JP4674048B2 - Coloring composition for forming color filter and color filter - Google Patents

Description

  The present invention relates to a color composition used for forming a filter segment and a black matrix constituting a color filter used in a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter using the same.

In the manufacture of color filters that make up liquid crystal displays (LCDs), it is necessary to apply a coating solution on a transparent substrate to form a uniform coating film with a thickness of about 1 to 3 μm when dried. A spin coating method is generally used.
In the spin coating method, the coating liquid is dropped on the transparent substrate while rotating the transparent substrate at a constant rotation speed, and the coating liquid is thinly extended by centrifugal force, and the coating film has a film thickness determined by the coating liquid viscosity, the rotation speed, etc. Is a coating method of forming on the surface of the transparent substrate.

  The spin coating method includes an open air type and a closed cup type, but both methods have a drawback that the coating film thickness of the rotation center portion and the peripheral portion of the transparent substrate is too thick compared to the intermediate portion. As a composition that eliminates this drawback and can form a coating film having a small surface difference between the central portion and the peripheral portion when coated by a spin coating method and having excellent surface smoothness, pigments, binder polymers, and radiation sensitive materials. A compound in which a compound is dissolved or dispersed in a specific solvent is known (for example, see Patent Document 1).

The difference in film thickness of the coating film is reduced by using the composition, but in the spin coating method, only a few percent of the coating solution dropped on the transparent substrate is applied to the surface of the transparent substrate, Since the remaining 90% of the coating solution is discharged from the transparent substrate, there is a disadvantage that there is a lot of waste, and this disadvantage has become a big problem with the recent increase in substrate size.
In order to eliminate the drawbacks of the spin coating method, a die coating method has been studied in recent years. The die coating method has the advantage that the coating solution supply circuit is all sealed up to the tip of the coating head, in addition to less waste of the coating solution than the spin coating method.
Japanese Patent Laid-Open No. 10-10724

However, in the die coating method, since the coating solution is exposed to the outside air at the slit opening at the head tip, the coating solution is liable to dry and solidify at the head tip, and the solidified product of the coating solution is clogged with slit nozzles or a transparent substrate. It causes the occurrence of vertical stripe unevenness (vertical application stripes in the application direction) of the coating film applied thereon. In addition, there is a drawback that the solidified product of the coating solution is detached from the tip of the head, and the coating quality is lowered such as being brought into the coated film as a foreign substance. Furthermore, when such a defect occurs, it is often necessary to remove the coating head from the apparatus main body and disassemble and clean it. When disassembly and cleaning are performed, since a considerable time is required from the stoppage of the apparatus to the return, a reduction in operating rate cannot be ignored.
This problem is difficult to solve by diverting a composition suitable for the spin coating method.
Accordingly, an object of the present invention is to provide a coloring composition that is difficult to solidify at the tip of the coating liquid discharge port in a die coating type coating apparatus and is suitable for preventing the occurrence of coating defects.

（式（１）中、Ｒ₁はハロゲン原子を表し、Ｒ₂は置換基を有しても良い炭素数１〜４のアルキル基を表す。）
The coloring composition of the present invention comprises a pigment, a resin, a photopolymerization initiator (however, a hexaarylbiimidazole compound represented by the formula (1) , 2,2′-bis (2-chlorophenyl) -4, 4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole , and tetra-n-butylammonium methyltris (4-methylnaphthyl) borate ), and a colored composition, wherein the solvent is The solvent (a) in which the difference between the solubility parameter of the resin and the solubility parameter of the solvent is 0 (cal / cm ³ ) ^1/2 or more and less than 1.5 (cal / cm ³ ) ^1/2, and the solubility of the resin The solvent and the solubility parameter of the solvent are 1.5 (cal / cm ³ ) ^1/2 or more and less than 5.0 (cal / cm ³ ) ^1/2 and the solvent (b) The content is based on the total amount of solvent. Characterized in that 0.5 wt% or more 30 wt% or less Te.
In addition, the color filter of the present invention includes a filter segment formed from the colored composition. The color filter of the present invention includes a black matrix formed from the colored composition. It is characterized by.
Formula (1)

(In Formula (1), R ₁ represents a halogen atom, and R ₂ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent.)

