JP4585781B2 - Coloring composition and color filter - Google Patents

Description

  The present invention relates to a color filter used for, for example, a color liquid crystal display device, a color image pickup tube element, and the like, and a coloring composition that can be used therefor.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

Therefore, 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. The color filter is mainly produced by the following two methods. Is manufactured.
In the first method, a colored composition in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, a pattern exposure of one filter color is performed, and The exposed portion is removed in the development step to form a first color pattern, and after processing such as heating as necessary, the same operation is sequentially repeated for all filter colors to produce a color filter.

  In the second method, a colored composition in which a pigment is dispersed in a transparent resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, and then a resist such as a positive resist is applied on the coating film. , Pattern exposure of one filter color is performed and developed to form a resist pattern. Using this as an etching resist, the pigment-dispersed coating film without the resist pattern is removed with an etching solution, and the resist coating film is peeled off. To form a first color pattern. After processing such as heating as necessary, the same operation is sequentially repeated for all filter colors to produce a color filter. Note that the development of the resist and the etching of the pigment-dispersed coating film can be performed simultaneously.

In the production of such a color filter, the dispersibility of the pigment in the colored composition is important, and when a color filter is produced using a colored composition having a low dispersibility, it causes a decrease in contrast.
Therefore, for the production of the filter segment, a coloring composition containing a dispersant is used. As a dispersant, a sulfonated product of CI Pigment Yellow 138 is free or is a salt formed by neutralizing with a metal alkali aqueous solution or an amine aqueous solution. Sulfonated derivatives of Pigment Yellow 138 are known (see, for example, Patent Documents 1 and 2).
JP-A-9-176511 JP 2002-179799 A

However, it has been used in the past in situations where there are increasing demands on the physical properties of the colored composition used in the production of color filters, such as dispersion stability, storage stability, and coating uniformity when forming filter segments. In the case of colored compositions, it is difficult to cope with them. Particularly in recent years, liquid crystal display devices have been applied for television monitor applications, and in order to produce panels, high-density color filters containing a large amount of pigment are required.
Therefore, the present invention has an object of a colored composition having excellent dispersion stability and particularly high storage stability, and a color filter using the same.

The colored composition in the present invention is not made of a sulfonated dye derivative with a free acid type or a salt-forming type with an organic amine, but is made of aluminum, not an alkali metal such as Na or K, or an alkaline earth metal such as Ca or Ba. By using a salted product, high storage stability is exhibited.
That is, the coloring composition of the present invention comprises a pigment carrier made of a transparent resin, a precursor thereof or a mixture thereof, an organic pigment dispersed in the pigment carrier, and an aluminum salt of a sulfonated dye derivative. To do.
Here, the pigment constituting the aluminum salt of the sulfonated pigment derivative is desirably CI Pigment Yellow 138.
Furthermore, it is desirable to contain a resin type dispersant.
As the resin type dispersant, a basic resin type dispersant is desirable.
Furthermore, it is desirable to contain a resin obtained by copolymerizing a compound (a) represented by the following general formula (1) and another compound (b) having an ethylenically unsaturated double bond.

General formula (1)
(R ₁ is H or CH ₃ , R ₂ is an alkylene group, R ₃ is H or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring)

  The color filter of this invention comprises the filter segment formed from the said coloring composition, It is characterized by the above-mentioned.

According to the present invention, a colored composition having excellent dispersion stability and particularly high storage stability can be obtained.
And the color filter which comprises a uniform filter segment can be manufactured by using the coloring composition of this invention.

  The aluminum salt of the sulfonated dye derivative used in the coloring composition of the present invention is formed by forming a salt with aluminum after sulfonating the dye, and is excellent in dispersing the pigment and preventing reaggregation of the pigment after dispersion. Great effect. Therefore, when a colored composition obtained by dispersing an organic pigment in a pigment carrier using an aluminum salt of a sulfonated dye derivative, a color filter having excellent stability can be obtained.

  Examples of the dye constituting the sulfonated dye derivative include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, and indanthrone. Anthraquinone dyes such as pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metals And complex dyes.

The dye also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. In addition, a pigment | dye is not limited to these.
Among the dyes, quinophthalone dyes, particularly quinophthalone yellow pigment CI Pigment Yellow 138 is a product of coloring composition containing an aluminum salt of a sulfonated dye derivative composed of the dye, dispersion stability, heat resistance, light resistance It is preferable because of its excellent solvent resistance.
An aluminum salt of a sulfonated dye derivative composed of the quinophthalone yellow pigment CI Pigment Yellow 138 is a compound represented by the following general formula (2), and has a bluish yellow color.

General formula (2)

The aluminum salt of the sulfonated dye derivative is synthesized by a conventional method, but the following method is industrially advantageous.
That is, a dye is added to concentrated sulfuric acid or fuming sulfuric acid, and the mixture is heated to perform sulfonation. Next, the reaction solution is poured into a large amount of ice water, and the sulfonic acid derivative precipitated is filtered off with a filter press or the like and washed with water. The resulting aqueous paste of sulfonic acid derivative was redispersed in a large amount of water, adjusted to a weak alkali with aqueous sodium hydroxide solution, and then gradually added with aqueous aluminum sulfate solution to form sulfonic acid, This is a method of forming a salt. Thereafter, a powdered aluminum salt of a sulfonated dye derivative can be obtained through steps of filtration, washing with water, drying, and pulverization.

As the organic pigment used in the coloring composition, commercially available ones can be used, and dyes, natural pigments, and inorganic pigments can be used in combination according to the hue of the filter segment to be formed.
As the organic pigment, those having high color developability and high heat resistance, particularly high heat decomposition resistance are preferably used. An organic pigment etc. can be used individually or in mixture of 2 or more types.
Further, the organic pigment may be refined by salt milling, acid pasting or the like.
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.

When forming a red filter segment from the colored composition of the present invention, CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, Red pigments such as 81: 3, 146, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272 can be used.
When forming a green filter segment from the colored composition of the present invention, green pigments such as CI Pigment Green 7, 10, 36, 37 can be used.
When forming a blue filter segment from the colored composition of the present invention, use a blue pigment such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 80 or the like. Can do.

When forming yellow filter segments from the colored composition of the present invention, CI 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, 16
Use yellow pigments such as 9, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 198, 213, 214, etc. Can do.

When forming a magenta filter segment from the colored composition of the present invention, CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2 81: 3, 146, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and the like.
When forming a cyan filter segment from the colored composition of the present invention, a pigment such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 80 or the like is used. Can do.

  In addition, the coloring composition has titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, Inorganic pigments such as bengara (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black can be contained.

  When the coloring composition contains two or more kinds of pigments, etc., the coloring composition is mixed with two or more kinds of pigments, and then the obtained pigment mixture is finely dispersed in a pigment carrier by a known method. Can be manufactured. The coloring composition can also be produced by mixing finely dispersed pigments in a pigment carrier.

  In the coloring composition, the aluminum salt of the organic pigment and the sulfonated dye derivative is usually 50:50 to 99.5: 0.5, preferably 60:40 to 99: 1, more preferably 70:30 to 50% by mass. It is contained in a ratio of 98: 2, more preferably 80:20 to 97: 3. If the amount of the aluminum salt of the sulfonated dye derivative is less than the above range, the pigment dispersion stabilizing effect is not exhibited. Conversely, if the amount is more than the above range, the hue of the filter segment may change undesirably. This is also a problem in terms of manufacturing cost.

  It is preferable that the coloring composition further contains a resin-type pigment dispersant. 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, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polycarboxylic acid esters Siloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by the reaction of poly lower alkylene imine and polyester having a free carboxyl group, salts thereof, and the like are used. . In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are also used. These can be used alone or in admixture of two or more.

  Resin-type dispersants used in coloring compositions are adsorbed on the surface of aluminum salts of organic pigments and sulfonated dye derivatives with acidic groups or basic groups as anchors, and the repulsive effect of the polymer effectively acts to stabilize the dispersion. A polymer having an acidic group or a basic group is preferable because of the retention. The acidic group is preferably a sulfone group from the viewpoint of excellent adsorption characteristics, and the basic group is preferably an amino group from the viewpoint of excellent adsorption characteristics. In particular, a basic resin type dispersant having a basic group is preferable because of its good compatibility with a pigment carrier.

