JP5410146B2 - Color filter color resist manufacturing method, color filter color resist manufactured by the manufacturing method, and color filter - Google Patents

Description

    The present invention relates to a method for producing a color resist for a color filter used for forming a filter segment constituting a color filter used in a color liquid crystal display device and a solid-state imaging device, a color resist for a color filter produced by the production method, and The present invention relates to a color filter obtained using the color resist for color filter.

At present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used. In the pigment dispersion method, for example, a pigment dispersion in which a pigment is dispersed in a transparent resin or a solvent is prepared, and a photopolymerizable monomer, a photopolymerization initiator, and the like are mixed and adjusted to the color resist. Is used.

  Further, a member having a function of expressing a color by transmitting light, such as a color filter, is required to have a high transmittance, a high contrast ratio, light resistance, and the like, and generally a finer pigment is used. Particularly in recent years, since a higher luminance and a higher contrast ratio are required for a liquid crystal display device, a pigment in which the primary particle size is reduced by using a finer treatment to the limit has been used. Since some of the primary particles of such a finely-treated pigment are aggregated to produce secondary particles, generally, the pigment is dispersed in a transparent resin or solvent by using a disperser, so that The next particle is loosened. However, when the pigment is dispersed in the transparent resin or the solvent, if the dispersion is excessive, the primary particles are crushed in parallel with the secondary particles being loosened to the primary particles, and the resulting pigment dispersion Stability is reduced. In addition, pigment dispersions produced as intermediates for color resists for color filters improve the solubility of photopolymerizable monomers and photopolymerization initiators added in the post-process and improve the degree of composition freedom of color resists for color filters. For this reason, the pigment concentration and the solid content are often adjusted. Therefore, in the pigment dispersion, the interaction between the pigment, the resin, and the solvent becomes large, and it is more difficult to control the degree of dispersion and viscosity of the pigment dispersion than the final color resist for color filter. Therefore, when the color resist for color filter is adjusted using such a pigment dispersion, a massive pigment solid having a size causing a pixel defect of the liquid crystal display device may be formed.

  In addition, since each color filter segment such as RGB (red, green, blue) forming a color filter generally cannot obtain a target spectral spectrum only with a single pigment, a pigment dispersion containing two or more pigments is used. Although often used, different types of pigments tend to cause heteroaggregation, and it is particularly difficult to obtain a stable pigment dispersion when two or more types of fine pigments are included.

  In particular, zinc halide phthalocyanine pigments that have been attracting attention as colorants that satisfy high lightness and high contrast ratio in recent years are used in color resists for color filters used in the formation of green filter segments. Therefore, for example, as described in Patent Document 1, a pigment dispersion of a yellow pigment is often mixed to adjust the spectral spectrum. However, it is known that zinc halide phthalocyanine pigments are pigments that are difficult to disperse even with only a single color. When a pigment dispersion using this pigment is mixed with a pigment dispersion of a yellow pigment, the balance of the dispersion system is further increased. It is very difficult to obtain a colored resist for a color filter that has a high contrast ratio and is stable over time.

JP 2003-161828 A

An object of the present invention is to provide a colored resist for a color filter that is excellent in fluidity and storage stability with time, and that suppresses the increase in viscosity and the decrease in contrast ratio over time.
Another object of the present invention is to provide a color filter having a high contrast ratio.

  The method for producing a color resist for a color filter according to the present invention comprises wet treatment of a green organic pigment A containing a halogenated zinc phthalocyanine pigment, a pigment composition A containing a transparent resin or an organic solvent, and a yellow organic pigment B in a transparent resin and an organic solvent. The pigment dispersion B obtained by mixing the pigment dispersion B obtained by dispersion, and further producing the pigment dispersion C by wet dispersion using a media-type wet disperser; and the pigment dispersion obtained in step (a) The process (b) which mixes a photopolymerizable monomer with the body C is characterized by the above-mentioned.

 In the method for producing a color resist for a color filter of the present invention, the pigment composition A is preferably a pigment dispersion A obtained by wet-dispersing a green organic pigment A containing a halogenated zinc phthalocyanine pigment, a transparent resin, and an organic solvent. .

  Moreover, in the manufacturing method of the color resist for color filters of this invention, it is preferable that the pigment composition A or the pigment dispersion B contains the pigment dispersant.

 In the method for producing a color resist for color filter of the present invention, the content of the green organic pigment A contained in the pigment dispersion C is preferably in the range of 68 to 95% by weight based on the total pigment weight. .

 The color resist for color filter of the present invention is manufactured by the method for manufacturing a color resist for color filter.

 In addition, the color filter of the present invention includes a filter segment formed using the color resist for color filter.

  According to the method for producing a color resist for a color filter of the present invention, a pigment composition A containing a green organic pigment A containing a halogenated zinc phthalocyanine pigment and a yellow organic pigment B were uniformly wet dispersed in advance in a transparent resin and an organic solvent. By mixing with pigment dispersion B and further wet-dispersing using a media-type wet disperser, the color filter coloring resist has good storage stability with time, reduced contrast ratio with time, and increased viscosity with time. Can be manufactured. Further, according to the present invention, a color filter having a high contrast ratio can be obtained.