The coloring composition of the present invention focuses on the solubility of the resin in the solvent, and since a combination of a solvent having a high solubility in the resin and a low solvent is used in combination, it is dried at the tip of the coating liquid discharge port of the die coating type coating apparatus. There is no solidification.
Therefore, when the colored composition of the present invention is used, a uniform coating film can be formed without causing coating film defects such as vertical stripes due to solidification of the coating solution. In addition, when the colored composition of the present invention is used, there is no thickening over time, and stable production can be performed even after long-term storage.
Therefore, by using the colored composition of the present invention, it is possible to improve the equipment operation rate and to manufacture a high-quality color filter and a black matrix substrate with a high yield.

（式（１）中、Ｒ₁はハロゲン原子を表し、Ｒ₂は置換基を有しても良い炭素数１〜４のアルキル基を表す。）
First, the coloring composition of this invention is demonstrated concretely.
The colored composition of the present invention comprises a pigment, a resin, a photopolymerization initiator (a hexaarylbiimidazole compound represented by the formula (1) , 2,2′-bis (2-chlorophenyl) -4, 4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole , and tetra-n-butylammonium methyltris (4-methylnaphthyl) borate ), and a solvent. In order to prevent a coating film defect due to drying and solidification of the coloring composition at the tip of the coating liquid discharge port of the coating apparatus, the solvent has a difference between the solubility parameter of the resin and the solubility parameter of the solvent of 0 (cal / Cm ³ ) ^1/2 or more and less than 1.5 (cal / cm ³ ) ^1/2 and the difference between the solubility parameter of the resin and the solubility parameter of the resin is 1.5 (cal / cm ³ ) ^1/2 or more and less than 5.0 (cal / cm ³ ) ^1/2 and the content of the solvent (b) is 0.5% by weight or more and 30% or more based on the total amount of the solvent. % By weight or less.
Formula (1)

(In Formula (1), R ₁ represents a halogen atom, and R ₂ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent.)

The resin contained in the colored composition of the present invention includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in admixture of two or more.
The resin solubility parameter in the present invention is a value calculated by the Fedors method. When two or more kinds of resins are used in combination, the solubility parameter value of the mixed resin calculated from the following formula is used as the resin solubility parameter. It is a parameter.

_{δ Pmix = a 1 δ P1 +} a 2 δ P2 + a 3 δ P3 + ··· + a n δ Pn
δ _Pmix : Solubility parameter of mixed resin δ _P1 : Solubility parameter of resin 1 δ _P2 : Solubility parameter of resin 2 δ _P3 : Solubility parameter of resin 3
・
・
δ _Pn : Solubility parameter of resin n a ₁ : Weight fraction of resin 1 in mixed resin a ₂ : Weight fraction of resin 2 in mixed resin a ₃ : Weight fraction of resin 3 in mixed resin
・
・
a _n: weight fraction of the resin n in the mixed resin

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  In the case of patterning the coloring composition by a photolithography method, it is preferable to use an alkali-soluble resin capable of alkali development. As the alkali-soluble resin, a methacrylic copolymer containing methacrylic acid and 2-hydroxyethyl methacrylic acid as a copolymerization component is preferable from the viewpoint of patterning characteristics, pigment dispersibility, solvent resistance, and the like.

