KR101291480B1 - Photosensitive composition and color filter formed from photosensitive composition - Google Patents

Abstract

The present invention is to provide a photosensitive composition having less occurrence of wrinkles and excellent surface smoothness, and a color filter having a pattern formed by the photosensitive composition, comprising: an alkali-soluble resin, A photosensitive composition containing a photopolymerizable monomer, a photoinitiator, and a coloring agent, and used for forming a thick film having a thickness of 1 µm or more, contained an effective amount of acrylic resin in order to prevent occurrence of wrinkles in the thick film.

Photosensitive composition, color filter

Description

Photosensitive composition and the color filter formed by this photosensitive composition {PHOTOSENSITIVE COMPOSITION AND COLOR FILTER FORMED FROM PHOTOSENSITIVE COMPOSITION}

The present invention relates to a photosensitive composition. Specifically, it relates to the photosensitive composition used for formation of the colored pattern in a color filter.

Red (R), green (G), and blue (B) color filters are used for displays, such as a liquid crystal display. In this color filter, a black matrix is formed in order to give contrast of each of these colors.

In recent years, color filters are often formed by lithography. Specifically, it manufactures by apply | coating, exposing, and developing the photosensitive resin composition which colored each layer of the black matrix, R, G, and B by each color sequentially, and forming a pattern in a predetermined position. In particular, in the black matrix, further thickening of the film is required in order to obtain a predetermined optical density (0D value).

In recent years, attention has been paid to the production of color filters by an inkjet method in which exposure is unnecessary and only a necessary portion can be coated with a coloring material. Especially in this inkjet system, using black matrix itself as a partition is examined (refer patent document 1).

Patent Document 1: Japanese Patent Application Laid-Open No. 2005-345667

However, as the film thickness becomes thicker, there arises a problem that wrinkles occur on the surface of the film. If wrinkles occur on the surface of the film, the display device may adversely affect each pixel.

Among them, the black matrix is required to have a higher 0D value, and further thickening, in particular, a film thickness of 1 µm or more is required. However, when wrinkles generate | occur | produce in a black matrix, it may adversely affect formation of a subsequent layer of each color.

The same applies to the case where wrinkles occur in the layers of each color, and in addition, may adversely affect the display color of the display device.

In addition, when forming a color filter using an inkjet system, the black matrix needs to be a thick film of 1 micrometer or more in thickness.

In view of the above problems, it is an object of the present invention to provide a photosensitive composition having less generation of wrinkles and excellent in surface smoothness. Moreover, an object of this invention is to provide the color filter which has a pattern formed with this photosensitive composition.

The present inventors have found that an acrylic resin is effective in suppressing the occurrence of wrinkles, and have completed the present invention. Specifically, the following are provided.

The present invention relates to a photosensitive composition containing an alkali-soluble resin, a photopolymerization initiator, and a coloring agent, wherein the alkali-soluble resin includes a photosensitive composition containing an acrylic resin for suppressing generation of wrinkles, and a photosensitive composition. A color filter having a pattern is provided.

Moreover, this invention provides the method of using acrylic resin as a wrinkle inhibitor in the said photosensitive composition. Moreover, this invention provides the wrinkle inhibitor which has an acrylic resin as a main component as a wrinkle inhibitor added in order to suppress wrinkles in the resin film of the thick film of 1 micrometer or more in thickness.

According to this invention, by containing acrylic resin as a wrinkle inhibitor, it becomes possible to obtain the colored layer with few generation | occurrence | production of a wrinkle.

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

The photosensitive composition which concerns on this invention contains alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and a coloring agent, and also contains acrylic resin for suppressing generation | occurrence | production of wrinkles as alkali-soluble resin.

[Alkali Soluble Resin]

It does not restrict | limit especially as alkali-soluble resin, It can select arbitrarily from what can be normally used as a film formation material in the photosensitive resin composition.

≪ Acrylic resin &

The photosensitive composition of this invention contains acrylic resin as alkali-soluble resin.

By adding this acrylic resin, generation | occurrence | production of the wrinkle in the black matrix formed from the composition of this invention can be suppressed. That is, this acrylic resin can be said to function as a wrinkle inhibitor.

This acrylic resin is a polymer of the monomer containing an acrylic monomer at least. As this acryl-type monomer, methacrylate, benzyl methacrylate, methyl methacrylate, 2-ethylhexyl methacrylate, acrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl Methacrylate and 2-isocyanatoethyl methacrylate are mentioned.