Hereinafter, the present invention will be described in detail.
The method for producing a color resist for color filter according to the present invention comprises wet treatment of a green organic pigment A containing a halogenated zinc phthalocyanine pigment, a pigment composition A containing a transparent resin or an organic solvent, and a yellow organic pigment B in a transparent resin and an organic solvent. The pigment dispersion B obtained by mixing the pigment dispersion B obtained by dispersion, and further producing the pigment dispersion C by wet dispersion using a media-type wet disperser; and the pigment dispersion obtained in step (a) The process (b) which mixes a photopolymerizable monomer with the body C is characterized by the above-mentioned.

<Method for Producing Pigment Dispersion C: Step (a)>
First, the process (a) which manufactures the pigment dispersion C is demonstrated.
In the method for producing a color resist for a color filter of the present invention, the step (a) of producing a pigment dispersion C includes a green organic pigment A containing a halogenated zinc phthalocyanine pigment and a pigment composition A containing a transparent resin or an organic solvent. And a pigment dispersion B obtained by wet-dispersing the yellow organic pigment B in a transparent resin and an organic solvent, and further wet-dispersing using a media-type wet disperser.

(Production of Pigment Composition A and Pigment Dispersion A)
The pigment composition A of the present invention comprises a green organic pigment A containing a halogenated zinc phthalocyanine pigment and a transparent resin or organic solvent, and may contain both a transparent resin and an organic solvent.
The pigment composition A can be produced simply by mixing the green organic pigment A and the transparent resin or organic solvent with a stirrer or the like, but is produced by wet-dispersing the green organic pigment A, the transparent resin and the organic solvent, Since it becomes a high contrast ratio when it uses as the pigment dispersion A, it is preferable.

(Production of Pigment Dispersion B)
The pigment dispersion B is a pigment dispersion obtained by wet-dispersing the yellow organic pigment B in a transparent resin and an organic solvent.

In the production of the pigment dispersion A and the pigment dispersion B, the wet dispersion is performed by mixing an organic pigment, a transparent resin, an organic solvent, and, if necessary, a pigment dispersant, an additive, etc., into a three roll mill, a two roll mill, Media type wet disperser such as bead mill such as Banbury mixer, kneader, single screw extruder, twin screw extruder, ultrasonic disperser, cylindrical disperser horizontal type, vertical type, and annular type (annular type) This can be done by dispersing. In addition, the pigment dispersion A and the pigment dispersion B may be pigment dispersions manufactured in the form of a colored chip containing an organic pigment and a thermoplastic resin. The colored chip is a three-roll mill after mixing organic pigment, thermoplastic resin and other components such as a pigment dispersant as necessary using a Henschel mixer, cooler mixer, nauter mixer, drum mixer, tumbler, etc. It is manufactured by heating and kneading with a two-roll mill, Banbury mixer, kneader, single-screw extruder, twin-screw extruder, etc., and pulverizing after cooling. The colored chips thus produced are refined as necessary using various grinding devices such as a hammer mill, a turbo crusher, and an air jet mill, and are easily dissolved only by stirring and dissolving in an organic solvent. The colored chip can be used as it is, and further can be dispersed in an organic solvent by a media type wet disperser such as a bead mill.
The method using a colored chip is preferable because the effect of improving the contrast ratio of the obtained color filter is increased.

(Production of Pigment Dispersion C)
The pigment dispersion C is produced by mixing the pigment composition A or pigment dispersion A and the pigment dispersion B, and further wet-dispersing using a media-type wet disperser.
Media type wet dispersers include horizontal, vertical and annular (annular) cylindrical dispersers such as paint conditioners, attritors, sand mills, dyno mills, ball mills, super apex mills, and coball mills. Bead mills such as diamond fine mill, DCP mill, OB mill, Eiger mill, spike mill, and picogren mill. Among them, a super apex mill, an Eiger mill, a DCP mill, a picogren mill, etc., which are annular (annular) dispersers are preferable.

  The material of the medium is not particularly limited as long as it is a rigid body, and generally used glass, steel, stainless steel, ceramics, zircon, zirconia and the like can be mentioned. The media particle size is preferably 1.0 mmφ or less in order to achieve fine dispersion and a high contrast ratio. When media in the range of 0.5 to 0.05 mmφ is used, the effect of higher contrast ratio is exhibited. It is preferable because it is easy to do. It is also preferable in terms of dispersion efficiency to disperse in a wet disperser using a medium having a large particle diameter in advance and then perform multistage wet dispersion using a medium having a smaller particle diameter. As a dispersion method, either circulation or path dispersion can be used.

  In this way, the yellow organic pigment B is wet-dispersed in advance in a transparent resin and an organic solvent, and the pigment dispersion B in which the pigment is uniformly dispersed and the pigment composition A containing the green organic pigment A containing the zinc halide phthalocyanine pigment are mixed. Furthermore, by performing wet dispersion using a media-type wet disperser, two or more kinds of fine pigments dispersed in a transparent resin and an organic solvent can stably exist, and the viscosity increases with time. , And a reduction in contrast ratio can be suppressed. As a result, the colored resist for color filter produced by the production method of the present invention comprising the step (b) of mixing the photopolymerizable monomer with the pigment dispersion C obtained in the step (a) is also fluid, Excellent storage stability over time.

<Constituent Materials for Pigment Composition A, Pigment Dispersion A, and Pigment Dispersion B>
Hereinafter, each component constituting the pigment composition A, the pigment dispersion A, and the pigment dispersion B of the present invention will be described.