The solvent contained in the colored composition of the present invention comprises a solvent (a) having a high solubility in the resin used and a solvent (b) having a low solubility. In the solvent (a), the difference between the solubility parameter of the resin and the solubility parameter of the solvent is 0 (cal / cm ³ ) ^1/2 or more and less than 1.5 (cal / cm ³ ) ^1/2 , preferably 0 (cal / cm ³ ) It is selected from solvents that are ^1/2 or more and less than 1.3 (cal / cm ³ ) ^1/2 . In the solvent (b), the difference between the solubility parameter of the resin and the solubility parameter of the solvent is 1.5 (cal / cm ³ ) ^1/2 or more and less than 5.0 (cal / cm ³ ) ^1/2 , preferably 1 It is selected from the solvents that are 7 (cal / cm ³ ) ^1/2 or more and less than 4.0 (cal / cm ³ ) ^1/2 .

The solubility parameter of the solvent is a value obtained from the physical quantity of the solvent (e.g. heat of evaporation), and values described in various documents can be used.
Content of the solvent (b) in a coloring composition is 0.5 to 30 weight% on the basis of the whole quantity of a solvent, and it is preferable that it is 1 to 25 weight%. If it exceeds 30% by weight, the solubility of the resin in the mixed solvent consisting of the solvent (a) and the solvent (b) is lowered, and it becomes easy to solidify at the tip of the coating liquid discharge port in the coating apparatus. Moreover, if it is less than 0.5 weight%, the temporal stability of a coloring composition may be inferior.

As the solvent, dichlorodifluoromethane (5.5), n-butane (6.8), n-pentane (7.0), n-hexane (7.2), 1,1,2-trichlorotrifluoro Ethylene (7.3), n-heptane (7.4), diethyl ether (7.4), propylene glycol ethyl ether acetate (7.5), n-octane (7.6), methylcyclohexane (7.8) ), Isopentyl acetate (7.8), dipropylene glycol dimethyl ether (7.9), dodecane (7.9), dioctyl phthalate (7.9), diisobutyl ketone (8.1), cyclohexane (8.2) , Dibutyl ketone (8.2), sec-butylbenzene (8.3), amyl acetate (8.3), 1-chlorobutane (8.5), methylal (8.5), 1,1,1- Lichloroethane (8.6), n-butylbenzene (8.6), methyl-i-amyl ketone (8.6), methyl isobutyl ketone (8.6), 4-heptanone (8.7), m-diethylbenzene (8.7), o-diethylbenzene (8.7), p-diethylbenzene (8.7), diethylene glycol diethyl ether (8.7), n-butyl acetate (8.7), ethylbenzene (8.8), m-xylene (8.9), ethylene glycol monobutyl ether acetate (8.9), toluene (8.9), propylene glycol diacetate (8.9), 2-heptanone (9.0), o-xylene ( 9.0), cyclohexylamine (9.1), furan (9.1), ethyl acetate (9.1), trans-dichloroethylene (9.2), chloroform (9.2), propylene glycol monomethyl ether acetate (9.2), benzene (9.2), styrene (9.3), propylene ethylene glycol monomethyl ether acetate (9.3), methyl ethyl ketone (9.3) , Diethylene glycol dimethyl ether (9.4), dipropylene glycol monomethyl ether (9.4), tetrahydrofuran (9.55), tetralin (9.5), ethylene glycol monomethyl ether acetate (9.6), acetophenone (9.7) ), M-dichlorobenzene (9.8), acetone (9.8), ethyl chloride (9.8), propylene glycol monoethyl ether (9.8), 2-ethylhexanol (9.9), ethylene glycol Monomethyl ether acetate (9. 9), cyclohexane (9.9), dichloromethane (9.9), 2-nitropropane (10.0), o-dichlorobenzene (10.0), dioxane (10.0), 1,2,3- Trichloropropane (10.1), diacetone alcohol (10.2), β-β-dichloroethyl ether (10.3), butoxyethanol (10.3), 2-ethylbutanol (10.4), diethylene glycol mono Ethyl ether (10.4), cyclohexanone (10.4), nitrobenzene (10.4), benzaldehyde (10.4), n-heptanol (10.6), cyclohexanol (10.9), diethylene glycol monomethyl ether ( 11.1), nitroethane (11.1), acetonitrile (11.9), n-propanol (12. 0), dimethylformamide (12.1), methyl cellosolve (12.1), nitromethane (12.3), γ-butyrolactone (12.9), dimethyl sulfoxide (12.9), n-butyl alcohol (14 0.0), ethanolamine (15.5) (in parentheses are solubility parameters). Unit: (cal / cm ³ ) ^1/2 ) and the like. As the solvent, two or more kinds of solvents that satisfy the conditions may be mixed and used.