As this acrylic resin, the polymer which has a carboxyl group is used preferably, for example. As a specific example of the alkali-soluble copolymer which has such a carboxyl group, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2- Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macro monomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl Methacrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer, (meth Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2- Doxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macro monomer copolymer, methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaremido copolymer, ( Meta) acrylic acid / zucchini mono (2-acryloyloxyethyl) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / zucchini mono (2-acryloyloxyethyl) / Styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / benzyl (meth) acrylate / N-phenyl maleimide / styrene / glycerol mono (meth) acrylate copolymer Can be mentioned. Especially, the copolymer containing (meth) acrylic acid is used preferably. It is preferable that 50 mol% or more and 90 mol% or less are contained in this (meth) acrylic acid, and it is more preferable that they are 60 mol% or more and 85 mol% or less.

Moreover, it is more preferable to use the copolymer containing the said (meth) acrylic acid and benzyl (meth) acrylate or styrene.

It is preferable that it is 1000 or more, and, as for the mass mean molecular weight of acrylic resin, it is more preferable that it is 5000 or more. Moreover, as the upper limit, it is preferable that it is 50000 or less, and it is more preferable that it is 20000 or less. By making a mass mean molecular weight 1000 or more, the effect which suppresses generation | occurrence | production of a wrinkle can be improved. Moreover, applicability | paintability can be improved by making a mass mean molecular weight 50000 or less.

Moreover, it is preferable to contain 15 mass% or more in alkali-soluble resin, and, as for acrylic resin, it is more preferable to contain 20 mass% or more. By making content into 15 mass% or more, the effect which suppresses generation | occurrence | production of a wrinkle can be improved. Moreover, it is preferable to set it as less than 60 mass%, and, as for an upper limit, it is more preferable to set it as 50 mass% or less. Moreover, by making content less than 60 mass%, photo characteristic (especially image development margin etc.) can be improved. In addition, development margin means the magnitude | size of the optimal time width for performing one favorable image development process in image development processing.

Since the said acryl-type resin does not have photopolymerizability, it can be called non-photopolymerizable alkali-soluble resin.

Moreover, it is preferable that it is 10 mass% or more and 80 mass% or less with respect to solid content in the photosensitive composition, and, as for the said alkali-soluble resin, it is more preferable that it is 20 mass% or more and 70 mass% or less. By setting it as said range, there exists a tendency which is easy to balance the sensitivity, developability, and resolution, and it is preferable.

<Photopolymerizable alkali-soluble resin>

As alkali-soluble resin, photopolymerizable alkali-soluble resin is mentioned. Preferred examples of the photopolymerizable alkali-soluble resin include an epoxy compound (a) having an epoxy group (hereinafter also referred to as component (a)), an unsaturated group-containing carboxylic acid or an anhydride thereof (b) (hereinafter, also referred to as component (b)). Resin obtained by reacting the reactant (c) (hereinafter also referred to as (c) component) with the polybasic carboxylic acid or its anhydride (d) (hereinafter also referred to as (d) component). have.

As said epoxy compound (a), what has two or more epoxy groups is preferable. Moreover, as this epoxy compound (a), what is derived from bisphenols is preferable. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (-4) having two or more epoxy groups and derived from bisphenols -Hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5- Dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl Hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) Dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2, 2-bis (4-hydr Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5 -Dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether and the like, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis ( 4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene , 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy Hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibro Morphenyl) Fluorine Compound, or the like and, further, may be mentioned compounds containing 4,4'-biphenol, 3,3'-biphenol and the like. Moreover, a phenol novolak-type epoxy compound, a cresol novolak-type epoxy compound, etc. can also be used. This (a) component may combine single or 2 types or more. As an unsaturated group containing carboxylic acid or its anhydride (b) which reacts with the said epoxy compound (a), monocarboxylic acid or its anhydride containing reactive unsaturated double bonds, such as an acryl group and a methacryl group, is preferable in a molecule | numerator. As such unsaturated-group containing carboxylic acid, acrylic acid, methacrylic acid, (beta)-styryl acrylic acid, (beta) -furfuryl acrylic acid, (alpha)-cyano cinnamic acid, cinnamic acid etc. are mentioned, for example.

You may use (b) component individually or in combination of 2 or more types.

The component (c) can be prepared by reacting the component (a) and the component (b).

