KR20100014122A - Colored photosensitive resin composition, color filter and liquid crystal display - Google Patents

Abstract

assignment

Provided is a colored photosensitive resin composition capable of effectively suppressing surface defects and surface roughness of a coating film when the coating film is dried under reduced pressure, a color filter having a pattern formed using the colored photosensitive resin composition, and a liquid crystal display display having the color filter. do.

Resolution

The coloring photosensitive resin composition which concerns on this invention contains a photopolymerizable compound (A), a photoinitiator (B), a coloring agent (C), and a solvent (S). The solvent (S) is at least one low boiling point solvent (L) having a boiling point of less than 170 ° C at atmospheric pressure, at least one first boiling point solvent (H1) having a boiling point of at least 170 ° C and less than 180 ° C, and at atmospheric pressure. A boiling point consists of at least 1 type 2 high boiling point solvent (H2) which is 180 degreeC or more, and the ratio of the said 1st high boiling point solvent (H1) in a solvent (S) is 60 weight% or more.

Description

Colored photosensitive resin composition, color filter, and liquid crystal display display {COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY}

The present invention relates to a colored photosensitive resin composition, a color filter having a pattern formed using the colored photosensitive resin composition, and a liquid crystal display display having the color filter.

A display 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. A color filter including pixel regions of each color such as red (R), green (G), and blue (B) is formed inside one substrate. In this color filter, a black matrix is formed so as to partition each pixel area of red, green, and blue.

Generally, a color filter is manufactured by the lithographic method. In this lithography method, black coloring photosensitive resin composition is first apply | coated on a board | substrate, and a coating film is dried under reduced pressure with a vacuum drying apparatus (VCD), and it exposes and develops and forms a black matrix. Subsequently, coating, drying, exposure, and development are repeated for each of the colored photosensitive resin compositions of each color of red, green, and blue, and pixel regions of each color are formed at predetermined positions to produce color filters.

Moreover, in recent years, the method of manufacturing a color filter by the inkjet system is examined in order to improve the productivity of a color filter. In this inkjet method, a black matrix is first formed by the lithography method. Next, the colored photosensitive resin composition of each color of red, green, and blue is discharged from an inkjet nozzle to each pixel area partitioned by the black matrix, and a color filter is manufactured by hardening the gathered colored photosensitive resin composition with heat or light. do.

Patent Document 1: Japanese Patent Application Laid-Open No. 2006-349981

However, as mentioned above, after apply | coating a coloring photosensitive resin composition on a board | substrate, although a coating film is dried under reduced pressure by a vacuum drying apparatus (VCD), when drying a coating film under reduced pressure, it becomes the cause of dolby of a solvent, aggregation of a coloring agent, etc., There existed a problem that surface defect and surface roughening generate | occur | produce in a coating film.

Therefore, in order to prevent the dolby of a conventional solvent, the coloring photosensitive resin composition which contains dipropylene glycol dimethyl ether in the ratio of 5 weight% or more and 40 weight% or less is disclosed (refer patent document 1).

However, even with the solvent composition disclosed in this patent document 1, the surface defect and surface roughness suppression effect which generate | occur | produce still in a coating film were not enough. In particular, when there is much content of a coloring agent, or when the decompression rate is raised for shortening a tact, surface defects and surface roughness of a coating film become conspicuous.

This invention is made | formed in view of the above subject, The color filter which has the coloring photosensitive resin composition which can effectively suppress the surface defect and surface roughness of the coating film at the time of drying under reduced pressure, and the pattern formed using this coloring photosensitive resin composition. And a liquid crystal display having the color filter.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to solve the said subject. As a result, the inventors have found that the above problems can be solved by setting the solvent in the colored photosensitive resin composition to a specific composition, and have completed the present invention. Specifically, the present invention provides the following.

