KR100860432B1 - Black photosensitive composition - Google Patents

Abstract

Provided are black photosensitive compositions capable of forming a black matrix having high shape stability against heat. Moreover, this invention provides the black matrix formed from this black photosensitive composition, the partition for inkjet type color filters, and the spacer for liquid crystal display elements. In the black photosensitive composition containing a photopolymerizable compound, a photoinitiator, and a black pigment, the organic pigment was contained as a shape stabilizer.

Shape stability, black matrix, black photosensitive composition, color filter, bulkhead

Description

Black photosensitive composition {BLACK PHOTOSENSITIVE COMPOSITION}

Patent Document 1: Japanese Patent Application Laid-Open No. 6-289216

The present invention relates to a black photosensitive composition. Specifically, it relates to a black photosensitive composition for forming a light shielding film such as a black matrix.

A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which paired electrodes are formed to face each other. Then, inside one substrate, a color filter having pixels consisting of colors such as red (R), green (G), and blue (B) is formed. In this color filter, in order to prevent mixing of different colors in each pixel, or to hide a pattern of electrodes, a matrix shape is usually formed so as to partition pixels of R, G, and B colors. A black matrix arranged as is formed. In general, color filters are formed by lithography. Specifically, first, a black photosensitive composition is coated, exposed and developed on a substrate to form a black matrix. Subsequently, application | coating, exposure, and image development are repeated for every photosensitive composition of red (R), green (G), and blue (B), and the pattern of each color is formed in a predetermined position, and a color filter is formed.

Moreover, in order to provide light-shielding property, the conventional photosensitive composition for black matrix formation may contain organic pigment as an auxiliary pigment other than carbon black (refer patent document 1).

However, in order to provide high light-shielding property to a black matrix, it is necessary to increase the content of the light-shielding material or to increase the film thickness. Therefore, optical density became high, and light might not reach the deep part of a film | membrane at the time of exposure, and photocuring (photosensitive reaction) did not fully advance. As a result, development margin narrowed, the linearity of a pattern became low, a pattern peeled off from a board | substrate, and the dregs might generate | occur | produce on a board | substrate.

In addition, in the case of forming a color filter using an ink jet method which has been attracting attention in recent years, in the conventional black matrix, when the ink composition is sprayed from above, the ink composition may come out of the pattern. Therefore, in order to prevent this ink composition from coming off, it was necessary to enlarge the film thickness of a black matrix.

As described above, when the black matrix is a thick film, there is a problem that wrinkles occur on the pattern surface. In addition, when the black matrix is a thin film, it is difficult to occur, but there is a problem that the film is deformed during the heat treatment.

In view of the above problems, it is an object of the present invention to provide a black photosensitive composition for forming a black matrix capable of forming a black matrix having high shape stability against heat. Moreover, an object of this invention is to provide the black matrix formed from this black photosensitive composition, the partition for inkjet type color filters, and the spacer for liquid crystal display elements.

The inventors found that incorporating a shape stabilizer into the black photosensitive composition is effective for stabilizing the shape of the black matrix. Specifically, it has been found that it is effective to contain an organic pigment as a shape stabilizer, and the present invention has been completed.

The present invention provides a black photosensitive composition containing a photopolymerizable compound, a photopolymerization initiator, and a black pigment, a black photosensitive composition containing an organic pigment as a shape stabilizer, a black matrix formed from the black photosensitive composition, a partition for an inkjet type color filter, and It is to provide a spacer for a liquid crystal display device.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

The black photosensitive composition which concerns on this invention contains a photopolymerizable compound, a photoinitiator, and a black pigment, and contains the organic pigment as a shape stabilizer.

[Photopolymerizable Compound]

A "photopolymerizable compound" means the substance which superposes | polymerizes and hardens | cures by irradiation of light, such as an ultraviolet-ray. As the photopolymerizable compound, a compound having an ethylene double bond is preferable.