  When a methacrylic copolymer having methacrylic acid and 2-hydroxyethyl methacrylic acid as a copolymerization component is used as the resin, the amount of solidified product of the colored composition during coating is less, so the solvent (b) A diethylene glycol solvent or a propylene glycol ester solvent is preferable.

As the pigment contained in the coloring composition of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be used for the coloring composition of this invention is shown with a color index number.

  Red pigmented compositions for forming red filter segments include, for example, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2. 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224 Red pigments such as 226, 227, 228, 240, 246, 254, 255, 264, and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

  Examples of the yellow coloring composition for forming the yellow filter segment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20. 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 It can be used yellow pigments such 168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199.

For example, an orange pigment such as CI Pigment orange 36, 43, 51, 55, 59, 61 can be used as the orange coloring composition for forming the orange filter segment.
As the green coloring composition for forming the green filter segment, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green coloring composition.

  Examples of blue coloring compositions for forming blue filter segments include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. Blue pigments can be used. Purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 can be used in combination with the blue coloring composition.

For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 or the like is used as a cyan coloring composition for forming a cyan filter segment. Can do.
For the magenta coloring composition for forming the magenta color filter segment, for example, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81 can be used. A yellow pigment can be used in combination with the magenta colored composition.

  Examples of the black coloring composition for forming the black matrix include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically CI pigment black 1, 6, 7, 12, 20, 31 and the like. Can be used. A mixture of a red pigment, a blue pigment, and a green pigment can also be used for the black coloring composition. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black coloring composition.

In addition, inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. And metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
In addition to the pigment, the coloring composition of the present invention may contain a dye for toning.

  When patterning the coloring composition by photolithography, a monomer or oligomer having photoreactivity is added. Photoreactive monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxy Ethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) a Acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) Various acrylates and methacrylates such as acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl ( Examples include meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

（式（１）中、Ｒ₁はハロゲン原子を表し、Ｒ₂は置換基を有しても良い炭素数１〜４のアルキル基を表す。）


Moreover, when patterning a coloring composition by photolithography using ultraviolet rays, a photopolymerization initiator or the like is added. Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone photopolymerization initiators such as zoyl-4′-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (to Chloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine and other triazine photopolymerization initiators, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators (however, Hexaarylbiimidazole compounds represented by formula (1) , 2,2′-bis (2-chlorophenyl) -4, 4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole , and tetra- n-butylammonium methyltris (4-methylnaphthyl) borate ) and the like are used.
Formula (1)

(In Formula (1), R ₁ represents a halogen atom, and R ₂ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent.)

  The above photopolymerization initiators can be used alone or in combination of two or more. As the sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10- Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone These compounds can also be used in combination.

  The coloring composition of the present invention comprises a three-roll mill in a resin and a solvent, together with a pigment or a pigment composition comprising two or more pigments, together with the photoreactive monomer or oligomer and a photopolymerization initiator as necessary. It can be manufactured by finely dispersing using various dispersing means such as a two-roll mill, a sand mill, a kneader, and an attritor. Moreover, the coloring composition containing 2 or more types of pigments can also be manufactured by mixing each pigment separately finely dispersed in a resin and a solvent. When the pigment is dispersed in the resin and the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. The dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition is used in which the pigment is dispersed in a resin and a solvent using the dispersion aid. In this case, a color filter having excellent transparency can be obtained.

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

  The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called pigments. Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

  The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition, and also improve the adhesion of a silane coupling agent or the like in order to enhance the adhesion to the transparent substrate. An agent can also be contained. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite.

