JP6365298B2 - Resin black matrix substrate and touch panel - Google Patents

Description

  The present invention relates to a resin black matrix substrate and a touch panel.

  As a black matrix for display, a resin black matrix capable of reducing cost and environmental pollution has been developed in recent years in place of a metal thin film using a chromium-based material. Resin black matrix is a photosensitive black resin composition containing a resin and a light-shielding material such as carbon black, coated on a transparent substrate such as glass and dried to form a black film, which is then formed into a lattice pattern by photolithography. It is formed by fine patterning. For example, in a recently proposed cover glass-integrated touch panel, a transparent electrode such as an ITO electrode is formed on a black matrix formed on the cover glass.

  In order to make the display area of the display wide, it is necessary to match the color of the black display part of the display with the resin black matrix on the cover glass. It was regarded as a problem that the boundary with the part became clear.

  As a technique for reducing the reflectance of the black matrix surface, a black matrix having two layers is known (Patent Documents 1 to 3). In addition, a technique of laminating a resin layer containing a black pigment on a resin layer containing a black dye is also known (Patent Document 4).

JP 2006-011180 A JP-A-7-134208 Japanese Patent Laid-Open No. 7-248412 Japanese Patent Application Laid-Open No. 7-073211

  However, the conventional two-layer black matrix requires the presence of a metal thin film layer or a light reflecting layer containing metal fine particles, and is used for touch panel applications that require high insulation. It was extremely difficult. Furthermore, it was insufficient in terms of color matching with the black display portion of the display.

  In addition, it is difficult to adjust the color tone of a black matrix in which a black pigment-containing resin layer is laminated on a black dye-containing resin layer, and the lower layer is inferior in chemical resistance and heat resistance. It was pointed out.

  The present invention provides a resin black matrix substrate comprising a resin black matrix that has a low reflectance and can match the color of the black display portion of the display despite its thin film thickness and high light shielding properties. With the goal.

(1) comprising: a transparent substrate; a first resin black matrix formed on the transparent substrate; and a second resin black matrix formed on the first resin black matrix, The first resin black matrix contains a blue pigment and a red pigment, or contains a purple pigment, the film thickness of the first resin black matrix is 0.7 μm or more, and transmission chromaticity coordinates Is in a range of 0.150 ≦ x ≦ 0.300 and 0.010 ≦ y ≦ 0.250, and is a two-layer resin black matrix optical system comprising the first resin black matrix and the second resin black matrix A resin black matrix substrate having a concentration of 3.5 or more.
(2) The resin black matrix substrate according to (1), wherein the optical density per 1 μm of the film thickness of the first resin black matrix is 0.5 to 2.0.
(3) The resin black matrix substrate according to (1) or (2), wherein the second resin black matrix contains a black pigment.
(4) The resin black matrix substrate according to (3), wherein the black pigment is carbon black or titanium nitride.
(5) A touch panel in which an insulating film and a transparent electrode are further formed on the resin black matrix substrate according to any one of (1) to (4).
(6) A color filter substrate in which red, green or blue pixels are formed in the opening of the resin black matrix substrate according to any one of (1) to (4).
(7) A liquid crystal display device in which the color filter substrate according to (6) above and a counter substrate are bonded, and a liquid crystal compound is filled in a gap between the two.
(8) A display device in which the color filter substrate according to (6) above and a light emitting element are bonded together.
(9) The light emitting device according to (8), wherein the light emitting element is an organic EL element.

  According to the resin black matrix substrate of the present invention, although the resin black matrix is thin and has a high light shielding property, the reflectance is low, and the color of the resin black matrix and the black display portion of the display are easily matched. It becomes possible. The resin black matrix substrate of the present invention is suitable for a touch panel because the thickness of the resin black matrix can be reduced.

It is a schematic diagram which shows the one aspect | mode of the touchscreen board | substrate using the resin black matrix board | substrate of this invention. It is a schematic diagram which shows another one aspect | mode of the touchscreen board | substrate using the resin black matrix board | substrate of this invention.

  The resin black matrix (hereinafter “resin BM”) substrate of the present invention includes a transparent substrate, a first resin BM (hereinafter “resin BM (A)”) formed on the transparent substrate, A second resin BM (hereinafter referred to as “resin BM (B)”) formed on the resin BM (A), and the film thickness of the resin BM (A) is 0.7 μm or more. And the transmission chromaticity coordinates are in the range of 0.001 ≦ x ≦ 0.300 and 0.001 ≦ y ≦ 0.250, and the two layers of the resin BM (A) and the resin BM (B) The optical density (hereinafter referred to as “OD value”) is 3.5 or more.

  The film thickness of the resin BM (A) needs to be 0.7 μm or more, preferably 0.7 to 2.0 μm, and more preferably 0.7 to 1.5 μm. When the film thickness of the resin BM (A) is less than 0.7 μm, the light reflected at the interface between the resin BM (A) and the transparent substrate is reflected at the interface between the resin BM (A) and the resin BM (B). The visibility of the resin BM from the transparent substrate side deteriorates due to the interference with the light. On the other hand, when the film thickness of resin BM (A) exceeds 2.0 micrometers, the transparent electrode for touchscreens, etc. on resin BM may break.

  The transmission chromaticity coordinates of the resin BM (A) must be in the range of 0.001 ≦ x ≦ 0.300 and 0.001 ≦ y ≦ 0.250, and 0.150 ≦ x ≦ 0.300 and 0 It is preferable to be in the range of .010 ≦ y ≦ 0.250. Here, “transmission chromaticity coordinates” refers to coordinates of transmission chromaticity in the CIE 1931 color system measured with a C light source and a two-degree field of view. The measurement of the transmission chromaticity coordinates of the resin BM (A) is performed using a microspectroscope in a state where only the coating film of the photosensitive colored resin composition for forming the resin BM (A) is formed on the glass substrate. This can be done by measuring the coating film. When the transmission chromaticity coordinates of the resin BM (A) are in the above range, the transmission chromaticity can be changed from blue to violet, and the resin BM visually recognized on the transparent substrate side can be made deeper black. . Note that the transmission chromaticity coordinates of the resin BM (A) on the resin BM substrate of the present invention on which a BM composed of two layers of the resin BM (A) and the resin BM (B) (hereinafter “two-layer BM”) is formed. In the two-layer BM, the portion where the first-layer resin BM (resin BM (A)) is exposed (the portion where the resin BM (B) is not laminated) This can be done by measuring using a vessel. When there is no exposed portion of the resin BM (A), the composition of the resin BM (A) is analyzed to reproduce the photosensitive colored resin composition used to form the resin BM (A), and glass Measure the coating film using a microspectroscope in a state where only the coating film of the photosensitive colored resin composition is formed on the substrate so as to have the same film thickness as the resin BM (A) to be measured. Thus, the transmission chromaticity coordinates can be obtained.