<Compound Having Ethylenic Double Bond>

Examples of the compound having an ethylenic double bond include acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, 2 -Hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate (ethyleneglycol monoethyl ether methacrylate), glycerol acrylic Glycerol methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate Acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacryl Rate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol di Acrylate (tetraethyleneglycol diacrylate), tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , Tetramethylolpropane tetra acrylate, tetramethylol propane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetrametha Krill Rate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate (1, 6- monomers, oligomers such as hexanediol diacrylate, 1,6-hexanediol dimethacrylate and cardo epoxy diacrylate; condensation of polyhydric alcohols with monobasic or polybasic acids A compound having a polyester (meth) acrylate, a polyol group and two isocyanate groups obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by Polyurethane (meth) acrylate, obtained by reacting (meth) acrylic acid after the reaction; bisphenol A (bisphenol A) type epoxy ), Bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycid Epoxy (meth) obtained by reacting (meth) acrylic acid with an epoxy resin such as a polyglycidyl polycarboxylate ester, a polyol polyglycidyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, or a dihydroxybenzene type epoxy resin An acrylate resin etc. are mentioned. Moreover, resin which made polybasic acid anhydride react with the said epoxy (meth) acrylate resin can be used. Since these compounds have acryloyl or methacryloyl groups introduced therein, the crosslinking efficiency is high, and the light resistance and chemical resistance of the coating film are excellent.

Especially, it is preferable to use resin which has a cardo structure in a molecule | numerator. Since resin which has a cardo structure has high heat resistance and chemical-resistance, it can improve the heat resistance and chemical resistance of a black photosensitive composition by using it for a photopolymerizable compound. It is preferable to use resin represented by following General formula (1) specifically ,.

In the formula, X is a group represented by the following general formula (2), Y is a residue excluding an carboxylic anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. , Z is a residue except two carboxylic anhydride groups in tetracarboxylic dianhydride, n is an integer from 1 to 20.

As a specific example of the said dicarboxylic acid anhydride (dicarboxylic acid anhydride before removing a carboxylic acid anhydride group) which induces said Y, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride (phthalic acid anhydride), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic acid anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc. Can be mentioned.

Moreover, as a specific example of the tetracarboxylic dianhydride (tetracarboxylic dianhydride before removing two carboxylic anhydride groups) which induces said Z, pyromellitic acid anhydride and benzophenone are mentioned, for example. Tetracarboxylic dianhydride, such as a tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, and a biphenyl ether tetracarboxylic dianhydride, etc. are mentioned.

Moreover, it is preferable that the compound which has the said ethylenic double bond has a mass mean molecular weight of 1,000 or more. By making a mass average molecular weight 1,000 or more, a coating film can be made uniform. Moreover, it is preferable that mass average molecular weight shall be 100,000 or less. Developability can be made favorable by making a mass mean molecular weight 100,000 or less. In this invention, the compound which has this mass average molecular weight 1,000 or more ethylenic double bond shall be called the high molecular compound which has ethylenic double bond.

Moreover, it is preferable to use the high molecular compound which has the said ethylenic double bond in combination with a photopolymerizable monomer. As this photopolymerizable monomer, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ethylene glycol diacrylate, and ethylene glycol dimethacrylate Ethylene (ethyleneglycol dimethacrylate), triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol Trimetacrylic Yite, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate 1,6-hexanediol diacrylate, benzyl acrylate, benzyl methacrylate, cardo epoxy diacrylate, acrylic acid, methacrylic acid, and the like. It is not limited to these. Especially, a polyfunctional photopolymerizable monomer is preferable. Thus, by combining the high molecular compound and the photopolymerizable monomer which have an ethylenic double bond, hardenability can be improved and pattern formation can be made easy.

In the above, although the molecule | numerator itself was mentioned as a photopolymerizable compound, in this invention, the mixture of a polymeric binder and a photopolymerizable monomer shall also be included in a photopolymerizable compound.

As a polymeric binder, it is preferable that it is a binder which can develop a base for ease of image development.

Specifically, a monomer having a carboxyl group such as acrylic acid and methacrylic acid as a polymer binder, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacryl Latex, 2-hydroxypropyl methacrylate, N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, Phenoxyacrylates, phenoxymethacrylates, isobonyl acrylates, isobonyl methacrylates, copolymers with glycidyl methacrylates, styrene, acrylamides, acrylonitrile and the like, and phenol novolacs (phenol novolak) type epoxy acrylate polymer, phenol novolak type epoxy methacrylate polymer, cresol novolak type Resin, such as an epoxy acrylate polymer, a cresol novolak-type epoxy methacrylate polymer, a bisphenol A (bisphenol A) type epoxy acrylate polymer, and a bisphenol S type epoxy acrylate polymer, is mentioned. As for content of the monomer component which has carboxyl groups, such as acrylic acid and methacrylic acid which comprise the said resin, the range of 5 mol%-40 mol% is preferable.