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

  The coloring composition can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. The colored resist material is obtained by dispersing a pigment in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and a solvent.

  When the filter segment and the black matrix are formed by a photolithography method, the pigment is preferably contained in the coloring composition at a ratio of 1.5 to 15% by weight. Moreover, when forming a filter segment and a black matrix by a printing method, it is preferable to contain in the ratio of 1.5 to 45 weight% in a coloring composition. Further, the pigment is preferably contained in the final filter segment and the black matrix in a proportion of 10 to 50% by weight, more preferably 20 to 45% by weight, and the remainder substantially consists of a resinous binder.

The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.
The colored composition of the present invention has a viscosity of 10 mPa · s or less measured at a rotation speed of 20 rpm using an E-type viscometer at 25 ° C. in order to obtain a uniform coating film without causing uneven coating. It is preferable to adjust so that it may become, and it is more preferable to adjust so that it may become 1 mPa * s or more and 8 mPa * s or less.

Next, a color filter comprising a filter segment or a black matrix formed from the colored composition of the present invention will be described.
The color filter of the present invention comprises a filter segment and a black matrix on a transparent substrate, and the filter segment and / or the black matrix is coated with the coloring composition of the present invention using a die coat type coating apparatus. As a result, it is formed on a transparent substrate.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  The formation of each color filter segment and the black matrix by photolithography is performed by the following method. That is, the coloring composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate using a die coating type coating apparatus so that the dry film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove the uncured portion and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples and comparative examples, “parts” means “parts by weight”.
First, preparation of acrylic resin solutions used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

(Preparation of acrylic resin solution)
A reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
2-hydroxyethyl methacrylic acid 60.0 parts
Methacrylic acid 60.0 parts
Methyl methacrylate 65.0 parts
Butyl methacrylate 65.0 parts
Azobisisobutyronitrile 10.0 parts After the addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added. The reaction was continued for 1 hour to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 40,000.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. To prepare an acrylic resin solution. The solubility parameter of this resin is 10.8 (cal / cm ³ ) ^1/2 .

[Example 1]
A mixture having the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a carbon black dispersion.
Carbon black (Degussa “Printex75”) 12.0 parts Dispersant (Zeneca “Solsperse 20000”) 2.4 parts Acrylic resin solution 28.0 parts Cyclohexanone 57.6 parts After stirring and mixing, the mixture was filtered through a 1 μm filter to obtain a black resist material.
Carbon black dispersion 55.4 parts Acrylic resin solution 2.1 parts Trimethylolpropane triacrylate 4.8 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy) 2.5 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts Cyclohexanone 19.0 parts Diethylene glycol diethyl ether 16.0 parts

[Examples 2-3 and Comparative Examples 1-4]
Except for changing the composition of the pigment, dispersant, resin, monomer, photopolymerization initiator, sensitizer, and solvent to the ratio shown in Table 1 (weight ratio with the total amount of the resist material being 100), the same as in Example 1. Thus, each color resist material was obtained.

Black pigment: Carbon black ("Printex75" manufactured by Degussa)
Red pigment: 5.08 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254)
("Irga Four Red B-CF" manufactured by Ciba Geigy)
Anthraquinone pigment (CI Pigment Red 177) 0.82 parts
(Ciba Geigy “Chromophthal Red A2B”)
Anthraquinone pigment (CI Pigment Yellow 199) 0.20 parts
(Ciba Geigy's “Chromoval Yellow GT-AD”)

Dispersant: “Solsperse 20000” manufactured by Zeneca
Monomer: Trimethylolpropane triacrylate (Shin Nakamura Chemical "NK Ester ATMPT")
Photopolymerization initiator: “Irgacure 907” manufactured by Ciba Geigy
Sensitizer: “EAB-F” manufactured by Hodogaya Chemical Co., Ltd.
Solvent A: Cyclohexanone (9.9 (cal / cm ³ ) ^1/2 )
Solvent B: Diethylene glycol diethyl ether (8.7 (cal / cm ³ ) ^1/2 )
Solvent C: Propylene glycol diacetate (8.9 (cal / cm ³ ) ^1/2 )
Solvent D: Isopentyl acetate (7.8 (cal / cm ³ ) ^1/2 )