(Organic pigment)
Specific examples of organic pigments used in the pigment composition A, pigment dispersion A, and pigment dispersion B are indicated by color index numbers.
The pigment composition A and the pigment dispersion A of the present invention are characterized by using a green organic pigment A containing a halogenated zinc phthalocyanine pigment. Representative zinc halide phthalocyanine pigments include C.I. I. And CI Pigment Green 58. By using a halogenated zinc phthalocyanine pigment, it is possible to obtain a high brightness not obtained with other green pigments.

The yellow organic pigment B is used for color adjustment and complementary color purposes, and examples of yellow pigments that can be used include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, and 214, and the like can be given.
Among these, C.I. I. It is preferable to use together CI Pigment Yellow 138, 139, 150, etc. in that the chromaticity region can be expanded.

  The content of the green organic pigment A contained in the pigment dispersion C obtained in the step (a) can be appropriately selected according to the use, and is 56 to 97 wt. Based on the total pigment weight (100 wt.%). %, Preferably 68 to 95% by weight. When the ratio of the organic pigment A is 95% by weight or less, the decrease in contrast ratio with time is small, and when the ratio of the organic pigment A is 68% by weight or more, the degree of thickening with time is small.

Moreover, it is preferable that the volume average primary particle diameter of the organic pigment used for the pigment composition A, the pigment dispersion A, and the pigment dispersion B is 20-100 nm, Especially preferably, it is the range of 25-85 nm. When the volume average primary particle diameter of the organic pigment is 20 nm or more, it is easy to disperse in an organic solvent, and when it is 100 nm or less, a sufficient contrast ratio can be obtained.
The volume average primary particle diameter in the present invention is obtained by measuring the short axis diameter and the long axis diameter of the primary particles of 100 pigments using a transmission (TEM) electron micrograph, and calculating the average of the short axis diameter and the long axis diameter. Is the particle size (d) of the pigment particles, then the volume (V) of each particle is determined assuming that each pigment is a sphere having the determined particle size, and this operation is performed for 100 pigment particles. From this, the volume average particle diameter (MV) obtained from the following formula is the average primary particle diameter.
MV = Σ (V · d) / Σ (V)

(Miniaturization of pigment)
The organic pigment used in the pigment composition A, the pigment dispersion A, and the pigment dispersion B is preferably refined by performing, for example, a salt milling process.
Salt milling is a process of heating a mixture of an organic pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, or a sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt works as a crushing aid, and it is thought that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Accordingly, during the kneading, the organic pigment is simultaneously crushed and crystal growth occurs, and the primary particle size and shape of the organic pigment obtained differ depending on the kneading conditions.

  From the viewpoint of the primary particle diameter and shape of the obtained organic pigment, the heating temperature is preferably 40 to 150 ° C. When the heating temperature is less than 40 ° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes close to amorphous, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds excessively and the primary particle diameter of the pigment becomes large, which is not preferable as a colorant for the color resist for color filters. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.

  As the water-soluble inorganic salt used for the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the organic pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the organic pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. . However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the organic pigment.

  When performing the salt milling treatment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the organic pigment.

(Pigment dispersant)
It is preferable that the pigment composition A or the pigment dispersion B in the present invention appropriately contains a pigment derivative, a pigment dispersant such as a resin-type pigment dispersant, and a surfactant. Pigment dispersants are excellent in dispersing organic pigments and have a great effect of preventing re-aggregation of organic pigments in pigment compositions and pigment dispersions. Therefore, by using a colored resist containing a pigment dispersant, transparency is improved. An excellent color filter can be obtained. Therefore, it is preferable that the pigment composition A and the pigment dispersion B contain a pigment dispersant.

  The pigment derivative is a compound represented by the following general formula (1), and there are those having a basic substituent and those having an acidic substituent.

General formula (1):
AB Formula (1)
A: Organic dye residue B: Basic substituent or acidic substituent

Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, or JP-B-5-9469. What is currently used can be used, These can be used individually or in mixture of 2 or more types.
The blending amount of the pigment derivative is preferably 0.1 to 30 parts by weight, and most preferably 0.5 to 25 parts by weight with respect to 100 parts by weight of the pigment. When the blending amount of the dye derivative is less than 0.1 parts by weight with respect to the total amount of the pigment, the dispersibility may be deteriorated, and when it exceeds 30 parts by weight, the heat resistance and light resistance may be deteriorated.

  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 dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye 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 alkyleneimines) 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.

  Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 3184, manufactured by Japan Lubrizol Corporation EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400405, manufactured by Efka Chemicals 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503 and the like.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more.

  When a resin type pigment dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the pigment. When the blending amount of the dispersion aid is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion aid is affected by an excessive dispersion aid. is there.

(Transparent resin)
The transparent resin is preferably a resin having a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Thermoplastic resin, thermosetting resin, ethylenically unsaturated double A photopolymerizable resin having a bond can be used.

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. And vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
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 photopolymerizable resin having an ethylenically unsaturated double bond include a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, and an amino group, and an isocyanate group, an aldehyde group, and an epoxy group. (Meth) acrylic compounds having reactive substituents such as cinnamic acid, a resin in which a photocurable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer, or styrene-anhydrous A resin obtained by half-esterifying a linear polymer containing an acid anhydride such as a maleic acid copolymer or an α-olefin-maleic anhydride copolymer with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate Etc.
When the color filter resist of the present invention is used in the form of an alkali development type colored resist, it is preferable to use a thermoplastic, thermosetting or photopolymerizable resin having an acidic group such as a carboxyl group as the transparent resin. .