The preferred range of the mass average molecular weight of the polymeric binder is from 1,000 to 100,000. By making a mass average molecular weight 1,000 or more, a coating film can be made uniform. Moreover, developability can be made favorable by making a mass mean molecular weight 100,000 or less.

When a polymeric binder and a photopolymerizable monomer are included as a photopolymerizable compound, it is preferable that a polymeric binder is mix | blended in the range of 10 mass parts to 60 mass parts per 100 mass parts of total of a polymeric binder, a photopolymerizable monomer, and a photoinitiator. By setting the blending amount to 10 parts by mass or more, it is possible to easily form a film during application and drying, and the film strength after curing can be sufficiently increased. Moreover, developability can be made favorable by making a compounding quantity 60 mass parts or less.

Moreover, it is preferable to mix | blend a photopolymerizable monomer in the range of 15 mass parts to 50 mass parts per 100 mass parts of total of a polymeric binder, a photopolymerizable monomer, and a photoinitiator. By making the said compounding quantity 15 mass parts or more, the photocuring defect can be prevented and sufficient heat resistance and chemical-resistance can be obtained. Moreover, coating film formation ability can be made favorable by using 50 mass parts or less.

[Photoinitiator]

As a photoinitiator, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy- 2-methyl- 1-phenyl propane- 1-one, 1- [4- (2-hydric, for example) Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl- 1-propane- 1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane 1-one, 1- ( 4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, 2, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (2-methyl 1- [4-methylmethyl) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl]-, 1- (O-acetyl oxime), 2, 4, 6- trimethyl benzoyl diphenyl phosphine oxide, 4- benzoyl-4'- methyl dimeth Sulfide, 4-dimethylamino benzoic acid, 4-dimethylamino benzoic acid methyl, 4-dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid butyl acid, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl Benzoic acid, benzyl- (beta)-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl- 1, 2- propanedione 2- (O-ethoxycarbonyl) oxime, O-benzoyl benzoate, 2, 4- diethyl tea Oak xanthene (2, 4-diethylthioxanthene), 2-chlorothioxanthene, 2, 4- dimethyl thioxanthene, 1-chloro-4-propoxy thioxanthene, thioxanthene, 2-chlorothioke Santhene, 2, 4-diethyl thioxanthene, 2-methyl thioxanthene, 2-isopropyl thioxanthene, 2-ethylanthraquinone, octamethyl anthraquinone, 1, 2-benzanthraquinone (1,2-benzanthraquinone), 2, 3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide (be nzoylperoxide, cumeneperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2 -(O-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4, 4 VIII-bisdiethylamino benzophenone, 4, 4- V-dichloro benzophenone, 3, 3- dimethyl- 4-methoxy benzophenone, benzyl, benzoin (benzoin), benzoin methyl ether, benzoin ethyl ether, benzo Phosphorus isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetphenone, 2, 2-diethoxy acetphenone, p-dimethylacetphenone, p-dimethylaminopropiophenone, dichloro Acetphenone, trichloroacetphenone, p-tert-butylacetphenone, p-dimethylaminoacetphenone, p-tert-part Trichloroacetphenone, p-tert- butyldichloroacetphenone, (alpha), (alpha)-dichloro- 4-phenoxyacephenone, thioxanthene, 2-methyl thioxanthene, 2-isopropyl thioxanthene, dibenzosuberon (dibenzosuberone), pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1, 7-bis- (9-acridinyl) heptane, 1, 5-bis- (9-arc) Ridinyl) pentane, 1, 3-bis- (9-acridinyl) propane, p-methoxytriazine, 2, 4, 6-tris (trichloromethyl) -s-triazine, 2-methyl-4 , 6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine), 2- (4- n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo- 4-methoxy) phenyl-s- Triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo -4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine (2,4 -Bis-trichloromethyl-6- (2-brome-4-methoxy) styrylphenyl-s-triazine) etc. are mentioned. You may use these photoinitiators individually or in combination of 2 or more types.

It is preferable that this photoinitiator is contained 1 mass part to 40 mass parts with respect to a total of 100 mass parts of the said photopolymerizable compound and a photoinitiator.