The 1st aspect of this invention is a coloring photosensitive resin composition containing a photopolymerizable compound (A), a photoinitiator (B), a coloring agent (C), and a solvent (S), The said solvent (S) has a boiling point in atmospheric pressure 170 1 or more types of low boiling point solvents (L) less than degrees C, 1 or more types of 1st high boiling point solvents (H1) whose boiling point in atmospheric pressure is 170 degreeC or more and less than 180 degreeC, and 1 or more types of 2nd high boiling points whose boiling point in atmospheric pressure is 180 degreeC or more. It consists of a point solvent (H2), and is the coloring photosensitive resin composition whose ratio of the said 1st high boiling point solvent (H1) in the said solvent (S) is 60 weight% or more.

The 2nd aspect of this invention is a color filter which has a pattern formed using the coloring photosensitive resin composition which concerns on this invention.

A third aspect of the present invention is a liquid crystal display having a color filter according to the present invention.

According to this invention, it has a coloring photosensitive resin composition which can effectively suppress the surface defect and surface roughness of a coating film when drying a coating film under reduced pressure, the color filter which has a pattern formed using this coloring photosensitive resin composition, and its color filter A liquid crystal display can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In addition, this invention is not limited to the following embodiment at all.

<Coloring Photosensitive Resin Composition>

The coloring photosensitive resin composition which concerns on this invention contains a photopolymerizable compound (A), a photoinitiator (B), a coloring agent (C), and a solvent (S). Hereinafter, each component contained in a coloring photosensitive resin composition is explained in full detail.

[(A) Photopolymerizable Compound]

As a photopolymerizable compound (A), resin or monomer which has an ethylenically unsaturated group is preferable, and it is more preferable to combine these. By combining the resin which has an ethylenically unsaturated group, and the monomer which has an ethylenically unsaturated group, hardenability can be improved and pattern formation can be made easy. In addition, in this specification, what has a weight average molecular weight of 1,000 or more among the compounds which have an ethylenically unsaturated group is called "resin which has an ethylenically unsaturated group", and what has a weight average molecular weight of less than 1,000 is called "monomer having an ethylenically unsaturated group". .

(Resin having an ethylenically unsaturated group)

Examples of the resin having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumaric acid, monoethyl fumaric acid, 2-hydroxyethyl (meth) acrylate, and ethylene glycol monomethyl ether (meth) acrylate. , Ethylene glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meta Oligomers into which acrylate, 1,6-hexanediol di (meth) acrylate, cardoepoxy diacrylate, and the like are polymerized; After (meth) acrylic acid is reacted with a polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid, a compound having a polyol and two isocyanate groups Polyurethane (meth) acrylate obtained by making it react; Bisphenol A type epoxy resin, 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 polyglycidyl ether, polyol polyglycol The epoxy (meth) acrylate resin etc. which are obtained by making (meth) acrylic acid react with epoxy resins, such as a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, and a dihydroxy benzene type epoxy resin, are mentioned. Moreover, resin which made polybasic acid anhydride react with epoxy (meth) acrylate resin can be used suitably.

Moreover, as resin which has an ethylenically unsaturated group, resin obtained by further reacting the reaction material of an epoxy compound and an unsaturated group containing carboxylic acid compound with a polybasic acid anhydride can be used suitably.

Especially, the compound represented by following formula (a1) is preferable. The compound represented by this formula (a1) is preferable at the point which itself has high photocurability.

In said formula (a1), X represents group represented by a following formula (a2).

In said formula (a2), R <^1a> represents a hydrogen atom, a C1-C6 hydrocarbon group, or a halogen atom each independently, R <^2a> represents a hydrogen atom or a methyl group each independently, W represents a single bond or the following formula ( The group represented by a3) is shown.

In addition, in said formula (a1), Y represents the residue remove | excluding the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endo methylene tetrahydrophthalic anhydride, chloric anhydride, methyltetrahydro phthalic anhydride, Glutaric anhydride etc. are mentioned.

In addition, in said formula (a1), Z represents the residue remove | excluding two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride and the like.

In addition, in said formula (a1), m shows the integer of 0-20.