As a polymer having an acidic group or a basic group, a comb polymer having a structure in which a branch polymer part is graft-bonded to a trunk polymer part having an acidic group or a basic group is an organic solvent due to the excellent steric repulsion effect of the branch polymer part. It is preferable because it is more soluble.
Furthermore, a comb polymer having a molecular structure in which two or more branch polymers are grafted to one molecule of the trunk polymer is more preferable for the above reason.

  Specific examples of the basic resin type dispersant include polyethyleneimine, polyethylene polyamine, polyxylylene poly (hydroxypropylene) polyamine, poly (aminomethylated) epoxy resin, amine-added glycidyl (meth) acrylate- (meth) acrylic acid Examples include esterified glycidyl (meth) acrylate copolymers. These synthesis methods are as follows, for example.

  Polyethyleneimine is obtained by ring-opening polymerization of ethyleneimine in the presence of an acid catalyst. Polyethylene polyamine can be obtained by polycondensation of ethylene dichloride and ammonia in the presence of an alkali catalyst. Poly (aminomethylated) epoxy resin aminates aromatic rings such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolak type epoxy resin after chloromethylation And is also called Mannich base. Specific examples of the amine used in the amination include monomethylamine, monoethylamine, monomethanolamine, monoethanolamine, dimethylamine, diethylamine, dimethanolamine, diethanolamine and the like.

  The amine-added glycidyl (meth) acrylate- (meth) acrylic esterified glycidyl (meth) acrylate copolymer is polymerized by radical polymerization of glycidyl (meth) acrylate, and then a part of the epoxy group in the polymer. An amine similar to that exemplified above is added to obtain poly [amine-added glycidyl (meth) acrylate], and then the remaining epoxy group is obtained by esterification with a carboxylic acid of (meth) acrylic acid.

  The branched polymer is preferably an organic solvent-soluble one. Specific examples thereof include a carboxylic acid at the polymer terminal, and can form a graft bond by amidation reaction with the amino group of the trunk polymer as described above. Examples thereof include ring-opening polymers such as poly (12-hydroxystearic acid), polyricinoleic acid, and ε-caprolactone, which are polymers. Further, when the backbone polymer has a vinyl group such as the above-mentioned amine-added glycidyl (meth) acrylate- (meth) acrylate esterified glycidyl (meth) acrylate copolymer, a polypolymer that can be graft-polymerized to the vinyl group. [Methyl (meth) acrylate], poly [(meth) ethyl acrylate] and the like can be exemplified as the branched polymer portion. These synthesis methods are as follows, for example.

  Poly (12-hydroxystearic acid) is obtained by a dehydration polycondensation polyesterification reaction of 12-hydroxystearic acid. Polyricinoleic acid is similarly obtained by a dehydration polycondensation polyesterification reaction of ricinoleic acid. A ring-opening polymer of ε-caprolactone is obtained by adding n-caproic acid, which is an aliphatic monocarboxylic acid, to ε-caprolactone to initiate ring-opening polymerization.

The pigment carrier for dispersing the organic pigment and the aluminum salt of the sulfonated dye derivative is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin. Alternatively, two or more kinds can be mixed and used.
When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition of the present invention.

  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 acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, 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.

  As monomers and oligomers, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa Various acrylic esters and methacrylic esters such as (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, (meth) acrylic acid, styrene, vinyl acetate, (meth) Examples include acrylamide, N-hydroxymethyl (meth) acrylamide, and acrylonitrile.

  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-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloro Til) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine photopolymerization initiators such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, and the like are used. .

  The above photopolymerization initiators are used alone or in admixture 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, 4,4′-diethylaminobenzophenone, etc. It can also be used together.

  The colored composition of the present invention contains a resin obtained by copolymerizing a compound (a) represented by the following general formula (1) and another compound (b) having an ethylenically unsaturated double bond. It is more preferable.

General formula (1)
(R ₁ is H or CH ₃ , R ₂ is an alkylene group, R ₃ is H or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring)

  The resin functions to prevent aggregation of the pigment in the photosensitive coloring composition and to maintain a finely dispersed state of the pigment, and is important for producing a color filter having high transmittance and high color purity. It is a thing.

The compound (a) represented by the general formula (1) which is a constituent component of the resin has good adsorption / orientation on the pigment surface due to the effect of π electrons of the benzene ring. In particular, when the compound (a) is paracumylphenol ethylene oxide or propylene oxide modified (meth) acrylate, its steric effect is added, and a better adsorption / orientation plane can be formed on the pigment. high. Further, it is preferable carbon number of the alkyl group of R ₃ is 1 to 20, more preferably 1 to 10. When the number of carbon atoms is from 1 to 10, the alkyl group becomes an obstacle to suppress the approach between the resins and promote the adsorption / orientation to the pigment. Even the adsorption / orientation to the pigment surface is hindered. This becomes more prominent as the chain length becomes longer, and when the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely lowered.

The specific structure of the resin is shown below.
Examples of the compound (a) include phenol ethylene oxide modified (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate and the like.

  As the compound (b), (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, (iso) pentyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate acid phosphooxyethyl (meth) Examples include acrylate, acid phosphooxypropyl (meth) acrylate, 3chloro 2-acid phosphooxyethyl (meth) acrylate, and acid phosphooxypolyethylene glycol mono (meth) acrylate.

  Since the resin exhibits an excellent dispersion effect in almost all pigments, when the color material layer of the color filter is formed using the photosensitive coloring composition of the present invention in which the pigment is dispersed with the resin, the pigment A color material layer with few aggregates can be obtained.

The colored composition of the present invention is produced by a method of dispersing an organic pigment in a pigment carrier solution, a method of dispersing an organic pigment in water or an organic solvent to prepare a pigment dispersion, and then mixing the pigment with the pigment carrier solution. Is done. The method for dispersing the pigment is not particularly limited, but a method using a sand mill, ball mill, three roll mill, two roll mill or the like is preferable. The aluminum salt of the organic pigment and the sulfonated dye derivative can also be mixed after being separately dispersed in the pigment carrier solution. However, in order to improve the dispersibility of the organic pigment, the sulfone pigment is dispersed when the organic pigment is dispersed. It is preferable to add an aluminum salt of a fluorinated dye derivative.
When the organic pigment is dispersed in the pigment carrier, a dispersion aid such as a surfactant and other dye derivatives can be appropriately used.

  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 Surfactant; Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaines and alkylimidazolines. These can be used alone or in admixture of two or more.

Another pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called dyes. Examples of the dye derivatives 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. You can use what you have. In particular, a pigment derivative having a basic group and a triazine derivative having a basic group are preferably used because they have a large pigment dispersion effect.
Specific examples of the basic group possessed by the dye derivative include substituents represented by the following general formulas (3), (4), (5) and (6).

General formula (3)

General formula (4)

General formula (5)

General formula (6)

(In the formula, X represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond. N represents an integer of 10 to 10. R ₁ and R ₂ represent each independently. In addition, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or a combination of R ₁ and R ₂ further contains a nitrogen, oxygen or sulfur atom R ₃ represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group R ₄ , R ₅ , R ₆ , R ₇ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group Y: —NR ₈ —Z—NR ₉ represents a direct bond or R ₈ , R ₉ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group, Z: an optionally substituted alkylene group, Represents an optionally substituted alkenylene group or an optionally substituted phenylene group P: represents a substituent represented by the general formula (7) or a substituent represented by the general formula (8) Q : Represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (7) or a substituent represented by the general formula (8).

General formula (7)

General formula (8)

  Examples of the organic dye constituting the dye derivative having a basic group include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, Anthraquinone dyes such as anthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, sulene System dyes and metal complex dyes. Moreover, the organic pigment illustrated previously may be sufficient.