  The transparent resin used for the pigment composition A, the pigment dispersion A, and the pigment dispersion B is preferably 17 to 710 parts by weight, more preferably 76 to 267 parts by weight with respect to 100 parts by weight of the pigment.

(Organic solvent)
Examples of the organic solvent used in the pigment composition A, the pigment dispersion A, and the pigment dispersion B include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3- Butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone , Ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl Acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Rubenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ -Butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol Cole monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, Cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobuty Ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene Glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclo Examples include hexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, etc., and these are used alone or in combination.
Preferred organic solvents are propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, cyclohexyl acetate, cyclohexanone, and ethyl 2-acetoxypropionate. is there. More preferable organic solvents are propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, cyclohexanone and cyclohexyl acetate.
When two or more organic solvents are used, the ratio is appropriately increased or decreased in consideration of the affinity with the pigment or resin, the drying property of the organic solvent, and the like.

  Further, the organic solvent used in the pigment dispersion preferably has a boiling point at 760 mmHg of 130 ° C. or higher so that the colored resist is dried in the coating apparatus and does not become a solid aggregate or dried film. Preferably it is 140 degreeC or more. Moreover, since it is easy to dry when applied to the substrate, the boiling point is preferably 190 ° C. or lower, more preferably 180 ° C. or lower.

  The organic solvent used in the pigment composition A, pigment dispersion A and pigment dispersion B is preferably 460 to 810 parts by weight, more preferably 490 to 590 parts by weight with respect to 100 parts by weight of the pigment.

<Method for Mixing Photopolymerizable Monomer into Pigment Dispersion C: Step (b)>
In the method for producing a colored resist for a color filter of the present invention, the step (b) comprises a step of mixing a photopolymerizable monomer with the pigment dispersion C obtained in the step (a).
In the step (b), when the color resist for color filter is cured by ultraviolet irradiation, a photopolymerization initiator is further mixed.

(Photopolymerizable monomer)
The photopolymerizable monomer used in the step (b) means a compound having an ethylenically unsaturated double bond that is cured by irradiation with active energy rays to form a transparent resin. Also included are low polymers having an average molecular weight of less than about 1000 and having an ethylenically unsaturated double bond.

As the photopolymerizable monomer, monofunctional (meth) acrylates, polyfunctional (meth) acrylates, epoxy (meth) acrylates, vinyl ethers and the like can be used. The photopolymerizable monomer may be an oligomer.
Specific examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and cyclohexyl. Examples include (meth) acrylate, dicyclopentanyl (meth) acrylate, and β-carboxyethyl (meth) acrylate.
Specific examples of bifunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol polyethylene glycol di (meth) acrylate, and polypropylene glycol. Examples include di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, and tripropylene glycol di (meth) acrylate.
Specific examples of trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. And dipentaerythritol hexa (meth) acrylate and the like.
Specific examples of epoxy (meth) acrylates include (meth) acrylic acid adducts of 1,6-hexanediol diglycidyl ether, (meth) acrylic acid adducts of neopentyl glycol diglycidyl ether, and glycerol diglycidyl ether. (Meth) acrylic acid adduct, glycerol triglycidyl ether (meth) acrylic acid adduct, bisphenol A type epoxy (meth) acrylic acid adduct, bisphenol F type epoxy (meth) acrylic acid adduct, and novolak type Examples include (meth) acrylic acid adducts of epoxy.
These (meth) acrylates may be modified with alkylene oxide, caprolactone or the like.

Specific examples of vinyl ethers include hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, and the like.
In addition, tris [2- (meth) acryloyloxyethyl)] isocyanurate, a reaction product of isocyanurate of diisocyanates and hydroxyalkyl (meth) acrylate; (meth) acrylic acid; styrene; vinyl acetate; (meth) acrylamide A monofunctional monomer having a nitrogen element such as N-hydroxymethyl (meth) acrylamide, N-vinylformamide, or acrylonitrile can be used as the photopolymerizable monomer.
Furthermore, what introduce | transduced the (meth) acryloyl group to oligomers, such as a polyurethane, polyester, a methylol melamine resin, polydimethylsiloxane, and rosin, can also be used.

(Photopolymerization initiator)
As a photopolymerization initiator,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone photopolymerization initiator;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal;
Benzophenone photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4'-methyldiphenyl sulfide;
A thioxanthone photopolymerization initiator such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 2,4-diisopropylthioxanthone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl (4′-methoxystyryl) -6 Triazine photopolymerization initiators such as triazine;
A borate photopolymerization initiator; a carbazole photopolymerization initiator; an imidazole photopolymerization initiator, or the like is used.
A photoinitiator can be used in the quantity of 5-150 weight part with respect to 100 weight part of pigments.
The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4′-diethylaminobenzophenone Can also be used together.
The sensitizer can be used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

(Optional component)
In the step (b), if necessary, the same transparent resin, organic solvent, leveling agent and other components as those used for the pigment dispersion can be added.
The transparent resin can be used in a range in which the amount contained in the finally obtained color filter coloring resist is 30 to 500% by weight based on the total weight of the pigment (100% by weight). If it is 30% by weight or more, the film formability and various resistances are good, and if it is 500% by weight or less, the pigment concentration becomes sufficient and color characteristics can be expressed, which is preferable.