The usage-amount ratio in reaction of (a) component and (b) component is a ratio of the epoxy equivalent of (a) component and the carboxylic acid equivalent of (b) component normally 1: 0,5-1: 2, Preferably Preferably 1: 0.8 to 1: 1.25, more preferably 1: 1. When the usage-amount ratio of (a) component and (b) component is 1: 0.5-1: 2 by said equivalent ratio, it exists in the tendency for bridge | crosslinking efficiency to improve, and it is preferable.

Next, the polybasic acid carboxylic acid or its acid anhydride (d) which reacts with (c) component is demonstrated.

As this (d) component, the carboxylic acid which has two or more carboxyl groups, its anhydride, etc. are mentioned. Examples of the carboxylic acid having two or more carboxyl groups include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, nitrate, maleic acid, fumaric acid, itaconic acid, citric acid, tartaric acid, phthalic acid, tetrahydrophthalic acid, Hexahydrophthalic acid, methyl end methylenetetrahydrophthalic acid, chloric acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonedicarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid And biphenyl dicarboxylic acid, biphenyl ether tetracarboxylic acid, and the like, and preferably anhydrides of tetrahydrophthalic acid, dianhydrides of benzophenone tetracarboxylic acid, and dihydrides of biphenyltetracarboxylic acid. .

The usage-amount ratio of (c) component and (d) component is the equivalence ratio of the number-of-moles of 0H group in (c) component, and the (d) acid anhydride group, It is usually 1: 1-1: 0,1, Preferably 1: 0.8 to 1: 0.2. When the usage-amount ratio of (c) component and (d) is 1: 1 thru | or 1: 0.1 on the said reference | standard, there exists a tendency for the solubility to a developing solution to become moderate, and it is preferable.

It is preferable to use resin represented by following General formula (1) also in the said photopolymerizable alkali-soluble resin.

[Formula 1]

........(1)

........(One)

In formula, X is group represented by following General formula (2).

[Formula 2]

........(2)

........(2)

Wherein Y is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl end methylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydro phthalic anhydride, glutaric anhydride It is a residue remove | excluding the carboxylic anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride called acid.

In addition, Z is remove | excluding two carboxylic anhydride groups from tetracarboxylic dianhydride, such as pyromellitic anhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, and a biphenyl ether tetracarboxylic dianhydride. Residue.

It is preferable to use 1000 or more as the mass mean molecular weight of said photopolymerizable alkali-soluble resin. By making a mass average molecular weight 1000 or more, it is possible to make a coating film uniform, and to make a mass average molecular weight 100000 or less. Developability can be made favorable by making a mass mean molecular weight 100000 or less.

<Photopolymerizable monomer>

It is preferable to add a photopolymerizable monomer to the photosensitive composition of this invention.

The photopolymerizable monomer has at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in a molecule. It is preferable that this photopolymerizable monomer has two or more polymerizable functional groups. By adding a photopolymerizable monomer, it becomes possible to improve the film strength of the formed film | membrane and adhesiveness with respect to a board | substrate.

As a photopolymerizable monomer, a monofunctional monomer, a polyfunctional monomer, etc. are mentioned.

As a monofunctional monomer, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy Methyl (meth) acrylamide, acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic acid, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylic Amidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, Glycerin mono (meth) acrylate, tetraha Drofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3 -Tetrafluoropropyl (meth) acrylate, the half (meth) acrylate of a phthalic acid derivative, N-methylol (meth) acrylamide, etc. are mentioned. In addition, these can be used individually or in combination of 2 or more types.

On the other hand, as a polyfunctional monomer, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol di (meth) ) Acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di ( Meta) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) Propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy 3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (Meta) Oh Relate, diethylene glycol glycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane ( Meth) acrylate (i.e., triylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc., and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acryl Polyfunctional monomers, such as a condensate of an amide methylene ether, a polyhydric alcohol, and N-methylol (meth) acrylamide, a triacyl hormar, etc. are mentioned. In addition, these can be used individually or in combination of 2 or more types.

5 mass% or more and 50 mass% or less are preferable with respect to solid content of the photosensitive composition, and, as for content of such a photopolymerizable monomer, 10 mass% or more and 40 mass% or less are more preferable. By the said range, it exists in the tendency to balance the sensitivity, developability, and resolution, and is preferable.