[Black pigment]

The black pigment is not particularly limited as long as it is a pigment having light shielding, and specifically, carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver Inorganic pigments, such as a metal oxide, a composite oxide, a metal sulfide, a metal lead sulfate, or a metal carbonate, etc. are mentioned. It is more preferable to use carbon black which has high light-shielding property among these black pigments.

As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, lamp black, can be used. Moreover, it is preferable to use resin coating carbon black.

Since the resin-coated carbon black has lower conductivity than carbon black without resin coating, leakage of current occurs when used as a black matrix of a liquid crystal display device such as a liquid crystal display. It is possible to form a small liquid crystal display with high reliability.

Moreover, it is preferable to use the polymer dispersing agent of a polyethyleneimine type | system | group, a urethane resin type, and an acrylic resin type as a dispersing agent.

As such a dispersing agent, for example, the brand name BYK-161, 162, 163, 164, 166, 170, 182, the product made by Vikchem Japan Co., Ltd. , S26000, S28000, and the like.

[Shape stabilizer]

The black photosensitive composition which concerns on this invention contains an organic pigment as a shape stabilizer. By containing this organic pigment, the black matrix stable with heat can be formed. Moreover, this organic pigment can also adjust the color of a black pigment. Moreover, by adding an organic pigment, even if it processes at high temperature, it becomes possible to form the pattern with stable shape.

Moreover, by adding this organic pigment, the taper angle of a pattern can be adjusted at the time of forming a black matrix.

As such an organic pigment, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists), specifically the following color index (C.I) number What is attached is mentioned.

CI pigment yellow 1 (hereinafter, "CI pigment yellow" describes the same number only), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 , 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 , 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 , 185;

CI pigment orange 1 (hereafter, "CI pigment orange" lists only the same numbers), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 , 49, 51, 55, 59, 61, 63, 64, 71, 73;

C. I. pigment violet 1 (hereinafter, "C. I. pigment violet" refers to the same number only), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

CI pigment red 1 (hereinafter, "CI pigment red" describes only the numbers in the same way), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 , 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 ： 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 ： 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 , 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215 , 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

CI pigment blue 1 (hereinafter "CI pigment blue" lists only number in the same way), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , 66;

C. I. pigment green 7, C. I. pigment green 36, C. I. pigment green 37;

C. I. pigment brown 23, C. I. pigment brown 25, C. I. pigment brown 26, C. I. pigment brown 28;

C. I. Pigment Black 1, Pigment Black 7.

Moreover, as mentioned above, an organic pigment may function not only as a shape stabilizer but as an auxiliary pigment of carbon black. As an auxiliary pigment, a phthalocyanine pigment, an azo pigment, a basic dye lake pigment, etc. are mentioned, for example.

It is preferable that it is 10:10, and 10:10 is more preferable, and, as for the mass ratio of an organic pigment and a black pigment, it is more preferable that it is 10:10.

Moreover, it is preferable that it is 60 mass%-120 mass% with respect to the total mass of a photopolymerizable compound and a photoinitiator, and, as for the total amount of the said organic pigment and the said black pigment, it is more preferable that it is 105 mass% at 70 mass%. Appropriate sensitivity can be obtained when total amount is 80 mass% or less. Moreover, when the total amount is 10 mass% or more, light shielding property is improved and the function as a black matrix is fully completed.

Preferred among the organic pigments include C. I. pigment blue 15: 6, C. I. pigment red 177, and C. I. pigment yellow 139. These organic pigments can promote the improvement of light-shielding property and the improvement of shape stability more.

[Other ingredients]

In the black photosensitive composition which concerns on this invention, an additive can be mix | blended as needed. Specifically, a sensitizer, a hardening accelerator, a photocrosslinker, a photosensitizer, a dispersing agent, a dispersion adjuvant, a filler, an adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, etc. are mentioned.

In addition, the density | concentration of a black pigment is adjusted so that OD (Optical_Density) value per 1 micrometer of film thickness of a black photosensitive composition may become 4 or more, when forming a black matrix using the black photosensitive composition concerning this invention as mentioned later. It is preferable. When the OD value per film thickness of 1 micrometer of a black photosensitive composition is four or more, sufficient display contrast can be obtained when it uses for the black matrix of a liquid crystal display.

