that the photopolymerizable monomer was sufficiently cured by ultraviolet rays, and it can be said that the composition is more excellent.
Moreover, the linearity of the black pattern formation part obtained by said method was confirmed with the 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 the superiority or inferiority of 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.

[Evaluation of shading and aesthetics]
The black compositions obtained in 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 to obtain an ultrahigh pressure. Using a mercury lamp, UV exposure was performed with an integrated exposure of 150 mJ / cm ² (Examples 18 and 23 to 300 mJ / cm ² ) except for Examples 18 and 21 to 23, and development was performed with an alkaline developer at 23 ° C. And washed with ion-exchanged water, then heated at 220 ° C. for 30 minutes and allowed to cool to obtain a coated substrate having a thickness of 2.5 μm.
Further, the visibility and aesthetics when the LED light source NSPW300BS manufactured by Nichia Chemical Co., Ltd. was turned on / off from the back surface of the obtained coating film were evaluated according to the following criteria. The evaluation was carried out in an indoor environment with an illuminance of 770 Lx with a white fluorescent lamp turned on.

Light shielding property ◯: The LED light source is hardly seen when the LED light source is turned off, and a good light shielding property is obtained.
Light shielding property Δ: The LED light source is slightly visible when the LED light source is turned off.
(The light-shielding property which is not a problem in practical use is obtained.)
Light-shielding property X: The LED light source can be seen even when the LED light source is turned off.

Aesthetic appearance: Good visual appearance with small difference in color when the LED light source is turned on / off.
Appearance Δ: Slight difference in color when LED light source is on / off.
(Beautiful aesthetics are obtained for practical use.)
Aesthetic appearance X: The difference in color when the LED light source is turned on and off is large, and the color appears to be greatly different when turned on.

  As shown in Table 9, a black composition containing carbon black (A), at least two types of organic pigments (B), a dye derivative (C) represented by the following general formula (1), and a binder resin (D) When the coating film is formed under the condition that the black composition has a film thickness of 1.0 μm, the maximum value of the light transmittance at a wavelength of 400 to 700 nm is 10% or less, and the wavelength is 400 to 700 nm. The black compositions of Examples 1 to 26 having a standard deviation of light transmittance of less than 3% have a low viscosity increase rate, good stability, and a black coating film excellent in light-shielding properties and aesthetics. did it.

  Especially, a black composition contains at least 3 sort (s) chosen from the organic pigment (B) and pigment | dye derivative (C) which satisfy | fill a formula (T1), (T2), and (T3), and at least 1 is pigment | dye derivative ( The black compositions of Examples 1-18 and 21-26, which are C), were particularly excellent in aesthetics.

  The carbon black (A) contains at least two types of carbon blacks having different particle diameters, and the carbon black (a1) having the smallest average primary particle diameter has the average primary particle diameter D1 and the carbon having the largest average primary particle diameter. When the average primary particle diameter of black (a2) is D2, the light-shielding properties of the black compositions of Examples 1-2 and 4-7 in which 8 nm ≦ D1 ≦ 20 nm and 21 nm ≦ D2 ≦ 40 nm are the same organic pigment It was higher than the light-shielding property of the black compositions of Examples 3 and 8 to 9 produced by combining these, and was a good result.

  In addition, the photopolymerization initiator (E) and the ethylenically unsaturated monomer (F), and the photopolymerization initiator ( E) When the weight ratio of the ethylenically unsaturated monomer (F) and the binder resin (D) is W1, W2, and W3, respectively, 0.10 ≦ W1 + W2 ≦ 0.45, 0.10 ≦ In the black compositions of Examples 1 to 20, 22 to 23 where W2 / W3 ≦ 1.10, the shape is better than the black compositions of Examples 24 to 25 where W1 + W2> 0.45. The sensitivity was good as compared with the black composition of Example 21 in which W2 / W3 <0.10.

  Moreover, in the black compositions of Examples 1 to 17, 19 to 23, and 26 using an oxime ester compound as a photopolymerization initiator, the black compositions of Examples 18 and 24 to 25 that do not use an oxime ester compound. The shape was good compared to the product.

  Furthermore, about the black composition of Example 26 which added antioxidant based on the black composition of Example 7, the value of X was small compared with the black composition of Example 7, and heat resistance was excellent. .