  Triazines constituting triazine derivatives having basic groups are alkyl groups such as methyl and ethyl groups, amino groups or dimethylamino groups, alkylamino groups such as diethylamino groups and dibutylamino groups, nitro groups, hydroxyl groups and methoxy groups. Group, alkoxy group such as ethoxy group and butoxy group, halogen such as chlorine or methyl group, methoxy group, amino group, dimethylamino group, phenyl group which may be substituted with hydroxyl group, methyl group, ethyl group, methoxy group 1,3,5-triazine which may have a substituent such as phenylamino group which may be substituted with ethoxy group, amino group, dimethylamino group, diethylamino group, nitro group, hydroxyl group and the like.

  The pigment derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the following formulas (9) to (12) into an organic dye, it reacts with the substituent to form a substituent represented by the general formulas (3) to (6). Amine components such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine- It can be obtained by reacting 2-ylamino] aniline or the like.

Formula (9): —SO ₂ Cl
Formula (10): -COCl
Formula (11): —CH ₂ NHCOCH ₂ Cl
Equation (12): -CH ₂ Cl

When the organic dye is an azo dye, the basic group is introduced by introducing the substituent represented by the general formulas (3) to (6) into the diazo component or the coupling component in advance and then performing a coupling reaction. An azo pigment derivative having the same can also be produced.
The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by the general formulas (3) to (6) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N It is obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  Examples of the amine component used for forming the substituents represented by the general formulas (3) to (8) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine. N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, di Butylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, Didecylamine, diallylamine, N, N-ethyl- 1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N , N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-di Propylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N , N-ethyl-hexyl Minoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isonicopentic acid, methyl isonicopentate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N -Aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N Butyl piperazine, N- methyl homopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentyl piperazine and the like.

  As other derivatives, those shown in Tables 1 to 10 can be used, but are not limited thereto. The pigment derivatives can be used alone or in admixture of two or more.

  In order to make it easy to form a filter segment by applying the colored composition on a transparent substrate such as a glass substrate so as to have a dry film thickness of 1 to 2.5 μm, it can contain a solvent. . Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.

  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 an organic pigment and an aluminum salt of a sulfonated dye derivative in a composition containing a thermosetting resin, a thermoplastic resin or a photosensitive resin, a monomer, and a photoinitiator.

  The organic pigment is preferably contained in the coloring composition at a ratio of 1.5 to 7% by mass when the filter segment is formed by a photolithographic method, and when the filter segment is formed by a printing method, It contains in the ratio of 1.5-40 mass% in a coloring composition. In any case, the organic pigment is preferably contained in the final filter segment in a proportion of 10 to 40% by mass, more preferably 20 to 40% by mass, with the remainder being substantially from the resinous binder provided by the pigment carrier. Become.

The coloring composition is used to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust by means of centrifugation, sintered filter, membrane filter or the like. Preferably it is done.
The pigment dispersion stability of the coloring composition can be evaluated by measuring the yield value. The yield value is determined by measuring the viscosity of the colored composition at different shear rates and using the Casson equation. It is estimated that the smaller the yield value, the smaller the degree of pigment aggregation. Since the pigment is preferably not aggregated as much as possible, the smaller the yield value, the better. Therefore, the yield value of the colored composition is preferably 1 × 10 ⁻² Pa or less, and more preferably 1 × 10 ⁻³ Pa or less.

Next, the color filter will be described.
The color filter of the present invention has a filter segment of three colors of R (red), G (green), and B (blue) formed on a transparent or reflective substrate, Y (yellow), and M (magenta). , C (cyan) three-color filter segments are formed, and the like. Each color filter segment can be formed by using the coloring composition of the present invention by a printing method or a photolithography method.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
As the reflective substrate, silicon or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on the transparent substrate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming each color filter segment by a photolithography method, the colored composition prepared as the solvent development type or alkali development type colored resist material is applied to a transparent substrate such as spray coat, spin coat, slit coat, roll coat, etc. By a coating method, coating is performed so that the dry film thickness is 0.2 to 5 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. Then, after immersing in a solvent or an alkali developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

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.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there.
The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

  If a black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast ratio of the liquid crystal display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, 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.

On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.
The color filter preferably has a small degree of depolarization, and the evaluation of the degree of depolarization can be performed by measuring the contrast ratio of the color filter. Such a contrast ratio can be obtained by sandwiching a color filter between two polarizing films, measuring the brightness of transmitted light when the polarizing axis of the polarizing film is parallel and perpendicular, and calculating the ratio. it can.

  The greater the contrast ratio, the smaller the degree of depolarization. The smaller the degree of depolarization of the color filter, in other words, the greater the contrast ratio of the color filter, the greater the contrast ratio of the liquid crystal display panel and the better the visibility. For this reason, it is preferable that the contrast ratio of the color filter is as large as possible. Specifically, it is preferably 1000 or more, more preferably 1200 or more, and further preferably 1500 or more.

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 portion, the injection port is sealed, and if necessary, a polarizing film or 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 for a liquid crystal display mode in which colorization is performed using a color filter.

Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.
(Synthesis of sulfonated dye derivative aluminum salt)
30 parts of quinophthalone-based yellow pigment CI Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was dissolved in 300 parts of 101% sulfuric acid and stirred at 70 ° C. for 8 hours to carry out a sulfonation reaction. The end point of the reaction was defined as the point at which no change in the spectrum was observed by measuring the spectrum of the sulfuric acid solution. Next, this reaction solution was poured into 3000 parts of ice water, and the precipitated sulfonated dye derivative was separated by filtration and washed with water to obtain a sulfonated dye derivative paste.
The obtained sulfonated dye derivative was subjected to LC-MASS analysis. In HPLC (column: “ODS-100S” manufactured by Tosoh Corporation), the molecular weight of the main peak occupying an area ratio of 80% is MW = 774 (electron spray method, negative mode), and a monosulfonated derivative of CI Pigment Yellow 138 Was consistent with the molecular weight. Further, it was identified by 1H-NMR as a sulfonated dye derivative having the following structure.

The obtained paste of the sulfonated dye derivative was redispersed in 10,000 parts of water (pH 2.5). Next, the solution was adjusted to pH 11 with an aqueous sodium hydroxide solution and dissolved to give a red solution. To this solution, 278 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. Precipitates appeared one after another from the dropped portion, and the pH decreased with the addition. At the end of the addition, pH 3.6 and bleed were not observed. The slurry containing the precipitate was separated by filtration and washed with water to obtain an aluminum salt of a sulfonated derivative of CI Pigment Yellow 138.
The yield after drying was 334 parts, and the yield was 99%. The resulting aluminum salt of the sulfonated dye derivative is presumed to have the following structure.

(Synthesis of ammonium salt of sulfonated dye derivative)
6 g of quinophthalone-based yellow pigment CI Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was added to 78 g of fuming sulfuric acid (25% SO 3) at 15 ° C. with stirring. After stirring for 3 hours, it was added on 150 g of ice. After standing for 30 minutes, the resulting suspension was filtered and the resulting product was washed with 30 ml of water. The product was put into 200 ml of water and neutralized with an aqueous ammonia solution (added with an aqueous ammonia solution until the pH reached 7). 45 g of ammonium chloride was added and stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystals were washed with water and then dried at 80 ° C. to obtain 10 g of an ammonium salt of a sulfonated derivative of CI Pigment Yellow 138.
The resulting ammonium salt of the sulfonated dye derivative is presumed to have the following structure.

(Preparation of acrylic resin solution 1)
A separable four-necked flask was equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube and a stirrer, charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. 13.3 parts of methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 2,2′-azobis A mixed solution of 0.4 part of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% and a weight average molecular weight of 26000.
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 mass. Thus, an acrylic resin solution 1 was prepared.

(Preparation of acrylic resin solution 2)
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.
Styrene: 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 reaction was further carried out at 100 ° C. for 3 hours. Then, 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain an acrylic resin solution having a mass average molecular weight of about 40000.
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 mass. Thus, an acrylic resin solution 2 was prepared.