Moreover, when forming a black matrix using the black photosensitive composition which concerns on this invention, the black photosensitive composition of this invention is apply | coated and dried on a board | substrate as mentioned later, and a film is formed. In order to improve the applicability at this time and to improve the physical properties after photocuring, in addition to the above components, a polymer binder may be further included as a binder. What is necessary is just to select a binder suitably according to the objective of improvement, such as compatibility, film formation property, developability, adhesiveness.

As thickness of the black matrix formed on the board | substrate, it can be set normally in the range of 0.5 micrometer-10 micrometers, Preferably it is 1 micrometer-5 micrometers, More preferably, it is 2 micrometers-4 micrometers. If the film thickness is 2 μm or more, it can be used not only as a black matrix for a normal color filter but also as a partition of an inkjet type color filter.

Moreover, when using this black matrix as a partition, it is preferable that profile angle is 50 degrees or more, and it is more preferable that it is 70 degrees or more. Moreover, it is preferable that this profile angle is less than 90 degrees. Here, a "profile angle" means the angle which the surface of a board | substrate and the inclined surface of a pattern make. In addition, the partition wall is formed to have an opening.

When forming a color filter by an inkjet system, an ink composition may come out of the opening part of a partition. However, by setting the profile angle to 50 DEG or more, it is possible to return the ink composition which has deviated even if the ink composition is slightly displaced into the opening, thereby preventing the deviation.

Moreover, the black photosensitive composition which concerns on this invention may add the solvent for dilution, a thermal polymerization inhibitor, an antifoamer, surfactant, etc.

Here, as the solvent which can be added to the black photosensitive composition, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol mono Methyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether , Dipropylene glycol mono-n-butyl ether, tripropylene glycol (Poly) alkyleneglycol monoalkyl ethers such as collonomethyl ether and tripropylene glycol monoethyl ether; ethyleneglycol monomethyl ether acetate, ethylene glycol monoethyl (Poly) alkylene glycol monoalkyl ether acetates such as ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate ether acetates; other ethers such as diethyleneglycol dimethyl ether, diethylene glycol methylethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone and cyclo Hexanon, 2-heptanone, 3-heptanone, etc. Ketones; alkyl sulfate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropionate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate (methyl 2 -hydroxy-3-methylbutanoate), 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-acetic acid i- Propyl, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl, N-butyl butyrate, methyl pyruvate, ethyl pirbate, n-pyruvate Other esters such as lofil, methyl acetoacetate, ethyl acetate, ethyl 2-oxobutyrate, aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone Amides such as (N-methylpyrrolidone), N, N-dimethylformamide, N, and N-dimethylacetamide, and the like. Such a solvent can be used individually or in mixture of 2 or more types.

Among them, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexa Non- and 3-methoxy butyl acetate are preferable since they show the outstanding solubility with respect to a photopolymerizable compound and a photoinitiator, and can make the dispersibility of insoluble components, such as a black pigment, favorable, and are propylene glycol monomethyl ether acetate, It is especially preferable to use 3-methoxybutyl acetate. A solvent can be used in 50 mass parts-500 mass parts with respect to a total of 100 mass parts of a photopolymerizable compound, a photoinitiator, and a coloring agent.

Moreover, hydroquinone, hydroquinone monoethyl ether, etc. can be used as a thermal polymerization inhibitor. Moreover, a silicone type, a fluorine-type compound can be used as an antifoamer, and various well-known thermal polymerization inhibitors, such as anionic, cationic, and nonionic, can be used as surfactant.

As a manufacturing method of the black photosensitive composition which concerns on this invention, it is obtained by mixing the above-mentioned photopolymerizable compound, a photoinitiator, a coloring agent, and all these with a stirrer. Moreover, you may filter using a filter so that the obtained mixture may become uniform.

[Formation of black matrix, spacer, and inkjet partition wall]

First, the black photosensitive composition according to the present invention is applied onto a substrate by a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or spinner (rotary coating device). And a non-contact type coating device such as a curtain flow coater. As the substrate, a substrate having light transmittance is used.

In order to improve the adhesiveness of a glass substrate and a black photosensitive composition, you may apply a silane coupling agent on a glass substrate previously. Or you may add a silane coupling agent at the time of preparation of a black photosensitive composition.