It is preferable that it is 10-150 mgKOH / g in resin solid content, and, as for the acid value of resin which has an ethylenically unsaturated group, it is more preferable that it is 70-110 mgKOH / g. By making the acid value 10 mgKOH / g or more, sufficient solubility in a developer can be obtained. Moreover, by setting an acid value to 150 mgKOH / g or less, sufficient sclerosis | hardenability can be obtained and surface quality can be made favorable.

Moreover, it is preferable that it is 1,000-40,000, and, as for the weight average molecular weight of resin which has an ethylenically unsaturated group, it is more preferable that it is 2,000-30,000. By setting the weight average molecular weight to 1,000 or more, heat resistance and film strength can be improved. Moreover, sufficient solubility to a developing solution can be obtained by making a weight average molecular weight 40,000 or less.

(Monomer having an ethylenically unsaturated group)

Monomers and monomers having an ethylenically unsaturated group include a monofunctional monomer and a polyfunctional monomer.

As monofunctional monomer, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymeth Methoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride , Citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( Meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) a Acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl ( Meta) acrylates, 2,2,2-trifluoroethyl (meth) acrylates, 2,2,3,3-tetrafluoropropyl (meth) acrylates, and half (meth) acrylates of phthalic acid derivatives; Can be mentioned. These monofunctional monomers may be used independently or may be used in combination of 2 or more type.

On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di ( Meta) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipene Taerythritol hexa (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 (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid Diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e. tolylene diisocyanate), trimethylhexamethylene diisocyanate Reactant of hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, the axis of polyhydric alcohol and N-methylol (meth) acrylamide Multi-functional monomers, such as water or the like can be given triacrylate formal. These polyfunctional monomers may be used independently or may be used in combination of 2 or more type.

It is preferable that it is 5-50 weight% with respect to solid content of a coloring photosensitive resin composition, and, as for content of a photopolymerizable compound (A), it is more preferable that it is 10-40 weight% or less. It exists in the tendency to balance the sensitivity, developability, and resolution by making it into the said range.

[Photopolymerization Initiator (B)]

Examples of the photopolymerization initiator (B) include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2. -Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone-1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphineoxide, 4- Benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoic acid, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4- Dimethylamino-2-isoamylbenzoic acid, benzyl-β-methok Ethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chloroti Oxanthone, 2,4-dimethyl thioxanthone, 1-chloro-4-propoxy city oxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthiooxane Ten, 2-isopropyl thioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene Peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imida Zolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl -4-methoxy benzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether Le, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropy Ophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α- Dichloro-4-phenoxycetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosveron, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1 , 7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) 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-tria Gin, 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-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 and 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) Styrylphenyl-s-triazine and the like can be used. Among these, it is especially preferable in terms of sensitivity to use an oxime-type photoinitiator. These photoinitiators may be used independently and may be used in combination of 2 or more type.

It is preferable that it is 0.5-30 weight% with respect to solid content of a coloring photosensitive resin composition, and, as for content of a photoinitiator (B), it is more preferable that it is 1-20 weight%. By setting it as said range, sufficient heat resistance and chemical-resistance can be obtained, and a film formation ability can be improved and a photocuring defect can be suppressed.

Colorant (C)

As the coloring agent (C), for example, a compound classified as a pigment in a color index (CI; issued by The'Society 'of' Dyers' and 'Colourists'), specifically, the following color index (CI) number is given. It can be used. This coloring agent may be used independently, and may be used in mixture of 2 or more type in order to adjust color tone.

C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" likewise describes numbers 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;

C.I. Pigment orange 1 (hereinafter, "CI pigment orange" lists only the numbers similarly), 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" likewise describes numbers only), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

C.I. Pigment Red 1 (hereinafter, "CI Pigment Red" likewise describes numbers only), 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" likewise describes numbers 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, C.I. Pigment Black 7.

Moreover, when forming the black matrix in a color filter, a black pigment is used as a coloring agent (C).

It is preferable to use carbon black or titanium black as a black pigment. Other than Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si and Al Inorganic pigments, such as various metal oxides, complex oxides, metal sulfides, metal sulfates, or metal carbonates, can also be used.