Viscosities of the resist materials obtained in Examples 1 to 4 and Comparative Examples 1 to 3 before and after storage at 40 ° C. for 7 days, the vertical streaks of the dried coating film formed using the resist material, and the head tips were detached. The presence or absence of the resist material solidified product was evaluated by the following method. The results are shown in Table 2.
[viscosity]
The resist material was stored at 40 ° C. for 7 days, and the viscosity at 25 ° C. before and after storage was measured using an E-type viscometer (manufactured by Tokimec) at a rotation speed of 20 rpm.

[Vertical smoothing of dry coating]
The obtained resist material was applied onto a 10 cm × 10 cm glass substrate using a die coater, and the obtained coated substrate was prebaked at 70 ° C. for 20 minutes to obtain a dried coating film. Vertical stripes (vertical application stripes in the application direction) of the obtained dried coating film were evaluated in three stages by visual observation.
○: No vertical stripes are observed.
Δ: Slight vertical stripes are observed.
X: Remarkably vertical stripes are observed.

[Presence / absence of solidified resist material desorbed from the head tip]
On the obtained dried coating film, the presence or absence of a solidified resist material detached from the tip of the head was evaluated in three stages by visual observation.
○: No solidified product is observed.
Δ: 1 or more and less than 10 solidified products.
X: 10 or more solidified products.

In the coating films obtained in Examples 1, 2, and 4, the resist material did not solidify at the tip of the coating head, so that no vertical stripes were generated and the coating film was uniform. In addition, thickening over time was not observed.
In the coating film obtained in Example 3, no occurrence of vertical stripes was observed, and while no thickening was observed over time, a slightly solidified resist material was observed.
The coating film obtained in Comparative Example 1 had slight vertical stripes. Many solidified resist materials were observed.
Since the resist material was solidified at the tip of the coating head, the coating film obtained in Comparative Example 2 had noticeable vertical stripes and was a non-uniform coating film.
The coating film obtained in Comparative Example 4 did not generate vertical stripes, but increased in viscosity over time.

Claims (5)

Pigment, resin, photopolymerization initiator (however, a hexaarylbiimidazole compound represented by the formula (1) , 2,2′-bis (2-chlorophenyl) -4, 4 ′ , 5,5′-tetraphenyl- 1, 2'-biimidazole , and tetra-n-butylammonium methyltris (4-methylnaphthyl) borate ), and a colored composition containing a solvent, wherein the solvent is a solubility parameter of the resin and a solvent The difference in solubility parameter between 0 (cal / cm ³ ) ^{1/2 and} less than 1.5 (cal / cm ³ ) ^1/2 and the difference between the solubility parameter of the resin and the solubility parameter of the solvent 1.5 (cal / cm ³ ) ^1/2 or more and less than 5.0 (cal / cm ³ ) ^{1/2 of the} solvent (b), and the content of the solvent (b) 0.5 wt% or more as standard 3 The color filter forming coloring composition being not more than% by weight.
Formula (1)

(In Formula (1), R ₁ represents a halogen atom, and R ₂ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent.)   2. The color filter forming material according to claim 1, wherein the resin is a methacrylic copolymer having methacrylic acid and 2-hydroxyethyl methacrylic acid as copolymerization components, and the solvent (b) is a diethylene glycol solvent or a propylene glycol ester solvent. Coloring composition.   The coloring composition for forming a color filter according to claim 1 or 2, wherein the pigment is carbon black.   A color filter comprising a filter segment formed from the colored composition according to claim 1. A color filter comprising a black matrix formed from the colored composition according to claim 1.