After apply | coating this black photosensitive composition, it dries and removes a solvent. The drying method is not particularly limited, and for example, (1) a method of drying for 60 seconds to 120 seconds at a temperature of 80 ° C to 120 ° C, preferably 90 ° C to 100 ° C in a hot plate, and (2) You may use the method of leaving to stand at room temperature for several hours, and (3) the method of removing a solvent in a warm air heater or an infrared heater in tens of minutes for several hours.

Next, through a negative mask, active energy rays, such as an ultraviolet-ray and an excimer laser light, are irradiated and partially exposed. Energy dose of irradiation is different according to the composition of the black photosensitive composition, for example, is about 2000mJ / cm ² preferably at 30mJ / cm ^2.

Next, the film after exposure is developed with a developing solution, and patterned to a desired shape. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. Examples of the developer include organic solvents such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Next, the post-baking pattern is post-baked at about 200 ° C. Moreover, it is preferable to expose the formed pattern to the whole surface.

As described above, a partition for forming a black matrix, a spacer, or an inkjet type color filter having a predetermined shape can be formed.

[Formation of color filter]

The manufacturing process of the color filter which has a black matrix formed by the said method is demonstrated.

(1) Formation of color filter by lithography method (lithography method)

On a substrate on which the black matrix is formed, a black photosensitive composition including colorants of three primary colors of R, G, and B is usually used to form colored layers sequentially in the same manner as the formation of the black matrix for each color. Thereby, a color filter can be formed.

(2) Formation of color filter by inkjet method

When forming a color filter by the ink jet method, the partition for inkjet type color filter formation formed from the black photosensitive composition of this invention is used. Since the partition is black, it also serves as a black matrix. The partition wall is formed to have an opening (part enclosed by the partition wall) for collecting ink.

Specifically, first, the ink of R, G, and B is discharged to the opening portion by an inkjet method and collected into the partition wall. Next, the collected ink is cured by heat or light. Thereby, a color filter can be formed.

The black photosensitive composition which concerns on this invention can suppress generation | occurrence | production of the wrinkle in the pattern surface at the time of forming a pattern. Thus, a good black matrix can be formed. In addition, in particular, the spacer is required to be accurate in the thickness (cell gap) of the liquid crystal layer. According to the spacer formed with the black photosensitive composition of this invention, generation | occurrence | production of a wrinkle is suppressed and it becomes possible to maintain a cell gap more correctly. Moreover, since the spacer formed from the black photosensitive composition of this invention has light shielding property, reflection of light can be suppressed. Thereby, the display apparatus which can display favorable can be manufactured.

Example

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated based on an Example.

Synthesis Example 1

56 parts by mass of benzyl methacrylate, 36 parts by mass of 2-hydroxyethyl methacrylate, and 78 parts by mass of glycidyl methacrylate were dissolved in 250 parts by mass of ethylene glycol monomethyl ether acetate, and azobisisobutyronitrile (azobisisobutyronitrile) ) 2 parts by mass was added to carry out heat polymerization.

Then, 40 mass parts of acrylic acid which melt | dissolved 2 mass parts of methylhydroquinone as a polymerization inhibitor was added, and it reacted. Next, 42 mass parts of tetrahydrophthalic anhydrides were added and reacted, and resin was obtained. The mass average molecular weight of obtained resin was 3000.

[Examples 1 to 6 and Comparative Example 1]

Each component of Table 1 was mixed, it adjusted with propylene glycol monomethyl ether acetate so that the density | concentration of solid content other than a solvent might be 25 mass%, and the black photosensitive composition was obtained.

Photopolymerizable compound Photopolymerization initiator Pigment dispersion Example 1 Resin A: 30 parts by mass DPHA: 10 parts by mass Irgacure 369: 10 parts by mass Blue dispersion: 193 parts by mass Carbon dispersion: 48 parts by mass Example 2 Resin A: 30 parts by mass DPHA: 10 parts by mass Irgacure 369: 10 parts by mass Red dispersion: 193 parts by mass Carbon dispersion: 48 parts by mass Example 3 Resin A: 30 parts by mass DPHA: 10 parts by mass Irgacure 369: 10 parts by mass Yellow dispersion: 193 parts by mass Carbon dispersion: 48 parts by mass Example 4 Resin A: 30 parts by mass DPHA: 10 parts by mass Irgacure 369: 10 parts by mass Blue dispersion: 100 parts by mass Red dispersion: 93 parts by mass Carbon dispersion: 48 parts by mass Example 5 Resin A: 30 parts by mass DPHA: 10 parts by mass Irgacure 369: 10 parts by mass Blue dispersion: 70 parts by mass Red dispersion: 70 parts by mass Yellow dispersion: 53 parts by mass Carbon dispersion: 48 parts by mass Example 6 Resin A: 30 parts by mass DPHA: 10 parts by mass Irgacure 369: 10 parts by mass Blue dispersion: 140 parts by mass Carbon dispersion: 100 parts by mass Comparative Example 1 Resin A: 30 parts by mass DPHA: 10 parts by mass Irgacure 369: 10 parts by mass Carbon dispersion: 208 parts by mass