As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, and lamp black, can be used, but channel black can be suitably used because of its excellent light shielding properties. Moreover, resin coated carbon black can also be used. Specifically, a resin-coated carbon black obtained by mixing a resin having reactivity with a carboxyl group, a hydroxyl group, and a carbonyl group present on the surface of the carbon black and the carbon black and heating at 50 to 380 ° C. or a water-organic solvent mixture system Or resin-coated carbon black obtained by dispersing an ethylenic monomer in a water-surfactant mixed system and radical polymerization or radical copolymerization in the presence of a polymerization initiator. Since the resin-coated carbon black has lower conductivity than that of the carbon black without resin coating, when used in a color filter, there is little leakage of current, and a highly reliable low power consumption liquid crystal display display can be formed.

Moreover, you may add an organic pigment as said auxiliary pigment to said inorganic pigment. The organic pigment can obtain the following effects by appropriately selecting and adding those having the complementary color of the inorganic pigment. For example, carbon black has a reddish black color. Therefore, the addition of the blue-pigmented organic pigment, which is a red complementary color, to the carbon black causes the redness of the carbon black to disappear, thereby making the overall black more desirable. It is preferable to use an organic pigment in 10-80 weight part with respect to a total of 100 weight part of an inorganic pigment and an organic pigment, 20-60 weight part is more preferable, 20-40 weight part is the most preferable.

As said inorganic pigment and organic pigment, the solution which disperse | distributed the pigment to appropriate density | concentration using the dispersing agent can be used. For example, as the inorganic pigment, carbon dispersion CF black (containing 20% carbon concentration) manufactured by Mikuni Dyestuffs Co., carbon dispersion CF black (containing 24% high resistance carbon) manufactured by Mikuni Dyestuffs Co., Ltd. titanium black dispersion CF black (black) manufactured by Mikuni Dyestuffs Co., Ltd. Titanium pigment 20%), etc. are mentioned. Moreover, as an organic pigment, the blue pigment dispersion liquid CF blue (20% of blue pigment containing) made by Mikuni dyestuff company, the violet pigment dispersion liquid (10% containing of violet pigment) made by Mikuni dyestuff company, etc. are mentioned, for example. As the dispersant, polyethyleneimine-based, urethane resin-based, and acrylic resin-based polymer dispersants are preferably used.

It is preferable that it is 1-70 weight% with respect to solid content of a coloring photosensitive resin composition, and, as for content of a coloring agent (C), it is more preferable that it is 20-60 weight%. By setting it as the said range, coloring performance can be improved, suppressing generation of hardening defect.

In addition, when using a black pigment as a coloring agent (C), it is preferable to adjust so that OD (Optical_Density) value per 1 micrometer of film thickness of the film formed may be 3.5 or more, Preferably it is 4.0 or more. When the OD value per 1 micrometer of film thickness is 3.5 or more, when it uses for the black matrix of a color filter, sufficient display contrast can be obtained and a required performance is obtained.

[Solvent (S)]

As the solvent (S), at least one low boiling point solvent (L) having a boiling point of less than 170 ° C, at least one first boiling point solvent (H1) having a boiling point of 170 ° C or more and less than 180 ° C, and at least one type of agent having a boiling point of 180 ° C or more. What consists of 2 high boiling point solvents (H2) is used. In addition, the boiling point shown in this specification is a value in atmospheric pressure. When the solvent (S) is such a composition, the surface defect and surface roughness of the coating film at the time of drying under reduced pressure the coating film of a coloring photosensitive resin composition can be suppressed effectively.

It is preferable that the boiling point of the low boiling point solvent (L) is less than 170 degreeC, and is 160 degrees C or less. Moreover, it is preferable that boiling point is 130 degreeC or more, and it is more preferable that it is 140 degreeC or more. Specifically as such a low boiling point solvent (L), 1 or more types chosen from cyclohexanone (AN) and propylene glycol monomethyl ether acetate (PGMEA) are preferable. Among these, propylene glycol monomethyl ether acetate (PGMEA) is more preferable.