The OD value of the two-layer BM needs to be 3.5 or more, and is preferably 4.0 or more. When the OD value of the two-layer BM is less than 3.5, the light shielding property is insufficient, and stray light from the metal wiring on the BM and the display on the back surface of the touch panel substrate is visually recognized. The OD value of the two-layer BM can be obtained by a known measurement method. Specifically, the intensity of each of the incident light and transmitted light of the two-layer BM formed on the transparent substrate using a microspectroscope can be measured and calculated from the following equation (1).
OD value = log ₁₀ (I ₀ / I) (1)
I ₀ : Incident light intensity I: Transmitted light intensity The OD value per 1 μm of film thickness of the resin BM (A) is preferably 0.5 to 2.0, and preferably 0.5 to 1.5. More preferred. If the OD value per 1 μm film thickness of the resin BM (A) is less than 0.2, the film thickness must be increased to obtain the desired transmission chromaticity and light shielding property, and the touch panel on the resin BM. There is a possibility that the transparent electrode for use will be disconnected. On the other hand, if the OD value per 1 μm film thickness of the resin BM (A) exceeds 2.0, it is necessary to increase the concentration of the pigment contained in the resin BM, and the reflectance of the resin BM becomes high.

  The OD value per 1 μm film thickness of the resin BM (B) is preferably 2.5 or more, and more preferably 3.0 to 6.0. If the OD value per 1 μm film thickness of the resin BM (B) is less than 2.5, it is necessary to increase the film thickness in order to obtain a desired light shielding property. May break.

  As a method of forming the resin BM (A) and the resin BM (B), for example, both of the resin BM (A) and the resin BM (B) are formed by a photolithography method using a photosensitive colored resin composition. Is mentioned.

  The photosensitive colored resin composition used for forming the resin BM contains a coloring material, an alkali-soluble resin, a photopolymerization initiator, and a solvent.

  Examples of the colorant contained in the photosensitive colored resin composition used for forming the resin BM (A), that is, the colorant contained in the resin BM (A) include organic pigments, inorganic pigments, and dyes. It is done. Organic pigments or inorganic pigments excellent in chemical resistance, heat resistance and light resistance are preferred, and blue pigments or purple pigments are more preferred. In particular, it is more preferable that it contains both a blue pigment and a red pigment, or is a violet pigment. The ratio of the blue pigment / red pigment is preferably 80/20 to 30/70, and more preferably 80/20 to 40/60 in terms of mass ratio. When the proportion of the blue pigment is too high, the reflection color tone becomes black with a strong bluish color, which is not preferable. On the other hand, when the ratio of the red pigment is too high, the reflection color tone is not preferable because it is a grayish black with strong redness.

  Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 or 79. I. CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 or 60 are preferred. I. Pigment Blue 15: 6 is more preferable.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 or 50. I. Pigment Violet 19 or 23 is preferred, and C.I. I. Pigment Violet 23 is more preferable.

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275 or 276. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 is preferred, and C.I. I. Pigment Red 177, 209, 224, 242 or 254 is more preferable.

  Resin BM (A) may contain other pigments in addition to these blue pigment, red pigment and purple pigment in order to adjust the reflection color more accurately. Examples of other pigments include green pigments, yellow pigments, and orange pigments.

  Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. I. Pigment Green 7, 36 or 58 is preferable.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207 or 208, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferable. I. Pigment Yellow 83, 138, 139, 150 or 180 is more preferable.

  Examples of the orange pigment include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79. I. Pigment Orange 38 or 71 is preferred.

The colorant contained in the resin BM (B) is preferably a black pigment in order to improve the light shielding property of the resin BM (B). Examples of the black pigment include carbon black, resin-coated carbon black, titanium black, chromium oxide, iron oxide, aniline black, perylene pigment, C.I. I. Solvent black 123; a composite oxide containing titanium, manganese, iron, copper, or cobalt; and a pseudo black pigment in which a colored pigment such as a red pigment, a blue pigment, or a green pigment is mixed. Carbon black or titanium black is preferable, and carbon black or titanium nitride is more preferable because it has high light shielding properties. These may be used alone or in combination. In order to achieve both high light shielding properties and high insulating properties, it is more preferable to use carbon black and titanium nitride in combination. The mixing range of carbon black / titanium nitride is preferably 10/90 to 50/50 by mass ratio.
Here, titanium black means titanium nitride represented by TiN, low-order titanium oxide represented by Ti _n O _2n-1 (1 ≦ n ≦ 20), TiN _x O _y (0 <x <2.0, 0. It refers to titanium oxynitride and titanium nitride expressed by 1 <y <2.0). Titanium nitride contains titanium nitride as a main component, and usually contains titanium oxide, low-order titanium oxide, and titanium oxynitride as subcomponents.

  Examples of the alkali-soluble resin contained in the photosensitive colored resin composition used for forming the resin BM include an epoxy resin, an acrylic resin, a siloxane resin, and a polyimide resin. An acrylic resin or a polyimide resin is preferred because of excellent heat resistance of the coating film and storage stability of the composition.

  As the acrylic resin, for example, an acrylic resin having a carboxyl group is preferable, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is more preferable.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and vinyl acetic acid.

  Examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, N-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, acrylic acid unsaturated carboxylic acid alkyl ester such as n-pentyl, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate or benzyl methacrylate; styrene, p-methylstyrene Aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene or α-methylstyrene; aminoalkyl esters of unsaturated carboxylic acids such as aminoethyl acrylate; glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate or glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile or α-chloroacrylonitrile; Aliphatic conjugated dienes such as 1,3-butadiene and isoprene; or acryloyl groups at the respective ends Alternatively, polystyrene having a methacryloyl group, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, or the like can be given.

  More specifically, a quaternary copolymer of monomers selected from the group consisting of methacrylic acid, acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate and styrene is preferable. In order to make the dissolution rate with respect to the alkaline developer appropriate, it is more preferable that the weight average molecular weight (Mw) is from 2,000 to 100,000 and the acid value is from 70 to 150 (mgKOH / g).

  An acrylic resin having an ethylenically unsaturated group in the side chain is preferable because the sensitivity during exposure and development is improved. As the ethylenically unsaturated group, an acryl group or a methacryl group is preferable. The acrylic resin having an ethylenically unsaturated group in the side chain can be obtained, for example, by adding an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to the carboxyl group of an acrylic resin having a carboxyl group. it can.