[Photopolymerization initiator]

Moreover, as a photoinitiator, acetophenone, 2, 2- diethoxy acetophenone, p-dimethyl acetophenone, p-dimethylamino propiophenone, dichloro acetophenone, trichloro acetophenone, p-tert- butyl acetophenone, etc. Benzophenones such as acetophenones, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl Benzoin ethers such as ether, benzyl dimethyl keta-ru, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropyl thioxanthene, and the like Sulfur compounds, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone, azobisisobutylonitrile, benzoylpaoxide, cou Organic peroxides such as menpaoxide and 2-mercaptobenzo Thiol compounds, such as a midazole and 2-mercapto benzo-okizazole 2-mercapto benzothiazole, or 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer Imidazolyl compounds such as biphenyl, triazine compounds such as 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- Such as triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine A triazine compound having a methyl group, the 2-benzyl-1- (4-morpholinophenyl) - there may be mentioned amino ketone compounds, such as butane -1-one. These photoinitiators may combine single or 2 types or more.

The content of the photopolymerization initiator is preferably 1 part by mass to 150 parts by mass, more preferably 5 parts by mass to 100 parts by mass, and even more preferably 100 parts by mass of the solid components other than the solvent. It is the range of 10 mass parts to 50 mass parts. By setting the content to 150 parts by mass or less, sufficient heat resistance and chemical resistance can be obtained, and by setting it to 1 part by mass or more, the coating film forming ability can be improved and the photocuring defect can be suppressed.

[coloring agent]

The photosensitive composition which concerns on this invention contains a coloring agent.

Examples of the colorant include compounds classified as pigments in color indexes (issued by The Society of Dyers and Colorists, Inc.), specifically those having the following color index (CI) numbers. It is preferable to use.

C.I. Pigment Yellow 1 (hereinafter referred to as "CI Pigment Yellow", only numbers), 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;

C.I. Pigment orange 1 (hereinafter "CI pigment orange" lists only the same number), 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;

C.I. Pigment red 1 (hereinafter "CI pigment red" lists only the same number), 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;

C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" refers to the same number only), 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.

In addition, when forming a black matrix, it is preferable to use carbon black as a black pigment. In addition, inorganic pigments such as metal oxides such as titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, composite oxides, metal sulfides, metal sulfate pressures or metal carbonates, etc. may also be mentioned. . Especially, it is more preferable to use the carbon black which has high light-shielding property.

As carbon black, although well-known carbon black, such as channel black, furnace black, thermal black, and lamp black, can be used, it is especially preferable to use channel black which is excellent in light-shielding property. Moreover, you may use resin coating carbon black.

Since resin-coated carbon black has lower conductivity than carbon black without resin coating, when used as a black matrix of a liquid crystal display device such as a liquid crystal display, there is less leakage of current and a highly reliable low power display can be produced. have.

In addition, in order to adjust the color tone of carbon black, you may add the said organic pigment suitably as an auxiliary pigment.

Moreover, in order to disperse | distribute a coloring agent uniformly, it is preferable to use the polymer dispersing agent of a polyethyleneimine system, a urethane resin system, and an acrylic resin system as a dispersing agent. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin dispersant as the dispersant.

In addition, although an inorganic pigment and an organic pigment may be used individually or in combination of 2 or more types, when using together, an organic pigment is used in 10 to 80 mass parts with respect to 100 mass parts of total amounts of an inorganic pigment and an organic pigment. It is preferable to, and it is more preferable that it is the range from 20 mass parts to 40 mass parts. It is preferable to make said inorganic pigment and organic pigment into the solution disperse | distributed to the suitable density | concentration using a dispersing agent, and to add to a photosensitive composition.

Moreover, as for the usage-amount of the coloring agent in the photosensitive composition of this invention, 5 mass% or more and 70 mass% or less are preferable with respect to solid content of the photosensitive composition, 25 mass% or more and 55 mass% or less are more preferable, 30 mass% or more 50 mass% or less is more preferable. By setting it as said range, a black matrix and each colored layer can be formed in a target pattern, and it is preferable.

When forming especially a black matrix, it is preferable to adjust the quantity of the black pigment in the photosensitive composition so that 0D value per film thickness of 1 micrometer may become 4 or more. When 0D value per 1 micrometer film thickness in a black matrix is 4 or more, sufficient display contrast can be obtained when it uses for the black matrix of a liquid crystal display.