It is preferable that it is less than 35 weight% with respect to the whole amount of the solvent S, and, as for content of the low boiling point solvent (L), it is more preferable that it is 30 weight% or less. Moreover, it is preferable that content is 5 weight% or more, It is more preferable that it is 10 weight% or more, It is further more preferable that it is 15 weight% or more. Since the low boiling point solvent (L) volatilizes for the first time when apply | coating a coloring photosensitive resin composition, by containing in such content, the efficiency at the time of drying under reduced pressure of the coating film of a coloring photosensitive resin composition can be improved.

The boiling point of the 1st high boiling point solvent (H1) is 170 degreeC or more and less than 180 degreeC. Specifically as such a 1st high boiling point solvent (H1), 1 or more types chosen from 3-methoxybutyl acetate (MA), dipropylene glycol dimethyl ether (DMM), and cyclohexanol acetate (CHXA) are preferable. . Among these, 3-methoxy butyl acetate (MA) and cyclohexanol acetate (CHXA) are more preferable, and 3-methoxy butyl acetate (MA) is especially preferable.

The content of the first high boiling point solvent (H1) is 60% by weight or more, preferably 63% by weight or more, and more preferably 65% by weight or more based on the total amount of the solvent (S). Moreover, it is preferable that content is 90 weight% or less, and it is more preferable that it is 85 weight% or less.

The boiling point of the second high boiling point solvent (H2) is 180 ° C or higher, preferably 190 ° C or higher, and more preferably 200 ° C or higher. Moreover, it is preferable that boiling point is 250 degrees C or less. As such a second high boiling point solvent (H2), specifically, propylene glycol diacetate (PGDA), gamma butyrolactone (GBL), dipropylene glycol methyl ether acetate (DPMA), diethylene glycol monoethyl ether acetate (EDGAC) ), 1,3-butylene glycol diacetate (BGDA) and diethylene glycol monobutyl ether acetate (BDGAC) are preferably at least one selected from the group. Among these, 1, 3- butylene glycol diacetate (BGDA) and diethylene glycol monobutyl ether acetate (BDGAC) are especially preferable.

Moreover, 15 TG% or less is preferable, as for the weight change rate of the 2nd high boiling point solvent (H2) at 100 degreeC, 10 TG% or less is more preferable, It is still more preferable that it is 8 TG% or less. Moreover, 2 TG% or more is preferable and, as for a weight change rate, 4 TG% or more is more preferable. Here, "weight change rate in 100 degreeC" refers to the weight change of the solvent per unit time. In this specification, it is measured by adding a solvent to the heat balance heat-retained at 100 degreeC, and obtaining the weight change amount of a solvent in air | atmosphere.

In addition, the second high boiling point solvent (H2) preferably has a dissolution parameter of 8.7 (cal / cm 3) ^1/2 or more. Since the second high boiling point solvent (H2) is hardly volatilized among the solvents (S), when the coating film of the colored photosensitive resin composition is dried under reduced pressure using a vacuum drying apparatus (VCD) or the like, it remains in the coating film until the end. At this time, when the dissolution parameter of the second high boiling point solvent (H2) is 8.7 (cal / cm 3) ^1/2 or more, the dispersibility of the colorant (C) is maintained satisfactorily until the end of the reduced pressure drying, resulting in surface defects and surface roughness of the coating film. This is suppressed. The solubility parameter is preferably 11 (cal / ㎤) ^1/2 or less, more preferably 10 (cal / ㎤) ^1/2 or less.

It is preferable that it is 0.1-10 weight% with respect to solvent (S) whole quantity, and, as for content of 2nd high boiling point solvent (H2), it is more preferable that it is 1-8 weight%.

It is preferable that the average boiling point of the solvent (S) is 165 degreeC or more, It is more preferable that it is 167 degreeC or more, It is more preferable that it is 168 degreeC or more. Moreover, it is preferable that an average boiling point is 200 degrees C or less, It is more preferable that it is 185 degrees C or less, It is further more preferable that it is 180 degrees C or less, It is especially preferable that it is 175 degrees C or less. Here, an "average boiling point" multiplies and averages the boiling point of each solvent with the content rate of the solvent with respect to the solvent (S) whole quantity.