(Preparation of yellow treated pigment 1)
A quinophthalone-based yellow pigment CI Pigment Yellow 138 ("Pariotol Yellow K0960-HD" manufactured by BASF): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 120 The mixture was kneaded at 2 ° C. for 2 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. 490 parts of yellow-treated pigment 1 were obtained.

(Preparation of green treated pigment 1)
A phthalocyanine-based green pigment CI Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless 1 gallon kneader (Inoue Seisakusho), 120 The mixture was kneaded at 2 ° C. for 2 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. 490 parts of green-treated pigment 1 were obtained.

[Example 1]
After the mixture having the composition shown in Table 11 was uniformly stirred and mixed, it was dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a pigment dispersion.

  Next, the mixture having the composition shown in Table 12 was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain an alkali developing yellow resist material.

[Comparative Example 1]
An alkali developable yellow resist material was produced in the same manner as in Example 1 except that the aluminum salt of the sulfonated derivative of CI Pigment Yellow 138 was changed to the ammonium salt of the sulfonated derivative of CI Pigment Yellow 138.
[Comparative Example 2]
An alkali development type yellow resist material was prepared in the same manner as in Example 1 except that the aluminum salt of the sulfonated derivative of CI Pigment Yellow 138 was changed to the sulfonated derivative of CI Pigment Yellow 138.
[Example 2]
An alkali developing type yellow resist material was produced in the same manner as in Example 1 except that the acrylic resin solution 1 was changed to the acrylic resin solution 2.

[Comparative Example 3]
Alkaline development type yellow as in Example 1, except that the aluminum salt of the sulfonated derivative of CI Pigment Yellow 138 was changed to the ammonium salt of the sulfonated derivative of CI Pigment Yellow 138 and the acrylic resin solution 1 was changed to the acrylic resin solution 2. A resist material was prepared.
[Comparative Example 4]
An alkali developing yellow resist material was prepared in the same manner as in Example 1 except that the aluminum salt of the sulfonated derivative of CI Pigment Yellow 138 was changed to the sulfonated derivative of CI Pigment Yellow 138 and the acrylic resin solution 1 was changed to the acrylic resin solution 2. Produced.
[Example 3]
An alkali-developable yellow resist material was prepared in the same manner as in Example 1 except that the yellow-treated pigment 1 was changed to the quinophthalone-based yellow pigment CI Pigment Yellow 138 ("Pariotole Yellow K0960-HD" manufactured by BASF).

[Comparative Example 5]
The yellow treated pigment 1 is changed to a quinophthalone-based yellow pigment CI Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), and an aluminum salt of a sulfonated derivative of CI Pigment Yellow 138 is converted to an ammonium salt of a sulfonated derivative of CI Pigment Yellow 138 An alkali development type yellow resist material was produced in the same manner as in Example 1 except that the change was made.
[Comparative Example 6]
The yellow treated pigment 1 was changed to a quinophthalone-based yellow pigment CI Pigment Yellow 138 ("Pariotol Yellow K0960-HD" manufactured by BASF), and the aluminum salt of a sulfonated derivative of CI Pigment Yellow 138 was changed to a sulfonated derivative of CI Pigment Yellow 138 Produced an alkali development type yellow resist material in the same manner as in Example 1.

[Example 4]
Except for changing the yellow treated pigment 1 to the quinophthalone yellow pigment CI Pigment Yellow 138 ("Pariotol Yellow K0960-HD" manufactured by BASF) and changing the acrylic resin solution 1 to the acrylic resin solution 2, the same procedure as in Example 1 was performed. An alkali development type yellow resist material was prepared.
[Comparative Example 7]
The yellow treated pigment 1 is changed to a quinophthalone-based yellow pigment CI Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), and an aluminum salt of a sulfonated derivative of CI Pigment Yellow 138 is converted to an ammonium salt of a sulfonated derivative of CI Pigment Yellow 138 In the same manner as in Example 1 except that the acrylic resin solution 1 was changed to the acrylic resin solution 2, an alkali development type yellow resist material was produced.

[Comparative Example 8]
The yellow treated pigment 1 was changed to the quinophthalone yellow pigment CI Pigment Yellow 138 ("Pariotol Yellow K0960-HD" manufactured by BASF), the aluminum salt of the sulfonated derivative of CI Pigment Yellow 138 was changed to the sulfonated derivative of CI Pigment Yellow 138, and acrylic An alkali development type yellow resist material was produced in the same manner as in Example 1 except that the resin solution 1 was changed to the acrylic resin solution 2.
[Example 5]
An alkali-developable green resist material was prepared in the same manner as in Example 1 except that the yellow-treated pigment 1 was changed to the green-treated pigment 1.

[Comparative Example 9]
Alkaline-developable green as in Example 1 except that the yellow treated pigment 1 was changed to the green treated pigment 1 and the aluminum salt of the sulfonated derivative of CI Pigment Yellow 138 was changed to the ammonium salt of the sulfonated derivative of CI Pigment Yellow 138. A resist material was prepared.
[Comparative Example 10]
An alkali developing type green resist material was prepared in the same manner as in Example 1 except that the yellow treated pigment 1 was changed to the green treated pigment 1 and the aluminum salt of the sulfonated derivative of CI Pigment Yellow 138 was changed to the sulfonated derivative of CI Pigment Yellow 138. Produced.

[Example 6]
An alkali-developable green resist material was prepared in the same manner as in Example 1 except that the yellow-treated pigment 1 was changed to the phthalocyanine green pigment CI Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.).
[Comparative Example 11]
The yellow treated pigment 1 is changed to the phthalocyanine green pigment CI Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), and the aluminum salt of the sulfonated derivative of CI Pigment Yellow 138 is changed to the ammonium salt of the sulfonated derivative of CI Pigment Yellow 138. An alkali development type green resist material was produced in the same manner as in Example 1 except for the change.

[Comparative Example 12]
Except for changing yellow treated pigment 1 to phthalocyanine green pigment CI Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.) and changing the aluminum salt of the sulfonated derivative of CI Pigment Yellow 138 to the sulfonated derivative of CI Pigment Yellow 138 Produced an alkali developing type green resist material in the same manner as in Example 1.
[Example 7]
An alkali-developable red resist material was prepared in the same manner as in Example 1 except that the yellow treated pigment 1 was changed to the diketopyrrolopyrrole red pigment CI Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba). .

[Comparative Example 13]
The yellow treated pigment 1 is changed to a diketopyrrolopyrrole red pigment CI Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba), and the aluminum salt of a sulfonated derivative of CI Pigment Yellow 138 is changed to a sulfonated derivative of CI Pigment Yellow 138. An alkali-developable red resist material was prepared in the same manner as in Example 1 except that the ammonium salt was changed.
[Comparative Example 14]
The yellow treated pigment 1 is changed to a diketopyrrolopyrrole red pigment CI Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba), and an aluminum salt of a sulfonated derivative of CI Pigment Yellow 138 is converted to a sulfonated derivative of CI Pigment Yellow 138 Alkaline development type red resist material was produced like Example 1 except having changed.

The yield value and thixo index of the resist materials obtained in Examples 1 to 7 and Comparative Examples 1 to 14 were measured using an E-type viscometer (“R110” manufactured by Toki Sangyo Co., Ltd.).
The resist materials obtained in Examples 1 to 7 and Comparative Examples 1 to 14 were spin-coated on a 360 mm × 465 mm size substrate having a plate thickness of 0.7 mm so that the average film thickness was 1.8 μm, and 70 ° C. After drying for 30 minutes, measure the film thickness at the center (referred to as A) and the average value (referred to as B) at 4 points of the film thickness of 200 mm from the center on the diagonal line. Evaluated.
(A−B) × 100 / {(A + B) / 2} [%]
The evaluation results are shown in Table 13.

  As can be seen from Table 13, the colored composition of this example is excellent in dispersion stability, storage stability, and the like.

[Example 8]
In order to produce a color filter comprising a red filter segment, a blue filter segment, and a green filter segment, a blue resist material was produced by the following method.
(Blue resist material)
After the mixture having the composition shown in Table 14 was uniformly stirred and mixed, it was dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a copper phthalocyanine dispersion.