(Leveling agent)
The leveling agent is added in order to improve the leveling property of the colored resist on the substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually 0.003 to 0.5% by weight based on the total weight of the colored resist (100% by weight).

(Other ingredients)
In the step (b), a storage stabilizer can be contained in order to stabilize the colored resist with time. Moreover, in order to improve adhesiveness with a board | substrate, adhesion improvement agents, such as a silane coupling agent, can also be contained.

[Storage stabilizer]
Examples of the storage stabilizer include benzyltrimethylammonium chloride and quaternary ammonium chlorides such as diethylhydroxyamine hydrochloride; organic acids such as lactic acid and oxalic acid; methyl esters of the above organic acids; t-butylpyrocatechol Pyrocatechols such as tetraethylphosphine and organic phosphines such as tetraphenylphosphine; phosphites and the like.
The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic pigment in the colored resist.

[Silane coupling agent]
As a silane coupling agent,
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, 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-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Aminosilanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane;
and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.
The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the organic pigment in the colored resist.

(Removal of coarse particles)
Pigment Dispersion A, Pigment Dispersion B, Pigment Dispersion C and Colored Color Resist for Color Filter are Coarse Particles of 5 μm or More, preferably 1 μm or More, by Means of Centrifugation, Sintering Filter, Membrane Filter, etc. More preferably, it is preferable to remove coarse particles of 0.5 μm or more and mixed dust. Particularly preferably, particles having a size of 0.3 μm or more are removed. In addition, the particle diameter here means the particle diameter measured by SEM.

<Color filter>
Below, the manufacturing method of the color filter using the color resist for color filters manufactured by the manufacturing method of this invention is demonstrated.
The color filter of the present invention includes a filter segment on a substrate, and can include, for example, a black matrix and red, green, and blue filter segments. The filter segment is formed on the substrate by applying a colored resist by a spin coating method or a die coating method, and then irradiating an active energy ray such as ultraviolet rays to cure the portion that becomes the filter segment, and then developing the portion. .

The color resist for color filter manufactured by the manufacturing method of the present invention is used for forming a green filter segment, and the red and blue filter segments are formed using a red color resist and a blue color resist.
As each color coloring resist other than green, it can be formed using each color coloring resist, the said transparent resin, and the usual each color coloring resist containing the said photopolymerizable monomer.
For example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, Red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 are used. Red coloring resist includes C.I. I. 20 such as Pigment Orange 43, 71, 73
An orange pigment can be used in combination.

Examples of the blue colored resist include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. For blue colored resists, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

  As a substrate for the color filter, glass plates such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc., which have high transmittance for visible light, and resins such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A plate is 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.

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 method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid buildup) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, after coloring resist is applied and dried, 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 due to oxygen. UV exposure can also be performed.

  If the black matrix is formed in advance before forming the filter segment on the substrate, the contrast ratio of the liquid crystal display panel can be further increased. Examples of the black matrix include, but are not limited to, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed. Alternatively, a thin film transistor (TFT) may be formed on a substrate in advance, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.
The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.
Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

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” and “%” mean “parts by weight” and “% by weight”, respectively.

  First, the acrylic resin solution, the refined pigment, the pigment composition A, the pigment dispersion A, the method for producing the pigment dispersion B, and the preparation of the pigment dispersant solution used in Examples and Comparative Examples will be described.

  In addition, the molecular weight of the acrylic resin was converted to polystyrene using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. The weight average molecular weight of

Further, the volume average primary particle diameter (MV) of the pigment was measured by measuring the short axis diameter and the long axis diameter of 100 primary particles of the pigment using a transmission (TEM) electron micrograph. The average of the axial diameter is defined as the particle diameter (d) of the pigment particles, and then the volume (V) of each particle is determined assuming that each pigment is a sphere having the determined particle diameter. It calculated about the pigment particle from the following formula.
MV = Σ (V · d) / Σ (V)

<Manufacture of acrylic resin solution>
70.0 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer, the temperature was raised to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. Then, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.) 7.4 from the dropping tube. And a mixture of 0.4 parts of 2,2′-azobisisobutyronitrile were added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26,000.
After cooling to room temperature, about 2 g of the acrylic resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the solid content was measured. Based on the measurement results, propylene glycol monomethyl ether acetate was added to the previously synthesized acrylic resin solution so that the solid content was 30% to obtain an acrylic resin solution.

<Manufacture of refined pigments>
(Production of green refined pigment (PG-1))
Green pigment C.I. I. 500 parts of Pigment Green 58 (“First Gain Green A110” manufactured by DIC Corporation), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green refined pigment (PG-1) was obtained. The obtained pigment had a volume average primary particle size of 25 nm.

(Manufacture of yellow refined pigment (PY-1))
Metal complex yellow pigment C.I. I. 500 parts of Pigment Yellow 150 (LANXESS "E4GN"), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow refined pigment (PY-1) was obtained. The obtained pigment had a volume average primary particle size of 28 nm.

(Manufacture of yellow refined pigment (PY-2))
Quinophthalone yellow pigment C.I. I. 500 parts of Pigment Yellow 138 ("Pariotol Yellow K0960-HD" manufactured by BASF), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow refined pigment (PY-2) was obtained. The obtained pigment had a volume average primary particle size of 26 nm.