The content of the solvent (S) is preferably an amount of 1 to 50% by weight, and more preferably an amount of 5 to 30% by weight of the solid content concentration of the colored photosensitive resin composition. By setting it as the said range, the film formation ability and applicability | paintability in a coloring photosensitive resin composition can be kept favorable.

[Other Ingredients]

The coloring photosensitive resin composition which concerns on this invention may contain an additive as needed. Examples of the additive include a thermal polymerization inhibitor, an antifoaming agent, a surfactant, a sensitizer, a curing accelerator, a photocrosslinker, a dispersant, a dispersing aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anticoagulant.

[Preparation method of colored photosensitive resin composition]

The coloring photosensitive resin composition which concerns on this invention can be obtained by mixing each said component with a stirrer. Moreover, you may filter using a filter so that the obtained mixture may become uniform.

According to the coloring photosensitive resin composition which concerns on this invention, it is possible to suppress surface defects and surface roughness of a coating film at the time of pressure reduction drying effectively. Especially, when a black pigment is used as a coloring agent (C), it is especially effective. The colored photosensitive resin composition containing the black pigment preferably has a high OD value as described above. However, even if the solvent (S) satisfies the above conditions, the content of the black pigment is increased for higher OD. It is possible to effectively suppress the risk of occurrence of surface defects and surface roughness.

<Color filter>

The color filter which concerns on this invention has a pattern formed using the coloring photosensitive resin composition which concerns on this invention. This color filter can be manufactured as follows, for example.

First, the colored photosensitive resin composition which concerns on this invention uses a contact transfer type | mold coating apparatus, such as a roll coater, a reverse coater, and a bar coater, and a non-contact type coating apparatus, such as a spinner (rotary coating apparatus), a slit coater, and a curtain flow coater, and a board | substrate. Apply on the top. Glass, polyethylene terephthalate, an acrylic resin, polycarbonate, etc. are mentioned as a material of a board | substrate.

Subsequently, the coating film of a coloring photosensitive resin composition is dried. Although a drying method is not specifically limited, For example, it vacuum-drys at room temperature using a vacuum drying apparatus (VCD), and for 60 to 120 second at the temperature of 80-120 degreeC, Preferably it is 90-100 degreeC on a hotplate after that. A method of drying is mentioned. According to the coloring photosensitive resin composition which concerns on this invention, even if it dried under reduced pressure in this way, the surface defect and surface roughness of a coating film can be suppressed effectively.

Next, this coating film is selectively exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. Although the energy dose to irradiate changes also with the composition of a coloring photosensitive resin composition, it is preferable that it is 30-2,000 mJ / cm <2>, for example.

Subsequently, the coating film after exposure is patterned with a developing solution to pattern into 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 developing solution 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, post-baking is performed about 220-250 degreeC, Preferably it is 230-240 degreeC about the pattern after image development. At this time, it is preferable to expose the formed pattern to the whole surface. As mentioned above, the black matrix which has a predetermined pattern shape can be formed.

The above operation is performed with respect to the coloring photosensitive resin composition of each color of red, green, and blue, and the pixel pattern of each color is formed. As a result, a color filter is formed.

In addition, when manufacturing a color filter, the ink of each color of red, green, and blue may be discharged from an ink jet nozzle to each pixel area partitioned by the black matrix, and the collected ink may be hardened by heat or light.

<Liquid crystal display display>

The liquid crystal display display which concerns on this invention has a color filter which concerns on this invention. In order to manufacture this liquid crystal display, first, the said color filter is formed on one board | substrate, and then an electrode, a spacer, etc. are formed sequentially. What is necessary is just to form an electrode etc. on the other board | substrate, and to inject | pour and seal a predetermined amount of liquid crystals by sticking both together.

Example

Hereinafter, examples of the present invention will be described, but the scope of the present invention is not limited to these examples.