[Other Ingredients]

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

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

Here, as the solvent which can be added to the photosensitive composition, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene 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 monomethyl 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 monomethyl ether, tripropylene glycol hair Ethyl ether and (poly) alkylene glycol monoalkyl ether; (Poly) alkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Lenglycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, acetic acid n-propyl, acetic acid i-propyl, acetic acid n -Butyl, i-butyl acetate, formic acid n-pentyl, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; Amides such as N-methylpyrrolidone, N, N-dimethyl formamide, and NN-dimethylacetamide. These solvents 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, cyclohexanone, 3- Since methoxy butyl acetate shows 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, propylene glycol monomethyl ether acetate, 3- Particular preference is given to using methoxybutyl acetate. A solvent can be used in 50 mass parts from 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. In addition, as a defoaming agent, various well-known thermal polymerization inhibitors, such as a silicone type, a fluorine type compound, and an anionic type, a cation type, a nonionic type, can be used as surfactant.

In addition, when forming a pattern using the photosensitive composition which concerns on this invention, as mentioned later, the photosensitive composition which concerns on this invention is apply | coated and dried on a board | substrate, and a film is formed. In order to improve the applicability at this time and to improve the physical properties after photocuring, a polymer binder may be added as a binder in addition to the above components. 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 set normally within the range of 1 micrometer-10 micrometers, Preferably it is 1.5 micrometers-8 micrometers, More preferably, it is 2 micrometers-5 micrometers. When the film thickness is 2 µm or more, it can be used not only as a black matrix for ordinary color filters, but also as a black matrix for color filters of the inkjet method.

As a manufacturing method of the photosensitive composition which concerns on this invention, it is obtained by mixing each component mentioned above with a stirrer. Moreover, you may filter using a filter so that the obtained mixture may become uniform.

[Formation method of color filter]

Hereinafter, the method of forming a color filter using the photosensitive composition concerning this invention is demonstrated.

(Formation of black matrix (black colored layer)]

First, a photosensitive composition (containing a black colorant) is placed on a substrate in a non-contact type such as a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, a spinner (rotary coating device), and a curtain flow coater. It apply | coats using a coating apparatus. As the substrate, a substrate having light transmittance is used.

In order to improve the adhesiveness of a glass substrate and a photosensitive composition, you may apply the silane coupling agent on a glass substrate previously. Alternatively, a silane coupling agent may be added at the time of preparing the photosensitive composition.

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

Subsequently, through a negative mask, active energy rays, such as an ultraviolet-ray and an excimer laser beam, are irradiated and partially exposed. Although the energy dose to irradiate changes also with the composition of the photosensitive composition, about 30 mJ / cm <2>-about 2000mJ / cm <2> are preferable, for example.

Subsequently, the film after exposure is patterned into a desired shape by developing with a developer. 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 compounds such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Subsequently, the black matrix is formed by post-baking the patterning after image development to about 200 degreeC. In addition, it is preferable to expose the formed pattern to the whole surface.

This formed black matrix can be used also as a spacer and a partition for inkjet according to the pattern shape and thickness.

(1) Formation of color filter by lithography method

On the board | substrate with which the said black matrix was formed, normally, using the photosensitive composition containing the coloring agent of three primary colors of R, G, and B, a colored layer is formed in order similarly to formation of the said black matrix for every one color. Thereby, a color filter can be formed.

(2) Formation of color filter by inkjet method

When forming a color filter by the inkjet system, the partition for forming an inkjet system color filter formed from the photosensitive composition concerning this invention (henceforth only a partition) is used. Since this partition is black, it also serves as a black matrix at the same time.

Specifically, first, the ink of R, G, and B is discharged by the inkjet method to the part enclosed by the said partition, and is stored in a partition wall. The stored ink is then thermally or photocured. Thereby, a color filter can be formed.

[Example]

Synthesis Example 1

The cardo resin represented by following General formula (1) was synthesize | combined.

(3)

........(1)

........(One)

In formula, X is group represented by General formula (2).

[Formula 4]

.......(2)

.......(2)

In 500 ml of four flasks, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tertbutyl-4-methylphenol and 72.0 acrylic acid The g was dissolved by heating from 90 ° C. to 100 ° C. while blowing air at a rate of 25 ml / min.

Next, while the solution was cloudy, the temperature was slowly raised to 120 ° C and completely dissolved. At this time, the solution gradually became transparent and viscous, but the stirring was continued as it was. At this time, acid value was measured and heating and stirring was continued for about 12 hours until it became less than 1.0 mgK0H / g. And it cooled to room temperature and obtained the colorless transparent solid bisphenol fluorene type epoxy acrylate represented by following General formula (3).