  Examples of the acrylic resin having an ethylenically unsaturated group in the side chain include Cyclomer (registered trademark) P (Daicel Chemical Industries, Ltd.), which is a commercially available acrylic resin, or an alkali-soluble cardo resin. In order to make the solubility in an ester solvent or an alkali developer appropriate, it is preferable that the weight average molecular weight (Mw) is 2,000 to 100,000 and the acid value is 70 to 150 (mgKOH / g). Here, the weight average molecular weight (Mw) is a weight average molecular weight obtained by measuring a measurement sample by gel permeation chromatography using tetrahydrofuran as a carrier and converting it using a calibration curve with standard polystyrene.

  The photosensitive colored resin composition used for forming the resin BM may further contain a monomer or an oligomer. Examples of the monomer or oligomer include polyfunctional or monofunctional acrylic monomers or oligomers. Examples of the polyfunctional acrylic monomer or oligomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, and 1,6-hexanediol (meth) adipic acid. Acrylic ester, phthalic anhydride propylene oxide (meth) acrylic ester, trimellitic acid diethylene glycol (meth) acrylic ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, full orange acrylate oligomer, tripropylene Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, tri Tyrolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2- Bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [4- (3-acryloxy-2-hydroxypropoxy) Phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4,4′-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] cyclohexane, 9 9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9- Bis [3-chloro-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol full orange acrylate or biscresol full orange methacrylate .

  By appropriately selecting and combining these polyfunctional or monofunctional acrylic monomers or oligomers, it is possible to control the sensitivity and processability during exposure and development. Among them, in order to improve sensitivity, a compound having a functional group of 3 or more is preferable, a compound having a functional group of 5 or more is more preferable, and dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate is more preferable. .

  When the photosensitive colored resin composition used for forming the resin BM contains a black pigment or the like that absorbs ultraviolet rays effective for photocrosslinking, dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate In addition, it is preferable to use a (meth) acrylate having a fluorene ring having a lot of aromatic rings and high water repellency in the molecule. In this case, it is preferable to use 90 to 40 parts by mass of (meth) acrylate having a fluorene ring and 10 to 60 parts by mass of dipentaerythritol hexa (meth) acrylate and / or dipentaerythritol penta (meth) acrylate.

  Examples of the photopolymerization initiator contained in the photosensitive colored resin composition used for forming the resin BM include benzophenone compounds, acetophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, Examples include oxime ester compounds, carbazole compounds, triazine compounds, phosphorus compounds; or inorganic photopolymerization initiators such as titanates.

  More specifically, for example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, Benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone), 379 (2- (dimethylamino) -2-[(4-methylphenyl) methyl) ] -1- [4- ( -Morpholinyl) phenyl] -1-butanone), OXE01 (1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)]), OXE02 (ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)) CGI-113 (2- [4-methylbenzyl] -2-dimethylamino-1 -(4-morpholinophenyl) -butanone) or CGI-242 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime); as described above, all manufactured by Ciba Specialty Chemicals Co., Ltd.), t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroant Quinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl)- ADEKA (registered trademark) Optomer N-1818, N-1919 or ADEKA ARCLES (registered trademark) NCI-831, which is carbazole-based compound manufactured by Asahi Denka Kogyo Co., Ltd., is available. Trademark) 379, OXE02, Adeka (registered trademark) OP It is preferable to use a photopolymerization initiator selected from the group consisting of Tomer N-1919 and Adeka Cruz NCI-831. Two or more photopolymerization initiators may be used in combination.

  The photosensitive colored resin composition used for forming the resin BM may contain an adhesion improving agent in order to improve adhesion to a glass plate or a silicon wafer. Examples of the adhesion improving agent include a silane coupling agent or a titanium coupling agent. The addition amount of the adhesion improving agent is generally about 0.2 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.

  The photosensitive colored resin composition used for forming the resin BM may contain a polymer dispersant in order to improve the dispersion stability of the colorant. Examples of the polymer dispersant include a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, and a polyallylamine polymer dispersant. The addition amount of the polymer dispersant is generally about 1 to 40 parts by mass with respect to 100 parts by mass of the colorant.

  The composition ratio of the colorant / resin component in the photosensitive colored resin composition used for forming the resin BM is preferably in the range of 80/20 to 40/60 in terms of mass ratio, and adhesion, pattern workability, and OD. In order to balance the values, the range of 75/25 to 50/50 is more preferable. Here, the resin component refers to a polymer, a monomer, an oligomer and a polymer dispersant contained in the photosensitive colored resin composition. If the resin component is too small, the adhesion between the resin BM and the substrate becomes poor. On the other hand, if the amount of the coloring material is too small, the optical density (OD value / μm) of the resin BM is lowered.

  As the solvent contained in the photosensitive colored resin composition used for forming the resin BM, water or an organic solvent can be appropriately selected according to the dispersion stability of the colorant to be dispersed and the solubility of the resin component to be added. . Examples of the organic solvent include esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents, or lactone polar solvents.

  Examples of the organic solvent when an acrylic resin is used as the alkali-soluble resin include diethylene glycol monobutyl ether acetate (boiling point 247 ° C.), benzyl acetate (boiling point 214 ° C.), ethyl benzoate (boiling point 213 ° C.), methyl benzoate (boiling point 200 ° C.). ), Diethyl malonate (boiling point 199 ° C.), 2-ethylhexyl acetate (boiling point 199 ° C.), 2-butoxyethyl acetate (boiling point 192 ° C.), ethylene glycol monobutyl ether acetate (boiling point 188 ° C.), diethyl oxalate (boiling point 185 ° C.) ), Ethyl acetoacetate (boiling point 181 ° C.), cyclohexyl acetate (boiling point 174 ° C.), 3-methoxy-butyl acetate (boiling point 173 ° C.), methyl acetoacetate (boiling point 172 ° C.), ethyl-3-ethoxypropionate 170 ° C. boiling point), 2-ethylbutyl acetate (162 ° C. boiling point), isopentylpropionate (160 ° C. boiling point), propylene glycol monomethyl ether propionate (160 ° C. boiling point), pentyl acetate (150 ° C. boiling point) or propylene glycol And monomethyl ether acetate (boiling point 146 ° C.).