  Next, the mixture having the composition shown in Table 15 was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue resist material.

  The red resist and material obtained in Example 7 were applied to a glass substrate by spin coating so as to have a film thickness of chromaticity (x, y) shown in Table 16. After drying, striped pattern exposure was performed with an exposure machine and development was performed with an alkaline developer for 90 seconds to form a striped red filter segment. The alkali developer is composed of 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“PERILEX NBL” manufactured by Kao) and 90% by weight of water. .

Next, the yellow resist material obtained in Example 1 and the green resist material obtained in Example 5 were mixed at a mass ratio of 1: 1 to prepare a green resist, and the chromaticity (x, y shown in Table 16) It was applied so as to have a film thickness of After drying, a striped pattern adjacent to the red filter segment was exposed with an exposure machine to form a striped green filter segment.
Further, a blue resist material was applied so as to have a film thickness of chromaticity (x, y) shown in Table 16 to form striped blue filter segments adjacent to the red and green filter segments.

The shape of each color filter segment was good, and the resolution was also good. Finally, the obtained color filter is heated in an oven at 230 ° C. for 30 minutes to completely react with the remaining polymerizable functional groups, and a red, green, and blue stripe-shaped stripe shape is formed on the transparent substrate. A color filter comprising filter segments was obtained.
Y of each color of the color filter obtained in Example 8 was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Moreover, when light is transmitted through all three colors, white light is obtained. The x, y, and Y of the white light were calculated from the x, y, and Y of each color. The results are shown in Table 16.

[Example 9]
In order to produce a color filter having a cyan filter segment, a magenta filter segment, and a yellow filter segment, cyan and magenta color resist materials were produced by the following method.
(Cyan resist material)
A cyan resist material was produced in the same manner as the blue resist material of Example 8 except that the ε-type copper phthalocyanine pigment was changed to the β-type copper phthalocyanine pigment CI Pigment Blue 16 (“Heliogen Blue D-7565” manufactured by BASF). .

(Magenta color resist material)
A magenta resist material was prepared in the same manner as the blue resist material of Example 8 except that the ε-type copper phthalocyanine pigment was changed to the quinacridone-based red pigment CI Pigment Red 122 (“Hosta Palm Pink E” manufactured by Ciba Geigy).
The obtained cyan color resist material, magenta color resist material, and yellow color resist material obtained in Example 1 were treated in the same manner as in Example 8 with the film thicknesses of chromaticity (x, y) shown in Table 17. In this way, a color filter having a stripe-shaped filter segment of three colors of cyan, magenta, and yellow on a transparent substrate was obtained.

  Y of each color of the color filter obtained in Example 9 was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). When light is transmitted through all three colors, white light is obtained. The x, y, Y of the white light was calculated from x, y, Y of each color. The results are shown in Table 17.

(Synthesis of sulfonated copper phthalocyanine)
Prepare 300 parts of 104% sulfuric acid from fuming sulfuric acid and 98% sulfuric acid, dissolve 30 parts of crude copper phthalocyanine pigment (CI Pigment Blue 15) at 30 ° C. or lower, and then stir at 50 ° C. for 5 hours for sulfonation. Reaction was performed. The end point of the reaction was determined by measuring the spectral spectrum of the sulfuric acid solution and predicting the time for the maximum absorption wavelength to reach a predetermined wavelength. This reaction solution was poured into 3000 parts of ice water, and the precipitate was separated by filtration and washed with water to obtain a water paste of a sulfonated dye derivative.
About the obtained sulfonated pigment derivative, the MASS spectrum was measured in ESI minus mode using a LC-MASS apparatus manufactured by WATERS. MW = 575, 654 to 655, 735 were detected and agreed with the molecular weight of the sulfonated product of copper phthalocyanine.

(Synthesis of Derivative B-1)
The obtained sulfonated dye derivative (sulfonated copper phthalocyanine) paste was reslurried in 10,000 parts of water, adjusted to pH 11 with an aqueous sodium hydroxide solution, and then 66 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. . After stirring at 90 ° C. for 2 hours, the resulting precipitate was filtered, washed with water, and dried to obtain a derivative B-1 having the following structure, which is an aluminum salt of a sulfonated derivative of copper phthalocyanine. The yield after drying was 35 parts.

(Preparation of derivative B-2)
The obtained sulfonated pigment derivative (sulfonated copper phthalocyanine) paste was filtered, washed with water, and dried to obtain derivative B-2.

(Synthesis of Derivative B-3)
The obtained paste of sulfonated dye derivative (sulfonated copper phthalocyanine) was reslurried in 10,000 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH was 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystal was washed with water and then dried at 80 ° C. to obtain a derivative B-3 which is an ammonium salt of a sulfonated derivative of copper phthalocyanine.

(Synthesis of isoindoline dyes)
1- (Cyano-p-chlorophenylcarbamoyl-methylene) -3-iminoisoindoline (3.3 parts) and methanolic acid (1.7 parts) were heated to reflux in 50 ml of glacial acetic acid for 2 hours. The obtained yellow reaction product was separated by filtration at 80 ° C., washed with methanol and water, and dried to obtain 3.1 parts of isoindoline dye.

(Synthesis of Derivative C-1)
The obtained isoindoline pigment 3.1 parts is reslurried in 300 parts of water, adjusted to pH 10 using an aqueous sodium hydroxide solution, 20 g of an aqueous aluminum sulfate solution (liquid sulfuric acid band) is gradually added, and the deposited precipitate is filtered. After washing with water and drying, a derivative C-1 having the following structure, which is an aluminum salt of a sulfonated derivative of isoindoline, was obtained.

(Synthesis of Derivative C-2)
The obtained isoindoline pigment 3.1 parts was reslurried in 300 parts of water and adjusted to pH 11 with an aqueous sodium hydroxide solution. Stirring was continued for 1 hour while appropriately adding an aqueous sodium hydroxide solution and maintaining the pH. Furthermore, it heated at 60 degreeC at pH11, and stirred for 3 hours. After adjusting the pH to 1 or less with hydrochloric acid, the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with water and dried to obtain a derivative C-2 which is a sulfonic acid derivative of isoindoline.

(Synthesis of Derivative C-3)
3.1 parts of the obtained isoindoline dye was reslurried in 300 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH was 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystal was washed with water and then dried at 80 ° C. to obtain a derivative C-3 which is an ammonium salt of a sulfonated derivative of isoindoline.

(Synthesis of chlorosulfonated diketopyrrolopyrrole dyes)
In 300 parts of chlorosulfonic acid, 30 parts of 1,4-diketo-3,6-diphenylpyrrolo- [3,4-c] -pyrrole (CI Pigment Red 255) is dissolved at 20 ° C. or lower over 20 minutes. The mixture was stirred at 50 ° C. for 2 hours to effect chlorsulfonation. The reaction solution was added to 5000 parts of ice water, and the resulting precipitate was filtered and washed with water to obtain an aqueous paste of chlorsulfonated diketopyrrolopyrrole pigment.

(Synthesis of Derivative D-1)
The obtained diketopyrrolopyrrole pigment chlorosulfonated aqueous paste was reslurried in 3000 parts of water, adjusted to pH 11 using an aqueous sodium hydroxide solution and heated to 80 ° C. to obtain a red solution. 120 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) is gradually added, stirred at 90 ° C. for 2 hours, filtered, washed with water, and dried to form an aluminum salt of a sulfonated derivative of a diketopyrrolopyrrole dye. 25 parts of the derivative D-1 was obtained.

(Synthesis of Derivative D-2)
The obtained aqueous paste of chlorosulfonated diketopyrrolopyrrole pigment was reslurried in 3000 parts of water and adjusted to pH 11 with an aqueous sodium hydroxide solution. Stirring was continued for 1 hour while appropriately adding an aqueous sodium hydroxide solution and maintaining the pH. Furthermore, it heated at 60 degreeC at pH11, and stirred for 3 hours. After adjusting the pH to 1 or less with hydrochloric acid, the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with water and dried to obtain a derivative D-2 which is a sulfonic acid derivative of a diketopyrrolopyrrole pigment.