Correspondence of the abbreviation of each component name in a table | surface, and a formal name is as follows.

DPHA: dipentaerythritol hexaacrylate

Irgacure 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1) (Ciba specialty chemical company make)

Blue dispersion liquid: Blue pigment dispersion liquid CF blue UM (C: I. pigment blue 15: 6, 20 mass% containing: Mikuni dye production)

Carbon dispersion liquid: "Carbon dispersion liquid CF black EX-1455" (24 mass% of high resistance carbon content: Mikuni dye production)

Red dispersion: "CF red EX-109" (C. I. pigment red 177, anthraquinone system red pigment 20 mass% containing)

Yellow dispersion: "CF yellow HM" (C.I. pigment yellow 139, 20 mass% of monoazo-based yellow pigments)

(Formation of black matrix)

The obtained black photosensitive composition was apply | coated on a glass substrate using a spin coater, and it dried at 90 degreeC for 2 minutes, and formed the black photosensitive composition layer.

Next, ultraviolet rays were selectively irradiated to this black photosensitive composition layer through a negative mask. Thereafter, the solution was developed with an aqueous 2.38% tetramethyl ammonium hydroxide solution and post-baked in an oven at 220 ° C. for 30 minutes to form a black matrix pattern having a thickness of 2.5 μm. It was.

(evaluation)

The formed black matrix was evaluated for the occurrence of wrinkles, the OD value, and the taper angle. The results are shown in Table 2.

Occurrence of wrinkles OD value Taper angle Example 1 radish 4.5 80 ° Example 2 radish 4.2 80 ° Example 3 radish 4.0 80 ° Example 4 radish 4.3 80 ° Example 5 radish 4.2 80 ° Example 6 radish 8 or more 70 ° Comparative Example 1 U 8 or more 20 °

According to the present invention, by including the shape stabilizer in the black photosensitive composition, it is possible to form a black matrix having high shape stability against heat. Moreover, by making a shape stabilizer into an organic pigment, it became possible to stabilize the shape of a black matrix, adjusting the black of a black pigment. Moreover, it became possible to adjust the taper angle of a black matrix by adding an organic pigment. As a result, it became possible to provide the black matrix which has a pattern which an ink composition easily enters, the partition for inkjet type color filters, and the spacer for liquid crystal display elements.

Claims (11)

As a black photosensitive composition containing a photopolymerizable compound, a photoinitiator, and a black pigment, The photopolymerizable compound is a resin having a cardo structure in the molecule, It contains an organic pigment as a shape stabilizer,  The mass ratio of the organic pigment and the black pigment is from 10: 2 to 10:10, The total amount of the said organic pigment and the said black pigment is 60 mass%-120 mass% with respect to all solid components other than a solvent, The black photosensitive composition whose profile angle of the pattern formed from the said black photosensitive composition is 50 degrees or more. The method of claim 1, The black pigment is a black photosensitive composition, characterized in that the carbon black. delete delete The method of claim 1, The organic photosensitive composition, wherein the organic pigment is a pigment based on at least one selected from C. I. Pigment Blue 15: 6, C. I. Pigment Red 177, and C. I. Pigment Yellow 139. The method of claim 1, A black photosensitive composition, characterized in that for forming a thick film of 2 µm or more. The black matrix formed from the black photosensitive composition of any one of Claims 1, 2, 5, and 6. The method of claim 7, wherein An optical density is 4 or more, The black matrix characterized by the above-mentioned. delete The partition for inkjet type color filters formed with the black photosensitive composition of any one of Claims 1, 2, 5, and 6. The liquid crystal display element spacer formed with the black photosensitive composition of any one of Claims 1, 2, 5, and 6.