<Example 1>

Synthesis of Photopolymerizable Compound

First, 235 g (epoxy equivalent 235) of bisphenol fluorene type epoxy resin, 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid were put into a 500 ml four-neck flask. It heated and melt | dissolved at 90 degreeC-100 degreeC, blowing air into this at the rate of 25 ml / min. Next, the solution was gradually warmed up in a cloudy state and heated to 120 ° C to completely dissolve it. The solution gradually became a clear viscous solution, but the stirring was continued as it was. In the meantime, the acid value was measured and heating and stirring were continued until it became less than 1.0 mgKOH / g. It took 12 hours to reach the target. And it cooled to room temperature and obtained bisphenol fluorene type epoxy acrylate.

Subsequently, 600 g of 3-methoxybutyl acetate is added to and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained, followed by dissolving 80.5 g of benzophenone tetracarboxylic acid anhydride and 1 g of tetraethylammonium bromide, and gradually It heated up and made it react at 110 degreeC-115 degreeC for 4 hours. After confirming the disappearance of the acid anhydride, 38.0 g of 1,2,3,6-tetrahydro phthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain Resin A-1 (weight average molecular weight: 3,400). Loss of acid anhydride was confirmed by IR spectrum.

[Preparation of Colored Photosensitive Resin Composition]

The following components were mixed so that solid content concentration might be 18 weight%, and it stirred with the stirrer for 2 hours, and filtered with a 5 micrometer membrane filter, and obtained the coloring photosensitive resin composition. The boiling point under atmospheric pressure of each solvent used for preparation of a coloring photosensitive resin composition, a dissolution parameter, and the weight change rate in 100 degreeC are as showing in Table 1.

(A): Resin A-1 (solid content: 55%, solvent: 3-methoxybutyl acetate). 23.6 parts by weight

Dipentaerythritol hexaacrylate 4.8 parts by weight

(B): IRGACURE® OXE # 02 (made by Chiba Specialty Chemicals Co., Ltd.) 1.4 parts by weight

(C): Carbon dispersion liquid ("CF black EX-1455", the Mikuni dye company, high resistance carbon: 24%, dispersing agent: 5%, solvent: 3-methoxybutyl acetate)... 100 parts by weight

(S): 3-methoxybutyl acetate / cyclohexanone / propylene glycol monomethyl ether acetate / 1,3-butylene glycol diacetate = 65: 15: 13: 7 (weight ratio)

<Examples 2-12, Comparative Examples 1-11>

A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the composition of the solvent (S) was changed as in Tables 2 and 3. In addition, the OD value of the coloring photosensitive resin composition used for the Example and the comparative example is 4.5. The boiling point under atmospheric pressure of each solvent used for preparation of a coloring photosensitive resin composition, a dissolution parameter, and the weight change rate in 100 degreeC are as showing in Table 1.

Here, the weight change rate was measured by adding a solvent to the thermal balance ("TG / DTA6200 (brand name), the product made by SII Nanotechnology, Inc.) insulated at 100 degreeC, and obtaining the weight change amount of the solvent in air | atmosphere.

<Evaluation>

After apply | coating the coloring photosensitive resin composition prepared in Examples 1-12 and Comparative Examples 1-11 on the glass substrate of 680 mm x 880 mm, it dried under reduced pressure at 66 Pa for 30 second, and then prebaked at 110 degreeC for 120 second. Thus, a coating film having a film thickness of about 1.0 μm was obtained. About this coating film, surface defect and surface roughness were evaluated as follows.

[Evaluation of Surface Defects]

The number of defects on the coating film surface was measured using the surface defect measuring apparatus (product name: "KLA-213X", the KLA-Tencor company make). The results are shown in Tables 2 and 3.

[Evaluation of Surface Roughness]

The surface roughness (Ra) of the coating film was evaluated using the atomic force microscope (SII nanotechnology company make). The results are shown in Tables 2 and 3. In Comparative Examples 3 to 11, the surface roughness was not evaluated because the number of defects on the surface of the coating film was remarkably large.