[Chemical Formula 5]

.........(3)

......... (3)

Subsequently, 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained, and 80.5 g of benzophenone tetracarboxylic dianhydride, and tetraethylammonium bromide. 1g was mixed and reacted at 110 to 115 degreeC for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydro anhydride phthalic acid was mixed and reacted at 90 DEG C for 6 hours to yield the above general formula (3). The cardo resin represented by) was obtained. And loss | disappearance of the acid anhydride group was confirmed by IR spectrum. This cardo resin was made into compound (1).

The compound (1) is a compound represented by the general formula (1), wherein X is a group represented by the general formula (2), and Y is an acid from 1,2,3,6-tetrahydrophthalic anhydride dianhydride. The moiety of Y and Z is the residue excluding anhydride group (-C0-0-C0-), Z is a residue excluding acid anhydride from 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride. , Y / Z = 50.0 / 50.0.

[Examples and Comparative Examples]

The cardo resin, the acrylic resin, the photopolymerizable monomer, and the pigment liquid are mixed as shown in Table 1, and mixed, and the solvent is 3-methoxybutyl acetate / PGMEA / cyclohexanone = 6: 2: 2 (mass ratio). The photosensitive composition was prepared by making the solid content concentration containing a pigment into 25 mass%.

[Table 1]

Acrylic resin: Examples 1-5: (meth) acrylic acid / benzyl (meth) acrylate (8: 2 (molar ratio)) copolymer

               Example 6: (meth) acrylic acid / styrene (8: 2 (molar ratio)) copolymer

Photopolymerizable monomer: pentaerythritol tetraacrylate

Photopolymerization initiator: Brand name OXE-01, manufactured by Chivas Specialty Chemicals

Pigment liquid: trade name CF Black TEN, 20 mass% of high-resistance carbon, manufactured by Mikuni Pigment Co., Ltd.

These samples were apply | coated to a glass substrate, and baked at 90 degreeC for 120 second, and the film | membrane of 2 micrometers in thickness was formed. Then, it exposed at the exposure amount of 150 mj / cm <2>, and developed for 60 second using alkaline developing solution (product name: N-A3K, Tokyo Chemical Industry Co., Ltd.), and formed the black matrix of 10 micrometers of line widths. Thereafter, post-baking was performed in a circulation oven at 220 ° C. for 30 minutes. The formed black matrix was examined for wrinkles on the surface and development margin by observing with an optical microscope. The results are shown in Table 2. Regarding the development margin, development was carried out for 60 seconds at the center for 10 seconds (50 seconds, 70 seconds) before and after the center.

The black matrix having a line width of 10 µm was pattern-formed at all the development times, and the pattern formation defects were partially formed at any one of the development times, for example, pattern missing, edge roughness, and the like. (Circle) and the thing in which the black matrix of 10 micrometers of line | wire widths are not pattern-formed at all the developing time were evaluated by making into x that there existed a defect.

[Table 2]

◎: Particularly good ○: Good △: Slightly good ×: Poor

Claims (8)

In the photosensitive resin composition containing alkali-soluble resin, a photoinitiator, a coloring agent, and a photopolymerizable monomer, The said alkali-soluble resin contains acrylic resin for suppressing generation | occurrence | production of wrinkles, and photopolymerizable alkali-soluble resin represented by General formula (1), 20 mass% or more and 50 mass% or less of acrylic resin for suppressing generation | occurrence | production of the said wrinkle is contained in the said alkali-soluble resin, Said acrylic resin is a copolymer containing 80 mol%-85 mol% of a (meth) acrylic acid unit, The photosensitive resin composition characterized by the above-mentioned.

..........(One) (Wherein n represents the number of repeat units in the structure in parentheses, and X is a group represented by the following general formula (2).)

..........(2) (Wherein, Y is a residue except the carboxylic anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. In the formula, Z is a residue except two carboxylic anhydride groups from tetracarboxylic dianhydride.) The method of claim 1, The mass average molecular weight of the said acrylic resin is 5000-50000, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The acrylic resin is methacrylate, benzyl methacrylate, methyl methacrylate, 2-ethylhexyl methacrylate, acrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, It is a polymer of the monomer containing at least 1 sort (s) chosen from 2-isocyanatoethyl methacrylate, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The said coloring agent contains a black pigment, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, It is used to form the thick film of 1 micrometer or more in thickness, The photosensitive resin composition characterized by the above-mentioned. The method according to claim 4 or 5, It is for formation of the black matrix of the color filter of an inkjet system, The photosensitive resin composition characterized by the above-mentioned. It has a pattern formed by the photosensitive resin composition of Claim 1, The color filter characterized by the above-mentioned. delete