  Examples of other solvents include ethylene glycol monomethyl ether (boiling point 124 ° C.), ethylene glycol monoethyl ether (boiling point 135 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), diethylene glycol monomethyl ether (boiling point 193 ° C.). ), Monoethyl ether (boiling point 135 ° C.), methyl carbitol (boiling point 194 ° C.), ethyl carbitol (202 ° C.), propylene glycol monomethyl ether (boiling point 120 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), propylene (Poly) alkylene glycol ether solvents such as glycol tertiary butyl ether (boiling point 153 ° C.) or dipropylene glycol monomethyl ether (boiling point 188 ° C.), ethyl acetate (boiling point 7 ° C), aliphatic esters such as butyl acetate (boiling point 126 ° C) or isopentyl acetate (boiling point 142 ° C), butanol (boiling point 118 ° C), 3-methyl-2-butanol (boiling point 112 ° C) or 3-methyl-3 Aliphatic alcohols such as methoxybutanol (boiling point 174 ° C.), ketones such as cyclopentanone or cyclohexanone, xylene (boiling point 144 ° C.), ethylbenzene (boiling point 136 ° C.) or solvent naphtha (petroleum fraction: boiling point 165 to 178) ° C).

  Furthermore, with the increase in the size of transparent substrates, application by a die coating apparatus has become mainstream, and in order to achieve moderate volatility and drying properties, a solvent having a boiling point of 150 to 200 ° C. contains 30 to 75% by mass. A mixed solvent is preferred.

  The photosensitive colored resin composition used for forming the resin BM may contain a surfactant in order to prevent Benard cells while ensuring applicability and smoothness of the colored coating. 0.001-10 mass parts is preferable with respect to 100 mass parts of coloring materials, and, as for the addition amount of surfactant, 0.01-1 mass part is more preferable.

  Examples of the surfactant include an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine; a cationic surfactant such as stearylamine acetate or lauryltrimethylammonium chloride; lauryldimethylamine oxide or lauryl. Amphoteric surfactants such as carboxymethylhydroxyethyl imidazolium betaine; Nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate; Silicone interfaces having polydimethylsiloxane as the main skeleton An activator; or a fluorosurfactant.

  The concentration of the solvent in the photosensitive colored resin composition used for forming the resin BM is preferably 2 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoints of coating properties and drying properties.

  Examples of the method for producing the photosensitive colored resin composition used for forming the resin BM include a method in which a pigment is directly dispersed in a resin solution using a disperser, or a pigment in water or an organic solvent using a disperser. A method of preparing a pigment dispersion by dispersing the pigment dispersion, and then mixing the pigment dispersion and the resin solution. Examples of the pigment dispersion method include a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill. A bead mill is preferred from the viewpoint of dispersion efficiency and fine dispersion. Examples of the bead mill include a coball mill, a basket mill, a pin mill, and a dyno mill. As beads used in the bead mill, for example, titania beads, zirconia beads, or zircon beads are preferable. The diameter of the beads used for dispersion is preferably 0.01 to 5.0 mm, more preferably 0.03 to 1.0 mm. When the primary particle diameter of the pigment or the secondary particles formed by agglomeration of the primary particles is small, the bead diameter used for dispersion is preferably as small as 0.03 to 0.10 mm. In this case, it is preferable to disperse using a bead mill having a separator by a centrifugal separation method capable of separating fine beads and a dispersion. On the other hand, when a pigment containing coarse particles of about submicron is dispersed, beads having a bead diameter of 0.10 mm or more are preferable in order to obtain a sufficient crushing force.

  The example of the manufacturing method of the resin BM board | substrate of this invention is shown below. First, a photosensitive colored resin composition is applied on a transparent substrate. Examples of the method for applying the photosensitive colored resin composition on the substrate include a dipping method, a roll coater method, a spinner method, a die coating method or a wire bar method, a method of immersing a substrate in a solution, or a solution on a substrate. The method of spraying is mentioned. In addition, when apply | coating the photosensitive coloring resin composition on a board | substrate, by processing the board | substrate surface with adhesion assistants, such as a silane coupling agent, an aluminum chelating agent, or a titanium chelating agent, a coating film and a board | substrate are carried out. Adhesive force can be improved.

  Examples of the transparent substrate include quartz glass, borosilicate glass, aluminosilicate glass, or inorganic glass such as soda lime glass whose surface is coated with silica; or an organic plastic film or sheet.

  After the photosensitive colored resin composition is applied onto the substrate, the coating film is heated and dried and cured by air drying, heat drying, vacuum drying, or the like to form a dry film. In order to suppress drying unevenness and transport unevenness when forming a dry film, it is preferable to heat cure after the substrate coated with the photosensitive colored resin composition is dried under reduced pressure with a vacuum dryer equipped with a heating device.

  The obtained dry film is subjected to pattern processing using a method such as photolithography after forming an oxygen blocking film as required. Thereafter, if necessary, after removing the oxygen blocking film, the resin BM is obtained by further drying by heating and curing. Although thermosetting conditions differ with resin, when using an acrylic resin, it is preferable to heat at 200-250 degreeC for 1 to 60 minutes.

  The reflection chromaticity of the resin BM is calculated from the CIE L * a * b * color system using the reflection spectrum for the standard C light source, measured from the surface on the substrate side, according to the method of JIS-Z8729. Generally, the chromaticity values (a *, b *) are used. However, since the resin BM in the resin BM substrate of the present invention is composed of multiple layers, the light reflected at the interface of each layer interferes, and the measured value may not match the visually recognized hue. Therefore, in the present invention, a sample BM formed with printing ink was used as a comparison object, and a judgment was made by visual sensory evaluation under sunlight. The reflected color tone is preferably less glossy and has a bluish reflective color tone.

  The touch panel substrate of the present invention is obtained by further forming an insulating film and a transparent electrode on the resin BM substrate of the present invention.

  A manufacturing example of a touch panel substrate manufactured using the resin BM substrate of the present invention will be described below with reference to FIGS. 1 and 2. First, after forming the first resin BM3 and the second resin BM4 on the transparent substrate 2, the jumper wiring 5 made of a transparent electrode such as ITO is formed on the transparent substrate 2. As a method for manufacturing the jumper wiring, for example, the following method can be used. First, an ITO film is formed on the transparent substrate 2 on which the two-layer BM is formed by a sputtering method or a vacuum evaporation method. A novolac positive resist is applied on the ITO film, the positive resist is dried, exposed and developed, and then the ITO film is etched with an acid to pattern the ITO film. Thereafter, the jumper wiring 5 is formed by peeling the positive resist with alkali.

  Subsequently, a first insulating film 6 is formed on the jumper wiring 5. Simultaneously with the formation of the first insulating film 6, the second insulating film 10 may be formed on the resin BM for the purpose of protecting the resin BM. As the insulating film, both an organic film and an inorganic film are preferably used. The insulating film made of an organic film is formed by applying, drying, exposing, developing, and heat-curing a general acrylic negative resist.