(Synthesis of Derivative D-3)
The obtained water paste of chlorosulfonated diketopyrrolopyrrole pigment was reslurried in 3000 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH was 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystals were washed with water and then dried at 80 ° C. to obtain a derivative D-3 which is an ammonium salt of a sulfonated derivative of a diketopyrrolopyrrole dye.

(Derivative E-1)
C. I. Pigment Yellow 115 (manufactured by Nippon Kayaku, kayaset2G). This pigment is an aluminum salt of a sulfonated derivative of a quinophthalone dye.

(Synthesis of sulphonated chlorosulfonates)
30 parts of selenium pigment (CI Pigment Blue 60) was added to 240 parts of chlorosulfonic acid, heated at 90 ° C. for 3 hours, and poured into 2000 parts of ice water. The obtained suspension was filtered and washed with water to obtain 180 parts of a water paste of sulphonated chlorosulfonated product.

(Synthesis of Derivative F-1)
The obtained sulphonated chlorosulfonated water paste was reslurried in 10,000 parts of water, adjusted to pH 11 with an aqueous sodium hydroxide solution, and stirred at 90 ° C. for 6 hours while appropriately adding to maintain pH 11. The pH is adjusted to 10 using hydrochloric acid, 50 g of an aqueous aluminum sulfate solution (liquid sulfuric acid band) is added, and the mixture is stirred at 90 ° C. for 2 hours, and then the deposited precipitate is filtered, washed with water, and dried. 25 parts of a derivative F-1 having the following structure as a salt was obtained.

(Synthesis of Derivative F-2)
The obtained sulphonated chlorosulfonated water paste was reslurried in 10,000 parts of water and adjusted to pH 11 with an aqueous sodium hydroxide solution. Stirring was continued for 1 hour while appropriately adding an aqueous sodium hydroxide solution and maintaining the pH. Furthermore, it heated at 60 degreeC at pH11, and stirred for 3 hours. After adjusting the pH to 1 or less with hydrochloric acid, the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with water and dried to obtain a derivative F-2 which is a sulfonic acid derivative of a selenium dye.

(Synthesis of Derivative F-3)
The resulting water paste of sulphonated chlorosulfonated product was reslurried in 10,000 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH reached 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystals were washed with water and then dried at 80 ° C. to obtain derivative F-3 which is an ammonium salt of a sulfonated derivative of a selenium dye.

(Synthesis of chlorsulfonated dianthraquinone dyes)
30 parts of dianthraquinone pigment (CI Pigment Red177) was added to 240 parts of chlorosulfonic acid, heated at 90 ° C. for 3 hours, and poured into 2000 parts of ice water. The resulting suspension was filtered and washed with water to obtain 180 parts of a water paste of a chlorsulfonated dianthraquinone dye.

(Synthesis of Derivative G-1)
The obtained water paste of chlorsulfonated dianthraquinone dye was reslurried in 10,000 parts of water, adjusted to pH 11 with an aqueous sodium hydroxide solution, and stirred at 90 ° C. for 6 hours while adding appropriately to maintain pH 11. Adjust to pH 10 using hydrochloric acid, add 50 g of an aqueous aluminum sulfate solution (liquid sulfuric acid band), and stir at 90 ° C. for 2 hours. Then, precipitate deposited is filtered, washed with water, dried, 25 parts of derivative G-1 having the following structure, which is an aluminum salt, was obtained.

(Synthesis of derivative G-2)
The obtained aqueous paste of chlorsulfonated dianthraquinone dye was reslurried in 10,000 parts of water and adjusted to pH 11 with an aqueous sodium hydroxide solution. Stirring was continued for 1 hour while appropriately adding an aqueous sodium hydroxide solution and maintaining the pH. Furthermore, it heated at 60 degreeC at pH11, and stirred for 3 hours. After adjusting the pH to 1 or less with hydrochloric acid, the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with water and dried to obtain a derivative G-2 which is a sulfonic acid derivative of a dianthraquinone dye.

(Synthesis of derivative G-3)
The obtained water paste of chlorsulfonated dianthraquinone dye was reslurried in 10,000 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH was 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystals were washed with water and then dried at 80 ° C. to obtain a derivative G-3 which is an ammonium salt of a sulfonated derivative of a dianthraquinone dye.

(Synthesis of dioxazine dye monochlorosulfonate)
To 100 parts of chlorosulfonic acid, 15 parts of dioxazine pigment (CI Pigment Violet 23) is added at 15 to 20 ° C., stirred at 60 to 70 ° C. for 3 hours, poured into 1000 parts of ice water, filtered, By washing with water, a water cake of a monoxol sulfonated dioxazine dye was quantitatively obtained.

(Synthesis of Derivative H-1)
The obtained water cake of monochlorosulfonated dioxazine dye was added to 3000 parts of water and reslurried, adjusted to pH 12 with an aqueous sodium hydroxide solution, and heated to 90 ° C. The mixture was stirred at 90 ° C. for 6 hours while adjusting with an aqueous sodium hydroxide solution to maintain pH 12. When the bleed was examined using filter paper, a very dark purple bleed was observed. Next, after adjusting the pH to 10 using hydrochloric acid, 30 g of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. With the addition, the bleed observed on the filter paper became thinner and finally no bleed was seen. The reaction slurry was heat-treated at 90 ° C. for 2 hours, then filtered, washed with water, and dried to obtain a derivative H-1 having the following structure, which is an aluminum salt of a sulfonated derivative of a dioxazine dye.

(Synthesis of derivative H-2)
The obtained water cake of monochlorosulfonated dioxazine dye was reslurried in 3000 parts of water and adjusted to pH 11 with an aqueous sodium hydroxide solution. Stirring was continued for 1 hour while appropriately adding an aqueous sodium hydroxide solution and maintaining the pH. Furthermore, it heated at 60 degreeC at pH11, and stirred for 3 hours. After adjusting the pH to 1 or less with hydrochloric acid, the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with water and dried to obtain a derivative H-2 which is a sulfonic acid derivative of a dioxazine dye.

(Synthesis of Derivative H-3)
The obtained water cake of monochlorosulfonated dioxazine dye was reslurried in 3000 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH was 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystal was washed with water and then dried at 80 ° C. to obtain a derivative H-3 which is an ammonium salt of a sulfonated derivative of a dioxazine dye.

(Synthesis of sulfonated quinacridone dyes)
To 100 parts of 98% sulfuric acid, 10 parts of an unsubstituted quinacridone pigment (CI Pigment Violet 19) was added at 30 ° C. or lower, and the mixture was stirred at 80 ° C. for 1 hour to carry out a sulfonation reaction. The solution was poured into 1000 parts of ice water, filtered and washed with water to quantitatively obtain a water cake of a sulfonated quinacridone pigment. Using a LC-MASS manufactured by WATERS, a molecular weight of MW = 311,391,471 was observed in ESI minus mode, and the mixture was a quinacridone dye having 0,1,2 sulfonic acid groups.

(Synthesis of Derivative I-1)
The obtained quinacridone dye sulfonated water cake was added to 3000 parts of water and reslurried, adjusted to pH 10.5 with an aqueous sodium hydroxide solution, and heated to 60 ° C. When the bleed was examined using filter paper, a deep red-purple bleed was observed. Subsequently, 50 g of an aluminum sulfate aqueous solution (liquid sulfuric acid band) was gradually added. With the addition, the bleed observed on the filter paper became thinner and finally no bleed was seen. The reaction slurry was heat treated at 90 ° C. for 2 hours, filtered, washed with water, and dried to obtain a derivative I-1 having the following structure, which is an aluminum salt of a sulfonated derivative of a quinacridone dye.

(Preparation of derivative I-2)
The obtained quinacridone dye sulfonated water cake was filtered, washed with water and dried to obtain a derivative I-2 which is a sulfonic acid derivative of a quinacridone dye.