<Preparation of pigment dispersant solution X>
A resin type dispersant (“Ajisper PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) was diluted with propylene glycol monomethyl ether acetate to prepare a pigment dispersant solution (X-1) having a solid content of 30%. Similarly, a resin-type dispersant (“BYK2001” manufactured by Big Chemie Japan) was diluted with propylene glycol monomethyl ether acetate to prepare a pigment dispersant solution (X-2) having a solid content of 30%.

<Production of Pigment Composition A and Pigment Dispersion A>
(Production of green pigment composition (A-1))
A mixture of 22.5 parts of green refined pigment (PG-1), 15.0 parts of pigment dispersant solution (X-1), 10.0 parts of acrylic resin solution, and 52.5 parts of propylene glycol monomethyl ether acetate The mixture was stirred and mixed uniformly with a disper for 1.0 hour to obtain a green pigment composition (A-1).

(Production of green pigment dispersion (A-2))
Green pigment composition (A-1) 57.8 parts, acrylic resin solution 8.9 parts using zirconia beads having a diameter of 0.5 mm, Eiger mill ("Mini Model M-" manufactured by Eiger Japan Co., Ltd.) as a media type wet disperser. 250 MKII ”) for 4 hours, and further 33.3 parts of propylene glycol monomethyl ether acetate was added and dispersed for 0.5 hour to obtain a green pigment dispersion (A-2).

(Production of green pigment dispersion (A-3))
A mixture of 35.8 parts of green refined pigment (PG-1), 23.9 parts of pigment dispersant solution (X-1) and 40.3 parts of acrylic resin solution was sufficiently mixed, and then kneaded in a two-roll mill. The meat was made into a sheet. The sheet was folded into several sheets and passed through a two-roll mill again. This process was repeated 10 to 40 times and then pulverized with a pulverizer to obtain a green pigment dispersion (A-3). The solid content of the obtained pigment dispersion (A-3) was measured and found to be 92%.

(Production of green pigment dispersion (A-4))
After mixing 21.7 parts of green pigment dispersion (A-3) and 45.0 parts of propylene glycol monomethyl ether acetate, Eiger Mill (Eiger Japan Co., Ltd.) was used as a media type wet dispersion machine using zirconia beads having a diameter of 0.5 mm. (Manufactured “Mini Model M-250 MKII”) for 4 hours, and further 33.3 parts of propylene glycol monomethyl ether acetate was added and dispersed for 0.5 hour to obtain a green pigment dispersion (A-4). .

<Production of Pigment Dispersion B>
(Production of yellow pigment dispersion (B-1))
A mixture of 10.0 parts of yellow refined pigment (PY-1), 6.7 parts of pigment dispersant solution (X-1), 26.7 parts of acrylic resin solution, and 23.4 parts of propylene glycol monomethyl ether acetate After stirring and mixing uniformly with a disper, using a zirconia bead with a diameter of 0.5 mm and dispersing for 4 hours using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser Then, 33.2 parts of propylene glycol monomethyl ether acetate was added to obtain a yellow pigment dispersion (B-1).

(Production of yellow pigment dispersion (B-2))
(Production of yellow pigment dispersion (B-1)), except that the yellow refined pigment was (PY-2) and the pigment dispersant solution (X-1) was changed to the pigment dispersant solution (X-2). A yellow pigment dispersion (B-2) was obtained in the same manner as above.

[Example 1]
30.0 parts of yellow pigment dispersion (B-1) is added to 70.0 parts of green pigment composition (A-1), and 0.5 mm diameter zirconia beads are used as an Eiger mill (media type wet disperser). Dispersion for 4.0 hours using “Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd., and further using an acrylic resin solution and propylene glycol monomethyl ether acetate so that the pigment content is 50% and the solid content is 18%. The pigment dispersion (DG-1) was obtained by adjusting and filtering with a 5.0 micrometer filter. Next, 60.0 parts of pigment dispersion (DG-1), 11.0 parts of acrylic resin solution, 4.2 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), photopolymerization initiator (Ciba Japan "Irgacure 907") 1.2 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.4 parts, and propylene glycol monomethyl ether acetate 23.2 parts The mixture was stirred and mixed to obtain a colored resist for color filter (CG-1).

[Example 2]
Add 80.2 parts of green pigment dispersion (A-2) and 19.8 parts of yellow pigment dispersion (B-1), and use zirconia beads having a diameter of 0.5 mm as an Eiger mill (Eiger Mill) Using “Mini Model M-250 MKII” manufactured by Japan Co., Ltd.) for 0.5 hour, and using acrylic resin solution and propylene glycol monomethyl ether acetate to adjust the pigment content to 50% and solid content to 18%. And it filtered with a 5.0 micrometer filter, and obtained the pigment dispersion (DG-2). Next, 60.0 parts of pigment dispersion (DG-2), 11.0 parts of acrylic resin solution, 4.2 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), photopolymerization initiator (Ciba Japan "Irgacure 907") 1.2 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.4 parts, and propylene glycol monomethyl ether acetate 23.2 parts Then, the mixture was stirred and mixed, and then filtered through a 1.0 μm filter to obtain a colored resist for color filter (CG-2).