  Next, the metal wiring 7 is formed on the resin BM and / or on the second insulating film. As a method for forming the metal wiring, for example, a metal film having a three-layer structure in which a Mo layer, an Al layer, and a Mo layer are sequentially formed is formed by sputtering, and then the metal film is patterned in the same manner as the jumper wiring. The method of performing is mentioned.

  Next, the transparent electrode 8 is formed on the transparent substrate 2 in the same manner as the jumper wiring 5 so as to be electrically connected to the metal wiring 7.

  Finally, the protective film 9 is formed so as to cover each member formed as described above. As the protective film 9, both an organic film and an inorganic film are preferably used.

  The color filter of the present invention is one in which red, green or blue pixels are formed in a portion (hereinafter referred to as an opening) where the two-layer resin BM is not formed on the resin BM substrate of the present invention.

  As a manufacturing method of the color filter substrate of the present invention, for example, after forming a two-layer resin BM on a transparent substrate, red, green or blue pixels are formed by a known method.

  Examples of the material of the pixel include an inorganic film whose film thickness is controlled so as to transmit only arbitrary light, or a colored resin film in which a dye or pigment is dispersed in a binder resin. Among these, a colored resin film in which a pigment is dispersed in a binder resin is preferable. Examples of the binder resin include acrylic copolymer, polyvinyl alcohol, polyamide, and polyimide. From the viewpoint of heat resistance and chemical resistance, polyimide is preferable.

  As the pigment, those excellent in light resistance, heat resistance and chemical resistance are preferable.

  Examples of red pigments include C.I. I. Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 190, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240 or 254.

  Examples of the orange pigment include C.I. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 or 71.

  Examples of yellow pigments include C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 83, 86, 93, 94, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 173, 180 or 185.

  Examples of purple pigments include C.I. I. Pigment violet 19, 23, 29, 30, 32, 36, 37, 38, 40 or 50.

  Examples of the blue pigment include C.I. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 22, 60, 64 or 80.

  Examples of the green pigment include C.I. I. Pigment green 7, 10, 36 or 58.

  These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment or the like, and a pigment derivative may be added as a dispersant as required.

  An overcoat film may be formed on the pixel as necessary. Examples of the overcoat film include an epoxy film, an acrylic epoxy film, an acrylic film, a siloxane polymer film, a polyimide film, a silicon-containing polyimide film, and a polyimidesiloxane film. A transparent conductive film may be further formed on the overcoat film. Examples of the transparent conductive film include an oxide thin film such as ITO having a film thickness of about 0.1 μm. Examples of the method for producing the ITO film include a sputtering method and a vacuum evaporation method.

A liquid crystal display device can be produced by laminating the color filter substrate and the counter substrate of the present invention and filling a gap between them with a liquid crystal compound.
May form a fixed spacer. The fixed spacer refers to a spacer that is fixed at a specific location on the color filter substrate and contacts the counter substrate when a liquid crystal display device is manufactured. Thus, a certain gap is maintained between the counter substrate and the liquid crystal compound is filled between the gaps. By forming the fixed spacer, it is possible to omit the step of dispersing the spherical spacer in the manufacturing process of the liquid crystal display device and the step of kneading the rod-shaped spacer in the sealing agent.

  A display device can be manufactured by bonding the color filter substrate of the present invention and a light emitting element.

  As the light emitting element, an organic electroluminescence element (hereinafter referred to as “organic EL element”) is preferable. The display device of the present invention effectively shields excess light from the light emitting element in black display and suppresses reflection of external light by utilizing the feature that the two-layer resin BM substrate has high OD and low reflection. A clear display with high contrast can be obtained.

  Furthermore, when a polyimide resin film is used as the transparent substrate of the resin BM substrate of the present invention, a flexible color filter substrate can be produced. A flexible display device can be obtained by bonding the flexible color filter substrate and the light emitting element. If an organic EL element is used as the light emitting element, a flexible organic EL display can be produced.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these.

<Evaluation method>
[Transparent chromaticity coordinates]
A resin BM having a desired film thickness is formed on a chemically tempered glass (Gorilla; manufactured by Corning) having a thickness of 0.7 mm and measured using a microspectroscope (MCPD2000; manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a two-degree field of view. The transmission chromaticity coordinates in the CIE 1931 color system were measured.

[OD value]
The OD value of the two-layer resin BM is determined by measuring the two-layer resin BM formed on the transparent substrate using a microspectroscope (manufactured by Otsuka Electronics Co., Ltd., MCPD300). It calculated from Formula (1).

The OD value per 1 μm thickness of the resin BM is such that a resin BM having a thickness of 1.0 μm is formed on a chemically tempered glass having a thickness of 0.7 mm, and the resin BM is obtained using a microspectroscope (manufactured by Otsuka Electronics, MCPD300) The intensity of each of the incident light and transmitted light from the coating surface was measured and calculated from the following formula (1).
OD value = log ₁₀ (I ₀ / I) (1)
I ₀ : Incident light intensity I: Transmitted light intensity.

[Reflection chromaticity]
A resin BM having a desired film thickness is formed on a chemically tempered glass having a thickness of 0.7 mm, and the reflection chromaticity from the glass surface is measured using a spectroscopic clock (UV-2500PC; manufactured by Shimadzu Corporation) (measurement). Wavelength region: 300 to 780 nm, sampling pitch: 1.0 nm, scan speed: low speed, slit width: 2.0 nm).

[Reflection color tone]
A black printing ink (GLS-912; manufactured by Teikoku Ink) was printed on a chemically tempered glass having a thickness of 0.7 mm using a 230 mesh plate so that the thickness after drying was 10 μm, and then at 150 ° C. for 30 minutes. Oven drying was performed to prepare a sample BM.

A desired resin BM was formed on a chemically tempered glass having a thickness of 0.7 mm, and visually compared with the above sample BM under sunlight, and the reflection color tone was determined based on the following criteria.
A: Very good visibility (black with deep black)
B: Good visibility (blue with bluish color)
C: Visibility is poor (grayish black)
(Synthesis of acrylic polymer (P-1))
100 parts by mass of the copolymer obtained after synthesizing a methyl methacrylate / methacrylic acid / styrene copolymer (mass composition ratio 30/40/30) by the method described in the literature (Japanese Patent No. 3120476; Example 1) On the other hand, 40 parts by mass of glycidyl methacrylate was added and reprecipitated with purified water. The obtained precipitate was filtered and dried to obtain an acrylic polymer (P-1) powder having an average molecular weight (Mw) of 10,000 and an acid value of 110 (mgKOH / g).