(Synthesis of Derivative I-3)
The resulting quinacridone dye sulfonated water cake was reslurried in 3000 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH reached 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystal was washed with water and then dried at 80 ° C. to obtain a derivative I-3 which is an ammonium salt of a sulfonated derivative of a quinacridone dye.

(Synthesis of sulfonated products of condensed azo dyes)
To 300 parts of 95% sulfuric acid, 20 parts of a condensed azo pigment (CI Pigment Red 214) was added at 20 ° C. or lower, and the mixture was stirred at 25 ° C. for 3 hours for sulfonation. The reaction solution was poured into ice water 2000, filtered and washed with dilute hydrochloric acid to obtain a water paste of a sulfonated product of a condensed azo dye.

(Synthesis of Derivative J-1)
The resulting sulfonated water paste of condensed azo dye was reslurried in 2000 parts of water, heated to 60 ° C. and adjusted to pH 9, and then 50 g of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. After stirring at 90 ° C. for 2 hours, filtration, washing with water and drying were performed to obtain a derivative J-1 having the following structure, which is an aluminum salt of a sulfonated derivative of a condensed azo dye.

(Preparation of derivative J-2)
The obtained water paste of the sulfonated product of the condensed azo dye was filtered, washed with water and dried to obtain a derivative J-2 which is a sulfonic acid derivative of the condensed azo dye.

(Synthesis of Derivative J-3)
The obtained water paste of the sulfonated condensed azo dye was reslurried in 2000 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH was 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystal was washed with water and then dried at 80 ° C. to obtain a derivative J-3 which is an ammonium salt of a sulfonated derivative of a condensed azo dye.

(Synthesis of intermediates of isoindolinone dyes)
In 150 parts of dimethyl sulfoxide, 12 parts of sodium phenol-4-sulfonate and 18 parts of 3,4,5,6-tetrachloro-2-cyanobenzoic acid methyl ester are dissolved, and 30% aqueous sodium hydroxide solution 8 is added over 1 hour. The part was dripped. The reaction mixture was stirred at 60 ° C. for 1 hour and then poured into 500 parts of water. Insoluble matter was removed by filtration, 200 parts of sodium chloride was added to the filtrate, and the salted out precipitate was filtered and washed with a 10% aqueous sodium chloride solution to obtain 15 parts of an aqueous paste of isoindolinone dye. .

(Synthesis of Derivative K-1)
The obtained aqueous paste of isoindolinone dye intermediate was added to a solution of 80 parts of methanol and 1.5 parts of sodium methylate and stirred for 30 minutes. Subsequently, 1.5 parts of p-phenylenediamine was added and a yellowish brown product was precipitated, and then the suspension was stirred for 15 hours and stirred at reflux temperature for 2 hours. After adding 300 parts of water and adjusting to pH 10 with hydrochloric acid, 20 parts of 5% aluminum chloride aqueous solution was added little by little, stirred at 90 ° C. for 2 hours, filtered, washed with water, dried, and sulfone of isoindolinone dye. A derivative K-1 having the following structure, which is an aluminum salt of a fluorinated derivative, was obtained.

(Synthesis of Derivative K-2)
The obtained aqueous paste of isoindolinone dye intermediate was added to a solution of 80 parts of methanol and 1.5 parts of sodium methylate and stirred for 30 minutes. Subsequently, 1.5 parts of p-phenylenediamine was added and a yellowish brown product was precipitated, and then the suspension was stirred for 15 hours and stirred at reflux temperature for 2 hours. Reslurried in 300 parts of water and adjusted to pH 10 with hydrochloric acid. Stirring was continued for 1 hour while maintaining the pH. Furthermore, it heated at 60 degreeC at pH10, and stirred for 3 hours. After adjusting the pH to 1 or less with hydrochloric acid, the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with water and dried to obtain a derivative K-2 which is a sulfonic acid derivative of an isoindolinone dye.

(Synthesis of Derivative K-3)
The obtained aqueous paste of isoindolinone dye intermediate was added to a solution of 80 parts of methanol and 1.5 parts of sodium methylate and stirred for 30 minutes. Subsequently, 1.5 parts of p-phenylenediamine was added and a yellowish brown product was precipitated, and then the suspension was stirred for 15 hours and stirred at reflux temperature for 2 hours. After adding 300 parts of water and adjusting the pH to 10 with hydrochloric acid, an aqueous ammonia solution was added little by little, and the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with water, dried, and ammonium salt of a sulfonated derivative of isoindolinone dye Derivative K-3 was obtained.

(Synthesis of chlorosulfonated anthraquinone)
To 100 parts of chlorosulfonic acid, 15 parts of anthraquinone was added at 15 to 20 ° C. and stirred at 40 to 50 ° C. for 3 hours, and then poured into 1000 parts of ice water, filtered and washed with water. A water cake was obtained quantitatively.
(Synthesis of Derivative L-1)
The obtained water cake of anthraquinone chlorosulfonated product was added to 3000 parts of water and reslurried, adjusted to pH 11 with an aqueous sodium hydroxide solution, and heated to 90 ° C. It stirred at 90 degreeC for 6 hours, adjusting with sodium hydroxide aqueous solution so that pH11 might be maintained. Next, after adjusting the pH to 10 using hydrochloric acid, 30 g of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. The reaction slurry was heat-treated at 90 ° C. for 2 hours, then filtered, washed with water, and dried to obtain a derivative L-1 having the following structure, which is an aluminum salt of a sulfonated derivative of an anthraquinone dye.

(Synthesis of Derivative L-2)
The obtained water cake of chlorosulfonated anthraquinone was reslurried in 3000 parts of water and adjusted to pH 11 with an aqueous sodium hydroxide solution. Stirring was continued for 1 hour while appropriately adding an aqueous sodium hydroxide solution and maintaining the pH. Furthermore, it heated at 60 degreeC at pH11, and stirred for 3 hours. After adjusting the pH to 1 or less with hydrochloric acid, the mixture was stirred at 90 ° C. for 2 hours, filtered, washed with water and dried to obtain derivative L-2 which is a sulfonic acid derivative of anthraquinone.

(Synthesis of Derivative L-3)
The obtained water cake of chlorosulfonated anthraquinone was reslurried in 3000 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH was 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystals were washed with water and then dried at 80 ° C. to obtain a derivative L-3 which is an ammonium salt of a sulfonated derivative of anthraquinone.

(Synthesis of acridone sulfonic acid derivatives)
When diphenyl-amine-2-carboxylic acid obtained by Ulmann condensation of 160 parts of O-chlorobenzoic acid and 100 parts of aniline is subjected to dehydration and ring closure in concentrated sulfuric acid, it is heated at 100 ° C. for 3 hours to give 100 parts of acridonesulfonic acid. Got.
(Synthesis of Derivative M-1)
The obtained acridone sulfonic acid was dissolved or uniformly dispersed in water or a dilute alkaline solution, and 200 g of an aluminum sulfate aqueous solution (liquid sulfuric acid band) was gradually added. The reaction slurry was heat-treated at 90 ° C. for 2 hours, filtered, washed with water, and dried to obtain a derivative M-2 having the following structure, which is an aluminum salt of a sulfonated derivative of acridone.

(Preparation of derivative M-2)
The obtained acridone sulfonic acid was filtered, washed with water and dried to obtain derivative M-2 which is a sulfonic acid derivative of acridone.
(Derivative M-3)
The obtained acridone sulfonic acid was dissolved or uniformly dispersed in water or a dilute alkaline solution, and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until the pH reached 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystal was washed with water and then dried at 80 ° C. to obtain a derivative M-3 which is an ammonium salt of a sulfonated derivative of acridone.