[Example 3]
23.6 parts of yellow pigment dispersion (B-1) and 49.5 parts of propylene glycol monomethyl ether acetate are added to 23.6 parts of green pigment dispersion (A-3), and zirconia beads having a diameter of 0.5 mm are used. Then, it is dispersed for 4.0 hours using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) as a media type wet disperser, and further a pigment content of 50 using an acrylic resin solution and propylene glycol monomethyl ether acetate. % And a solid content of 18%, and filtration through a 5.0 μm filter gave a pigment dispersion (DG-3). Next, 60.0 parts of pigment dispersion (DG-3), 11.0 parts of acrylic resin solution, 4.2 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), photopolymerization initiator (Ciba Japan "Irgacure 907") 1.2 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.4 parts, and propylene glycol monomethyl ether acetate 23.2 parts Then, the mixture was stirred and mixed, and filtered through a 1.0 μm filter to obtain a colored resist for color filter (CG-3).

[Example 4]
Add 19.9 parts of the yellow pigment dispersion (B-1) to 80.1 parts of the green pigment dispersion (A-4), and use zirconia beads having a diameter of 0.5 mm as a media type wet disperser ( Dispersion for 4.0 hours using “Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd., and further using an acrylic resin solution and propylene glycol monomethyl ether acetate so that the pigment content is 50% and the solid content is 18%. The pigment dispersion (DG-4) was obtained by adjusting and filtering with a 5.0 micrometer filter. Next, 60.0 parts of pigment dispersion (DG-4), 11.0 parts of acrylic resin solution, 4.2 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), photopolymerization initiator (Ciba Japan "Irgacure 907") 1.2 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.4 parts, and propylene glycol monomethyl ether acetate 23.2 parts Then, the mixture was stirred and mixed, and then filtered through a 1.0 μm filter to obtain a colored resist for color filter (CG-4).

[Examples 5 to 15]
A color resist for color filter (CG-5-15) was prepared in the same manner as in Example 1 except that the combination of the types of pigment composition A shown in Table 1 and pigment dispersion B and the mixing ratio were changed. Obtained.

[Comparative Example 1]
70.0 parts of the green pigment dispersion (A-1) and 30.0 parts of the yellow pigment dispersion (B-1) were stirred and mixed with a disper so as to be uniform. Do not pass through and do not perform dispersion treatment.) Further, adjust the pigment content to 50% and solid content to 18% using an acrylic resin solution and propylene glycol monomethyl ether acetate, and filter through a 5.0 μm filter. As a result, a pigment dispersion (DG-C1) was obtained. Next, 60.0 parts of a pigment dispersion (DG-C1), 11.0 parts of an acrylic resin solution, trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), 4.2 parts, a photopolymerization initiator (Ciba Japan "Irgacure 907") 1.2 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.4 parts, and propylene glycol monomethyl ether acetate 23.2 parts The mixture was stirred and mixed to obtain a color filter coloring resist (CG-C1).

[Comparative Example 2]
For color filters as in Comparative Example 1, except that the pigment dispersion (DG-C2) was obtained by changing the combination of pigment dispersion A and pigment dispersion B shown in Table 1 and the blending ratio. A colored resist (CG-C2) was obtained.

[Comparative Example 3]
10.4 parts of green refined pigment (PG-1), 2.0 parts of yellow refined pigment (PY-1), 8.3 parts of pigment dispersant solution (X-1), acrylic resin solution 17 .1 part and a mixture of 29.1 parts of propylene glycol monomethyl ether acetate were stirred and mixed uniformly, and then a Eiger mill (Eiger Japan Co., Ltd. “Mini Model” was used as a media type wet disperser using zirconia beads having a diameter of 0.5 mm. M-250 MKII ") for 4 hours, 33.1 parts of propylene glycol monomethyl ether acetate was added and dispersed for 0.5 hour, and further the pigment content was 50% using acrylic resin solution and propylene glycol monomethyl ether acetate. The pigment dispersion is prepared by adjusting to a solid content of 18% and filtering through a 5.0 μm filter. (DG-C3) was obtained. Next, 60.0 parts of pigment dispersion (DG-C3), 11.0 parts of an acrylic resin solution, trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), 4.2 parts of photopolymerization initiator (Ciba Japan "Irgacure 907") 1.2 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.4 parts, and propylene glycol monomethyl ether acetate 23.2 parts Then, the mixture was stirred and mixed, and filtered through a 1.0 μm filter to obtain a colored resist for color filter (CG-C3).

Below, the evaluation method of the coloring resist for color filters is demonstrated.
(Measurement of initial viscosity and viscosity increase with time)
The viscosity of the color resist for color filter is the viscosity (initial viscosity) at a rotation speed of 20 rpm using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. It was measured.
Then, for samples that were allowed to stand at 40 ° C. for 7 days from the day of color resist coloring resist adjustment, the sample temperature was returned to 25 ° C., and then the viscosity with time was measured according to the above viscosity measurement method. The viscosity was determined.
Thickening ratio with time = (viscosity with time) / (initial viscosity) x 100 (%)