On the other hand, the black compositions of Comparative Examples 1, 2, 6, and 7 that do not contain the dye derivative (C) represented by the general formula (1) have poor stability, and the standard deviation σ ( T) ≧ 3%, and in the aesthetic evaluation, the coating looked purple when the light source was turned on, and the aesthetic appearance was poor.
In the black composition of Comparative Example 3 which does not contain at least two kinds of organic pigments (B), the coating film was reddish when the light source was turned on, the appearance was bad, and the light source was visible and the light shielding property was poor even when the light source was turned off.
In the black composition of Comparative Example 4 that does not contain carbon black (A), the light-shielding property is small, and σ (T) ≧ 3% of the coating film. It was.
Further, the black composition of Comparative Example 5 in which the concentrations of organic pigment and carbon black were low and did not satisfy Tmax ≦ 10% also looked purple when the light source was turned on, and the appearance was poor.

  From the above results, the black composition of the present invention is a high-quality black coating film that is excellent in light-shielding properties and excellent in aesthetics and suitable for touch panel decoration when used as a display device. Was confirmed.

Claims (8)

A black composition containing carbon black (A), at least two types of organic pigments (B), a dye derivative (C) represented by the following general formula (1), and a binder resin (D), When the coating film is formed under the condition that the black composition has a film thickness of 1.0 μm, the maximum value of the light transmittance at a wavelength of 400 to 700 nm is 10% or less, and the standard deviation of the light transmittance at a wavelength of 400 to 700 nm. Is a black composition characterized by being less than 3%.

[In General Formula (1), Q represents an organic dye residue, X represents a direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ — ( Y ₂ represents an alkylene group that may have a substituent or an arylene group that may have a substituent.), Y ₁ represents —NH— or —O—, and Z represents n When is 1, it represents a hydroxyl group, an alkoxy group, a substituent represented by the following general formula (2), or —NH—XQ (where Q and X are as defined above), and n is 2 In the case of -4, it represents a hydroxyl group, an alkoxy group, or a substituent represented by the following general formula (2), R ₁ and R ₂ each independently represents an alkyl group which may have a substituent, R may form a heterocyclic ring containing at least nitrogen atom ₁ and and R ₂ are bonded to each other m represents an integer of 1 to 6, n represents an integer of 1 to 4.

[In General Formula (2), Y ₃ represents —NH— or —O—. M, R ₁ and R ₂ are as described above. ]] The black composition includes an organic pigment (B) and / or a dye derivative (C) that satisfy the following formulas (T1), (T2), and (T3), respectively, and at least one is a dye derivative (C) The black composition according to claim 1, wherein the black composition is present.

(T1): 400 nm ≦ λmin <500 nm
(T2): 500 nm ≦ λmin <600 nm
(T3): 600 nm ≦ λmin <700 nm

[In the formulas (T1), (T2), and (T3),
λmin is a wavelength at which the light transmittance at a wavelength of 400 nm to 700 nm is minimized. ]   The carbon black (A) contains at least two types of carbon blacks having different particle diameters, and the carbon black (a1) having the smallest average primary particle diameter has the average primary particle diameter D1 and the carbon black having the largest average primary particle diameter ( 3. The black composition according to claim 1, wherein the average primary particle diameter of a2) is 8 nm ≦ D1 ≦ 20 nm and 21 nm ≦ D2 ≦ 40 nm, where D2 is an average primary particle diameter.   Furthermore, the photopolymerization initiator (E) and the ethylenically unsaturated monomer (F), the photopolymerization initiator (when the weight of the solid content in the black composition is based on (1.0) ( E) When the weight ratio of the ethylenically unsaturated monomer (F) and the binder resin (D) is W1, W2, and W3, respectively, 0.10 ≦ W1 + W2 ≦ 0.45, 0.10 ≦ 4. The black composition according to claim 1, wherein W2 / W3 ≦ 1.10.   The black composition according to claim 4, wherein the photopolymerization initiator (E) contains an oxime ester-based initiator.   The black composition according to any one of claims 1 to 5, further comprising an antioxidant.   A black coating film formed using the black composition according to any one of claims 1 to 6.   It is an object for touchscreen decoration, The black coating film of Claim 7 characterized by the above-mentioned.