As can be seen from Tables 2 and 3, at least one low boiling point solvent (L) having a boiling point of less than 170 ° C, at least one first boiling point solvent (H1) having a boiling point of 170 ° C or more and less than 180 ° C, and a boiling point of 180 ° C or more Using the coloring photosensitive resin composition of Examples 1-12 which consists of 1 or more types of 2nd high boiling point solvents (H2), and also contains the solvent (S) whose ratio of a 1st high boiling point solvent (H1) is 60 weight% or more. When it did, the surface defect and surface roughness of the coating film at the time of drying under reduced pressure could be suppressed effectively. In particular, the effect of suppressing surface defects and surface roughness was improved by increasing the ratio of the second high boiling point solvent (H2) (Examples 1 to 4 and 5 to 7).

On the other hand, when using the colored photosensitive resin composition of Comparative Examples 1-5 and 10 which does not contain 2nd high boiling point solvent (H2), when a coating film is dried under reduced pressure, the surface defect of a coating film and surface roughening will arise remarkably. It was. Moreover, even if it contains the 2nd high boiling point solvent (H2), when using the coloring photosensitive resin composition of Comparative Examples 6-9 whose ratio of the 1st high boiling point solvent (H1) is 55 weight%, the coating film is dried under reduced pressure. When it did, the surface defect of the coating film occurred remarkably. Among these, the colored photosensitive resin compositions of Comparative Examples 8 and 9 have a higher average boiling point of the solvent (S) than, for example, Examples 1 and 5, but the ratio of the first high boiling point solvent (H1) is 60 even if the average boiling point is higher. In the case of less than% by weight, surface defects and surface roughness of the coating film could not be suppressed. Moreover, even when the coloring photosensitive resin composition of the comparative example 11 which does not contain a 1st high boiling point solvent (H1) and whose ratio of the low boiling point solvent (L) is 95 weight% is used, the surface of a coating film is dried under reduced pressure. The defect occurred remarkably.

Claims (9)

As colored photosensitive resin composition containing a photopolymerizable compound (A), a photoinitiator (B), a coloring agent (C), and a solvent (S), The solvent (S) is At least one low boiling point solvent (L) having a boiling point of less than 170 ° C at atmospheric pressure, 1 or more types of 1st high boiling point solvents (H1) which have a boiling point in atmospheric pressure from 170 degreeC or more and less than 180 degreeC, Consists of at least one second high boiling point solvent (H2) having a boiling point of at least 180 ℃ at atmospheric pressure, The coloring photosensitive resin composition whose ratio of the said 1st high boiling point solvent (H1) in the said solvent (S) is 60 weight% or more. The method according to claim 1, The coloring photosensitive resin composition whose ratio of the said 2nd high boiling point solvent (H2) in the said solvent (S) is 0.1-10 weight%. The method according to claim 1, The coloring photosensitive resin composition whose dissolution parameter of the said 2nd high boiling point solvent (H2) is 8.7 (cal / cm <3>) ^1/2 or more. The method according to claim 1, The coloring photosensitive resin composition whose average boiling point of the said solvent (S) is 165 degreeC or more. The method according to claim 1, The first high boiling point solvent (H1) is at least one selected from 3-methoxybutyl acetate (MA), dipropylene glycol dimethyl ether (DMM) and cyclohexanol acetate (CHXA), The second high boiling point solvent (H2) is propylene glycol diacetate (PGDA), gamma butyrolactone (GBL), dipropylene glycol methyl ether acetate (DPMA), diethylene glycol monoethyl ether acetate (EDGAC), 1,3 The coloring photosensitive resin composition which is 1 or more types chosen from butylene glycol diacetate (BGDA) and diethylene glycol monobutyl ether acetate (BDGAC). The method according to claim 1, The said low boiling point solvent (L) is the coloring photosensitive resin composition which is 1 or more types chosen from cyclohexanone (AN) and propylene glycol monomethyl ether acetate (PGMEA). The method according to claim 1, The coloring photosensitive resin composition in which the said coloring agent (C) contains a black pigment. The color filter which has a pattern formed using the coloring photosensitive resin composition of any one of Claims 1-7. The liquid crystal display which has a color filter of Claim 8.