(Measurement method of initial contrast ratio, change rate of contrast ratio with time)
Each color filter coloring resist is coated on a 10 cm × 10 cm glass substrate with a spin coater, left in an oven at 70 ° C. for 15 minutes, excess solvent is removed and dried, and a color filter having a thickness of about 2.0 μm. A glass substrate coated with a coloring resist was prepared, and the contrast ratio was measured by the following method.
A colored resist-coated substrate for a color filter is sandwiched between two polarizing plates, and light is irradiated from one polarizing plate side using a backlight unit for liquid crystal display. The light emitted from the backlight unit passes through the first polarizing plate, is polarized, then passes through the color filter colored resist coating substrate, and reaches the second polarizing plate. If the polarization planes of the first polarizing plate and the second polarizing plate are parallel, light passes through the first polarizing plate, but if the polarization plane is perpendicular, the light passes through the second polarizing plate. Are blocked by the polarizing plate. However, when the light polarized by the first polarizing plate passes through the colored resist coating substrate for the color filter, if the light is scattered by pigment particles and a part of the polarization plane is displaced, the polarizing plate becomes parallel. In this case, the amount of light transmitted through the second polarizing plate is reduced, and when the polarizing plate is perpendicular, a part of the light is transmitted through the second polarizing plate. The luminance of the transmitted light is measured with a luminance meter on the polarizing plate, and the ratio of the luminance when the polarizing plate is parallel to the luminance when the polarizing plate is perpendicular is taken as the contrast ratio.
Contrast ratio = (Luminance when parallel) / (Luminance when direct)

When scattering is caused by the pigment in the color resist coating film for color filter, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.
The luminance meter used was “Color Luminance Meter BM-5A” manufactured by Topcon Corporation, and the polarizing plate used was “Polarized Film LLC2-92-18” manufactured by Sanritsu. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.
Then, with respect to what was left standing at 40 ° C. for 7 days from the day of dispersion of the colored resist for color filter, the temporal contrast ratio was measured in the same manner as described above, and the temporal contrast ratio change rate was calculated from the following equation. .
Contrast ratio change ratio with time = Contrast ratio with time / Initial contrast ratio × 100 (%)

(Evaluation)
The stability with time was evaluated by the thickening ratio with time and the contrast ratio change with time. If the rate of thickening with time is 90% to 120%, it can withstand practical use. If the viscosity is reduced or increased beyond this range, when applying the color filter coloring resist to the glass substrate, it cannot be applied under the same coating conditions, resulting in problems in productivity. End up. More preferably, it is in the range of 95% to 105%. Further, the rate of change in contrast ratio with time is preferably 90% or more, and more preferably 95% or more. If it is 89% or less, it becomes a colored resist for a color filter having an extremely short life.
Table 2 shows the evaluation results of the time-dependent thickening rate and the time-dependent contrast ratio change rate of the color filter coloring resists (CG-1 to 15) obtained as described above.

  As in Examples, a green organic pigment A containing a halogenated zinc phthalocyanine pigment and a pigment composition A containing a transparent resin or an organic solvent, or a green organic pigment A containing a halogenated zinc phthalocyanine pigment are wetted in a transparent resin and an organic solvent. By mixing the pigment dispersion A obtained by the dispersion treatment and the pigment dispersion B obtained by wet-dispersing the yellow organic pigment B in the transparent resin and the organic solvent, and further performing wet dispersion using a media-type wet disperser. Thus, a color resist for color filters having a temporal viscosity increase rate of 90% to 120% and a temporal contrast ratio change rate of 90% or more and excellent in storage stability over time could be obtained.

In particular, when the pigment composition A is a pigment dispersion A obtained by wet-dispersing a green organic pigment A containing a halogenated zinc phthalocyanine pigment and a transparent resin or an organic solvent, the initial contrast ratio is high and good. It was.
Further, when the content of the organic pigment A is in the range of 68 to 95% on the basis of the total pigment weight of the pigment dispersion C, the viscosity increase ratio with time and the contrast ratio change ratio with time are more preferable ranges. The results are shown.
On the other hand, in the comparative example, when only the pigment dispersion A and the pigment dispersion B are mixed and stirred, especially when two kinds of pigments are dispersed together, the decrease in the contrast ratio with time is large and the life is extremely short. Colored resist for color filters.

Claims (6)

  Mixing a green organic pigment A containing a halogenated zinc phthalocyanine pigment, a pigment composition A containing a transparent resin or an organic solvent, and a pigment dispersion B obtained by wet-dispersing a yellow organic pigment B in a transparent resin and an organic solvent, Further, a step (a) of producing a pigment dispersion C by wet dispersion using a media type wet disperser, and a step of further mixing a photopolymerizable monomer into the pigment dispersion C obtained in the step (a) A method for producing a color resist for a color filter, comprising (b).   2. The colored resist for color filter according to claim 1, wherein the pigment composition A is a pigment dispersion A obtained by wet-dispersing a green organic pigment A containing a halogenated zinc phthalocyanine pigment, a transparent resin and an organic solvent. Production method. 3. The pigment composition A is a pigment dispersion A obtained by wet-dispersing a green organic pigment A containing a halogenated zinc phthalocyanine pigment, a transparent resin, and an organic solvent using a media-type wet disperser. The manufacturing method of the coloring resist for color filters of description. The method for producing a colored resist for a color filter according to any one of claims 1 to 3, wherein the pigment composition A is a pigment dispersion A in the form of a colored chip. The method for producing a color resist for a color filter according to any one of claims 1 to 4, wherein the pigment composition A or the pigment dispersion B contains a pigment dispersant. The color for color filter according to any one of claims 1 to 5, wherein the content of the green organic pigment A contained in the pigment dispersion C is in the range of 68% to 95% by weight based on the total pigment weight. Resist manufacturing method.