(Manufacture of colorant dispersion)
120 g of blue organic pigment PB15: 6 (manufactured by Toyo Ink Co., Ltd.), 114 g of a 35% by weight solution of propylene glycol monomethyl ether acetate (hereinafter “PMA”) of acrylic polymer (P-1), disperser as a polymer dispersant 100 g of Big LPN-21116 (DP-1; manufactured by Big Chemie; 40% by mass solution of PMA) and 666 g of PMA were charged in a tank and stirred for 20 minutes with a homomixer (manufactured by PRIMIX) to obtain a preliminary dispersion. Thereafter, the preliminary dispersion was supplied to an ultra apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 0.05 mmφ zirconia beads (YTZ balls; manufactured by Netulen) and dispersed for 3 hours at a rotational speed of 8 m / s. And a colorant dispersion DB-1 having a solid content concentration of 20% by mass and a colorant / resin (mass ratio) = 60/40 was obtained.

  A colorant dispersion DR-1 was obtained in the same manner as the colorant dispersion DB-1, except that a red organic pigment PR254 (manufactured by BASF) was used instead of the blue organic pigment PB15: 6 as the colorant.

  A colorant dispersion DV-1 was obtained in the same manner as the colorant dispersion DB-1, except that a purple organic pigment PV23 (manufactured by Clariant) was used instead of the blue organic pigment PB15: 6 as the colorant.

  175 g of high resistance carbon black (manufactured by Cabot Corporation), 171 g of 35% by weight PMA solution of acrylic polymer (P-1), 38 g of Dispersic LPN-21116 and 616 g of PMA as a polymer dispersant were charged in a tank, and a homomixer And stirred for 20 minutes to obtain a preliminary dispersion. Thereafter, the preliminary dispersion is supplied to an ultra apex mill equipped with a centrifugal separator filled with 0.05% φ zirconia beads 75%, and dispersed for 3 hours at a rotational speed of 8 m / s. / Resin (mass ratio) = 70/30 colorant dispersion DK-1 was obtained.

  200 g of titanium nitride particles (manufactured by Nissin Engineering Co., Ltd.) produced by a thermal plasma method, 114 g of a 35% by weight PMA solution of acrylic polymer (P-1), a tertiary amino group and a quaternary ammonium as a polymer dispersant Dispersic LPN-21116 having a base (25 g) and PMA (661 g) were charged into a tank and stirred with a homomixer for 20 minutes to obtain a preliminary dispersion. Thereafter, the pre-dispersed liquid was supplied to an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 75% 0.05 mmφ zirconia beads, and dispersed at a rotational speed of 8 m / s for 3 hours to obtain a solid concentration of 25 A colorant dispersion DK-2 having a mass% of colorant / resin (mass ratio) = 80/20 was obtained.

(Production of Colored Resin Composition A-1)
PMA (50.93 g) and Adeka Arcles (registered trademark) NCI-831 (1.25 g) as a photopolymerization initiator were added and stirred until the solid content was dissolved.

  Furthermore, 24.94 g of a 35% by weight PMA solution of acrylic polymer (P-1), 6.24 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, and KBM5103 (Shin-Etsu Chemical) as an adhesion improver 0.60 g of Co., Ltd.) and 0.40 g of PMA 10% by mass solution of silicone surfactant BYK333 as a surfactant were added and stirred at room temperature for 1 hour to obtain a photosensitive resist. By adding 6.25 g of blue pigment dispersion DB-1 and 9.38 g of red pigment dispersion DR-1 to this photosensitive resist, the total solid content concentration is 20%, and pigment / resin (mass ratio) = 10/90. A photosensitive colored resin composition A-1 having a blue pigment / red pigment (mass ratio) of 40/60 was prepared.

(Production of colored resin composition A-2)
1.06 g of Adeka Arcles (registered trademark) NCI-831 as a photopolymerization initiator was added to 42.00 g of PMA and stirred until the solid content was dissolved.

  Furthermore, 19.08 g of PMA 35 mass% solution of acrylic polymer (P-1), 5.29 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.), 0.60 g of KBM5103, silicone surfactant BYK333 0.40 g of a PMA 10 mass% solution was added and stirred at room temperature for 1 hour to obtain a photosensitive resist. By adding 12.63 g of the blue pigment dispersion DB-1 and 18.94 g of the red pigment dispersion DR-1 to this photosensitive resist, the total solid concentration is 20%, and the pigment / resin (mass ratio) = 20/80. A photosensitive colored resin composition A-2 having a blue pigment / red pigment (mass ratio) of 40/60 was prepared.

(Production of colored resin composition A-3)
0.67 g of Adeka Arcles (registered trademark) NCI-831 was added to 23.57 g of PMA and stirred until the solid content was dissolved.

  Further, 6.98 g of PMA 35% by mass solution of acrylic polymer (P-1), 3.35 g of dipentaerythritol hexaacrylate, 0.60 g of KBM5103, 0.40 g of PMA 10% by mass of silicone surfactant BYK333. The resultant was added and stirred at room temperature for 1 hour to obtain a photosensitive resist. By adding 25.77 g of the blue pigment dispersion DB-1 and 38.66 g of the red pigment dispersion DR-1 to this photosensitive resist, the total solid content concentration is 20%, and the pigment / resin (mass ratio) = 40/60. A photosensitive colored resin composition A-3 having a blue pigment / red pigment (mass ratio) of 40/60 was prepared.

(Production of colored resin composition A-4)
Similar to the colored resin composition A-2 except that 18.94 g of the blue pigment dispersion DB-1 and 12.63 g of the red pigment dispersion DR-1 were added, the total solid content concentration was 20%, and the pigment / resin ( A photosensitive colored resin composition A-4 having a mass ratio of 20/80 and a blue pigment / red pigment (mass ratio) of 60/40 was prepared.

(Production of colored resin composition A-5)
As the colored pigment dispersion, the same procedure as in the colored resin composition A-2 except that 31.57 g of the violet pigment dispersion DV-1 was added instead of the blue pigment dispersion DB-1 and the red pigment dispersion DR-1. A photosensitive colored resin composition A-5 having a total solid content concentration of 20%, a pigment / resin (mass ratio) = 20/80, and a purple pigment = 100 was prepared.

(Production of colored resin composition A-6)
Similar to the colored resin composition A-2 except that 25.26 g of the blue pigment dispersion DB-1 and 6.31 g of the red pigment dispersion DR-1 were added, a total solid content concentration of 20%, pigment / resin ( A photosensitive colored resin composition A-6 having a mass ratio) = 20/80 and a blue pigment / red pigment (mass ratio) = 80/20 was prepared.

(Production of colored resin composition A-7)
Similar to the colored resin composition A-2, except that the red pigment dispersion DR-1 was not added and 31.57 g of the blue pigment dispersion DB-1 was added. A photosensitive colored resin composition A-7 having a mass ratio of 20/80 and a blue pigment of 100 was prepared.

(Production of colored resin composition A-8)
The same as in the colored resin composition A-2 except that 6.31 g of the blue pigment dispersion DB-1 and 25.26 g of the red pigment dispersion DR-1 were added. A photosensitive colored resin composition A-8 having a mass ratio) = 20/80 and a blue pigment / red pigment (mass ratio) = 20/80 was prepared.

(Production of colored resin composition A-9)
1.35 g of Adeka Arcles (registered trademark) NCI-831 was added to 50.15 g of PMA and stirred until the solid content was dissolved.

  Furthermore, 20.50 g of PMA 35% by mass solution of acrylic polymer (P-1), 5.65 g of dipentaerythritol hexaacrylate, 0.60 g of KBM5103, and 0.40 g of PMA 10% by mass of silicone surfactant BYK333. The resultant was added and stirred at room temperature for 1 hour to obtain a photosensitive resist. 21.57 g of carbon black dispersion DK-1 is added to this photosensitive resist to give a photosensitive colored resin composition having a total solid concentration of 20%, pigment / resin (mass ratio) = 20/80, and carbon black = 100. A-9 was prepared.

(Production of colored resin composition A-10)
51.04 g of PMA and 1.14 g of Adeka Arcles (registered trademark) NCI-831 were added and stirred until the solid content was dissolved.

  Furthermore, PMA 35 mass% solution of acrylic polymer (P-1) 22.26 g, dipentaerythritol hexaacrylate 5.70 g, KBM 5103 0.60 g, silicone surfactant BYK333 PMA 10 mass% solution 0.40 g The resultant was added and stirred at room temperature for 1 hour to obtain a photosensitive resist. By adding 18.86 g of titanium nitride dispersion DK-2 to this photosensitive resist, a photosensitive colored resin having a total solid content of 20%, pigment / resin (mass ratio) = 20/80, and titanium nitride = 100 Composition A-10 was prepared.

(Production of colored resin composition B-1)
To 37.78 g of PMA, Adeka Arcles (registered trademark) NCI-831 (0.73 g) was added and stirred until the solid content was dissolved.

  Furthermore, 7.78 g of PMA 35% by mass solution of acrylic polymer (P-1), 3.63 g of dipentaerythritol hexaacrylate, 0.60 g of KBM5103, and 0.40 g of PMA 10% by mass of silicone surfactant BYK333. The resultant was added and stirred at room temperature for 1 hour to obtain a photosensitive resist. By adding 38.00 g of carbon black dispersion DK-1 and 11.08 g of titanium nitride dispersion DK-2 to this photosensitive resist, the total solid content concentration is 20%, pigment / resin (mass ratio) = 46 / 54, photosensitive colored resin composition B-1 having carbon black / titanium nitride (mass ratio) = 75/25 was prepared.

Example 1
The prepared photosensitive colored resin composition A-1 is filtered through a 2 μm Teflon (registered trademark) filter, and then applied onto a 0.7 μm thick chemically strengthened glass substrate so that the film thickness becomes 1.5 μm (after post-baking). It was applied with a spin coating apparatus 1H-DS manufactured by Mikasa Corporation. The substrate on which the photosensitive colored resin composition A-1 was applied was heat-treated for 2 minutes with pin-shaped protrusions on a 90 ° C. hot plate, and further pre-baked by leaving the substrate directly on the hot plate for 2 minutes. . A mask aligner (PEM-6M; manufactured by Union Optical Co., Ltd.) was used for the coating film, and ultraviolet rays were exposed at an exposure amount of 200 mJ / cm ² through a resolution test mask.

  Next, it developed with the alkaline developing solution of 0.045 mass% potassium hydroxide aqueous solution, and the patterning board | substrate was obtained by wash | cleaning a pure water subsequently. The obtained patterning substrate was held in a hot air oven at 230 ° C. for 30 minutes and post-baked to obtain a BM (A) -1 substrate.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -1 substrate. 1 was formed to prepare a two-layer BM-1.

(Example 2)
A BM (A) -2 substrate was obtained in the same manner as BM (A) -1, except that A-2 was used as the photosensitive colored resin composition.

  Except for using B-1 as the photosensitive colored resin composition, BM (B)-was used in the same manner as BM (A) -1 so that the film thickness was 1.4 μm on the BM (A) -2 substrate. 1 was formed to prepare a two-layer BM-2.

(Example 3)
A BM (A) -3 substrate was obtained in the same manner as BM-1, except that A-2 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -3 substrate. 1 was formed to prepare a two-layer BM-3.

Example 4
A BM (A) -4 substrate was obtained in the same manner as BM-1, except that A-2 was used as the photosensitive colored resin composition and the film thickness was 0.7 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -4 substrate. 1 was formed to prepare a two-layer BM-4.

(Example 5)
A BM (A) -5 substrate was obtained in the same manner as BM-1, except that A-3 was used as the photosensitive colored resin composition and the film thickness was 1.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -5 substrate. 1 was formed to prepare a two-layer BM-6.

(Example 6)
A BM (A) -6 substrate was obtained in the same manner as BM-1, except that A-3 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -6 substrate. 1 was formed to prepare a two-layer BM-6.

(Example 7)
A BM (A) -7 substrate was obtained in the same manner as BM-1, except that A-3 was used as the photosensitive colored resin composition and the film thickness was 0.7 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -7 substrate. 1 was formed to prepare a two-layer BM-7.

(Example 8)
A BM (A) -8 substrate was obtained in the same manner as BM-1, except that A-4 was used as the photosensitive colored resin composition and the film thickness was 1.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -8 substrate. 1 was formed to prepare a two-layer BM-8.

Example 9
A BM (A) -9 substrate was obtained in the same manner as BM-1, except that A-4 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -9 substrate. 1 was formed to prepare a two-layer BM-9.

(Example 10)
A BM (A) -10 substrate was obtained in the same manner as BM-1, except that A-4 was used as the photosensitive colored resin composition and the film thickness was 0.7 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -10 substrate. 1 was formed to prepare a two-layer BM-10.

(Example 11)
A BM (A) -11 substrate was obtained in the same manner as BM-1, except that A-5 was used as the photosensitive colored resin composition and the film thickness was 1.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -11 substrate. 1 was formed to prepare a two-layer BM-11.

(Example 12)
A BM (A) -12 substrate was obtained in the same manner as BM-1, except that A-5 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -12 substrate. 1 was formed to prepare a two-layer BM-12.

(Example 13)
A BM (A) -13 substrate was obtained in the same manner as BM-1, except that A-5 was used as the photosensitive colored resin composition and the film thickness was 0.7 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -13 substrate. 1 was formed to prepare a two-layer BM-13.

(Example 14)
A BM (A) -14 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 1.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -14 substrate. 1 was formed to prepare a two-layer BM-14.

(Example 15)
A BM (A) -15 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -15 substrate. 1 was formed to prepare a two-layer BM-15.

(Example 16)
A BM (A) -16 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 0.7 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -16 substrate. 1 was formed to prepare a two-layer BM-16.

(Example 17)
A BM (A) -17 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was 1.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -17 substrate. 1 was formed to prepare a two-layer BM-17.

(Example 18)
A BM (A) -18 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -18 substrate. 1 was formed to prepare a two-layer BM-18.

(Example 19)
A BM (A) -19 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was 0.7 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -19 substrate. 1 was formed to prepare a two-layer BM-19.

(Comparative Example 1)
A BM (A) -20 substrate was obtained in the same manner as BM-1, except that A-1 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -20 substrate. 1 was formed to prepare a two-layer BM-20.

(Comparative Example 2)
A BM (A) -21 substrate was obtained in the same manner as BM-1, except that A-2 was used as the photosensitive colored resin composition and the film thickness was 0.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -21 substrate. 1 was formed to prepare a two-layer BM-21.

(Comparative Example 3)
A BM (A) -22 substrate was obtained in the same manner as BM-1, except that A-3 was used as the photosensitive colored resin composition and the film thickness was 0.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness is 1.4 μm on the BM (A) -22 substrate. 1 was formed to prepare a two-layer BM-22.

(Comparative Example 4)
A BM (A) -23 substrate was obtained in the same manner as BM-1, except that A-4 was used as the photosensitive colored resin composition and the film thickness was 0.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -23 substrate. 1 was formed to prepare a two-layer BM-23.

(Comparative Example 5)
A BM (A) -24 substrate was obtained in the same manner as BM-1, except that A-5 was used as the photosensitive colored resin composition and the film thickness was 0.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -24 substrate. 1 was formed to prepare a two-layer BM-24.

(Comparative Example 6)
A BM (A) -25 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 1.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -25 substrate. 1 was formed to prepare a two-layer BM-25.

(Comparative Example 7)
A BM (A) -26 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness is 1.4 μm on the BM (A) -26 substrate. 1 was formed to prepare a two-layer BM-26.

(Comparative Example 8)
A BM (A) -27 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was 1.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -27 substrate. 1 was formed to prepare a two-layer BM-27.

(Comparative Example 9)
A BM (A) -28 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -28 substrate. 1 was formed to prepare a two-layer BM-28.

(Comparative Example 10)
A BM (A) -29 substrate was obtained in the same manner as BM-1, except that A-8 was used as the photosensitive colored resin composition and the film thickness was 1.5 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -29 substrate. 1 was formed to prepare a two-layer BM-29.

(Comparative Example 11)
A BM (A) -30 substrate was obtained in the same manner as BM-1, except that A-8 was used as the photosensitive colored resin composition and the film thickness was 1.0 μm.

  Except for using B-1 as the photosensitive colored resin composition, the same as BM (A) -1, BM (B)-so that the film thickness becomes 1.4 μm on the BM (A) -30 substrate. 1 was formed to prepare a two-layer BM-30.

(Reference Example 1)
Single layer BM so that the film thickness is 1.4 μm on the glass substrate in the same manner as BM (A) -1, except that A-1 is not used as the photosensitive colored resin composition and B-1 is used. -31 was formed.

(Reference Example 2)
A black printing ink (GLS-912; manufactured by Teikoku Ink Co., Ltd.) is printed on a chemically strengthened glass substrate with a thickness of 0.7 mm using a 230 mesh plate so that the thickness after drying is 10 μm, and then oven-dried at 150 ° C. for 30 minutes. A single layer BM-32 was formed.

Table 1 shows the composition of the colorant dispersion used in Examples 1 to 19 and Comparative Examples 1 to 12, and Table 2 shows the composition of the photosensitive colored resin composition. Tables 3 and 4 show the evaluation results of BM (A), BM (B), and two-layer BM prepared using the photosensitive colored resin composition. In addition, Examples 17-19 are comparative examples now, and Examples 1-16 are Examples of this invention.

  It can be seen that the two-layer BM produced in the example has a thin film thickness of 3.0 μm and a high light-shielding property of OD = 4.5 or more, but has a low reflectance and a good color tone of reflection. In addition, since a pigment is used as the coloring material, it is excellent in chemical resistance and heat resistance as compared with BM using a dye.

  The resin BM substrate of the present invention can be preferably used as a BM substrate and a decoration substrate of a display device such as a liquid crystal display device, an organic EL display device, an inorganic EL display device, or a plasma display display device. It can be used more preferably as a cover glass integrated touch panel resin BM substrate.

DESCRIPTION OF SYMBOLS 1 Touch panel substrate 2 Transparent substrate 3 1st resin black matrix 4 2nd resin black matrix 5 Jumper wiring 6 1st insulating film 7 Metal wiring 8 Transparent electrode 9 Transparent protective film 10 2nd insulating film

Claims (9)

A transparent substrate;
A first resin black matrix formed on the transparent substrate;
A second resin black matrix formed on the first resin black matrix,
The first resin black matrix contains a blue pigment and a red pigment, or contains a purple pigment,
The film thickness of the first resin black matrix is 0.7 μm or more, and the transmission chromaticity coordinates are in the ranges of 0.150 ≦ x ≦ 0.300 and 0.010 ≦ y ≦ 0.250. ,
A resin black matrix substrate, wherein an optical density of a two-layer resin black matrix comprising the first resin black matrix and the second resin black matrix is 3.5 or more.   The resin black matrix substrate according to claim 1, wherein the optical density per 1 μm of film thickness of the first resin black matrix is 0.5 to 2.0.   The resin black matrix substrate according to claim 1, wherein the second resin black matrix contains a black pigment.   The resin black matrix substrate according to claim 3, wherein the black pigment is carbon black or titanium nitride.   The touch panel in which the insulating film and the transparent electrode were further formed on the resin black matrix substrate as described in any one of Claims 1-4.   A color filter substrate in which red, green, or blue pixels are formed in the opening of the resin black matrix substrate according to claim 1.   A liquid crystal display device in which the color filter substrate according to claim 6 and a counter substrate are bonded together and a liquid crystal compound is filled in a gap between the two.   A display device comprising the color filter substrate according to claim 6 and a light emitting element bonded together.   The display device according to claim 8, wherein the light emitting element is an organic EL element.

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