(Synthesis of sulfonated benzimidazolone dyes)
In 300 parts of 96% sulfuric acid, 30 parts of a benzimidazolone pigment (CI Pigment Yellow 180) was dissolved at 10 ° C. or lower and stirred at 15 ° C. for 2 hours. The mixture was poured into 3000 parts of ice water, filtered, washed with a 1% aqueous sodium chloride solution, and then washed with water to such an extent that bleeding was observed, to obtain an aqueous paste of a sulfonated benzimidazolone dye.
(Synthesis of derivative N-1)
The resulting benzimidazolone dye sulfonated water paste was reslurried in 10,000 parts of water and adjusted to pH 10 with an aqueous sodium hydroxide solution, and then 20 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. The reaction slurry was heat-treated at 90 ° C. for 2 hours, filtered, washed with water, and dried to obtain a derivative N-1 having the following structure, which is an aluminum salt of a sulfonated derivative of a benzimidazolone dye.

(Preparation of derivative N-2)
The resulting benzimidazolone dye sulfonated water paste, filtered, washed with water, and dried to obtain a derivative N-2, which is a sulfonic acid derivative of a benzimidazolone dye.

(Synthesis of derivative N-3)
The obtained benzimidazolone dye sulfonated water paste was reslurried in 10,000 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia solution until pH was 7). The mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystals were washed with water and then dried at 80 ° C. to obtain a derivative N-3 which is an ammonium salt of a sulfonated derivative of a benzimidazolone dye.

(Preparation of yellow treated pigment 2)
Isoindoline-based yellow pigment CI Pigment Yellow 185 (BASF “Pariol Yellow D1155”): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) 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. 490 parts of yellow-treated pigment 2 were obtained.

(Preparation of yellow-treated pigment 3)
500 parts of isoindoline-based yellow pigment CI Pigment Yellow 139 (manufactured by BASF “Pariol Yellow D1819”), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) 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. 490 parts of yellow-treated pigment 3 were obtained.

(Preparation of yellow-treated pigment 4)
Benzimidazolone yellow pigment CI Pigment Yellow 194 ("Nova Palm Yellow F2G" manufactured by Clariant): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 120 The mixture was kneaded for 8 hours at 0 ° C. 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. 490 parts of yellow-treated pigment 4 were obtained.

(Preparation of yellow-treated pigment 5)
Benzimidazolone yellow pigment CI Pigment Yellow 180 (“Nova Palm Yellow P-HG” manufactured by Clariant): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho). And kneading 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. 490 parts of yellow-treated pigment 5 were obtained.

(Preparation of yellow-treated pigment 6)
Isoindolinone-based yellow pigment CI Pigment Yellow 109 (“Irgazine Yellow 2GLTE” manufactured by Ciba): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless 1 gallon kneader (Inoue Seisakusho), 120 The mixture was kneaded at 0 ° 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. 490 parts of yellow-treated pigment 6 were obtained.

(Preparation of green treated pigment 2)
Preparation of 500 parts of phthalocyanine green pigment CI Pigment Green 7 (“Lionol Green YS-07” manufactured by Toyo Ink Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol into a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel And kneading at 120 ° C. for 2 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. 490 parts of green-treated pigment 2 were obtained.

(Preparation of blue-treated pigment 1)
Preparation of 500 parts of phthalocyanine-based blue pigment CI Pigment Blue 15: 6 (“Lionol Blue ES” manufactured by Toyo Ink Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol into a 1 gallon kneader (manufactured by Inoue Seisakusho) And kneading 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. 490 parts of blue-treated pigment 1 were obtained.

(Preparation of blue-treated pigment 2)
Selenium blue pigment CI Pigment Blue 60 (Clarant “Hosta Palm Blue RL01”): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) at 120 ° C. Kneaded 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. 490 parts of blue-treated pigment 2 were obtained.

(Preparation of purple treated pigment 1)
Dioxazine-based purple pigment CI Pigment Violet 23 (“Hosta Palm Violet BL” manufactured by Clariant): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. Kneaded 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. 490 parts of purple-treated pigment 1 were obtained.

(Preparation of purple treated pigment 2)
Quinacridone-based purple pigment CI Pigment Violet 19 (“Hosta Palm Red E3B” manufactured by Clariant): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) at 120 ° C. Kneaded 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. 490 parts of purple-treated pigment 2 were obtained.

(Preparation of red treated pigment 1)
Diketopyrrolopyrrole red pigment CI Pigment Red 254 ("Irgaphore Red B-CF" manufactured by Ciba): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts on a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) Charged 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. 490 parts of red-treated pigment 1 were obtained.

(Preparation of red treated pigment 2)
Anthraquinone red pigment CI Pigment Red 177 ("Chromium phthalal red A2B" manufactured by Ciba): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. Kneaded 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. 490 parts of red-treated pigment 2 were obtained.

(Preparation of red treated pigment 3)
Condensed azo-based red pigment CI Pigment Red 214 (“Chromium Phtal Red BN” manufactured by Ciba): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) 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. 490 parts of red-treated pigment 3 were obtained.

(Preparation of magenta color treatment pigment 1)
Quinacridone-based magenta color pigment CI Pigment Red122 (“Hosta Palm Pink E” manufactured by Clariant): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a 1 gallon kneader (manufactured by Inoue Seisakusho) 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. 490 parts of magenta color-treated pigment 1 were obtained.

(Preparation of cyan pigment 1)
Phthalocyanine-based cyan pigment CI Pigment Blue 15: 3 (“Lionol Blue FG7351” manufactured by Toyo Ink Manufacturing Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts in a stainless steel 1 gallon kneader (Inoue Seisakusho) Charged 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. 490 parts of cyan-treated pigment 1 were obtained.

[Examples 10 to 37, Comparative Examples 16 to 49]
A mixture having the composition shown in Table 18 was stirred and mixed uniformly, then dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a pigment dispersion.

* 1: Treated pigments shown in Table 19 were used as pigments.
* 2: The dye derivatives shown in Table 19 were used as the dye derivatives.

(Alkali developable resist material)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain an alkali developing resist material.
Pigment dispersion shown in Table 18 60.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba) 1.2 parts Trimethylolpropane triacrylate 4.2 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 1.4 parts Acrylic resin solution 2 11.0 parts Cyclohexanone 23.2 parts

The yield value and thixo index of the resist materials obtained in Examples 10 to 37 and Comparative Examples 16 to 49 were measured using an E-type viscometer (“R110” manufactured by Toki Sangyo Co., Ltd.). The thixo index value representing the dispersion stability is preferably 1.5 or less.
Moreover, about the resist material obtained in Examples 10-37 and Comparative Examples 16-49, the film thickness uniformity and storage stability were evaluated by the following method. The evaluation results are shown in Table 19.
The uniformity of the film thickness is determined by spin-coating a resist material so that the average film thickness is 1.8 μm on a 360 mm × 465 mm size substrate having a plate thickness of 0.7 mm, drying at 70 ° C. for 30 minutes, A film thickness (assumed as A) and an average value (assumed as B) of four thicknesses at 200 mm from the center on a diagonal line were measured and evaluated by the following formula. The coating thickness uniformity is preferably less than 2%.
(A−B) × 100 / {(A + B) / 2} [%]
The storage stability was measured in four stages (◎: less than 1% change, ○: less than 1% change to less than 3%, Δ from the viscosity results before and after standing for 7 days at 40 ° C. in the dark. : 3% or more and less than 10%, x: 10% or more). ◎ and ○ are practical ranges, but 、 is preferable.

  As is clear from Table 19, in the case of the colored composition of this example, the thixo index values indicating dispersion stability are all 1.5 or less, and the film thickness uniformity is less than 2%. Furthermore, it can be seen that the storage stability is ◎ or ○, which is very good.

[Example 38]
A color filter including a red filter segment, a blue filter segment, and a green filter segment was produced by the following method.
The red resist and material obtained in Example 30 were applied to a glass substrate by spin coating so as to have a film thickness of chromaticity (x, y) shown in Table 20. After drying, striped pattern exposure was performed with an exposure machine and development was performed with an alkaline developer for 90 seconds to form a striped red filter segment. The alkali developer is composed of 8.0% sodium carbonate 1.5% sodium hydrogen carbonate 0.5% anionic surfactant ("Perrex NBL" manufactured by Kao Corporation) and 90% water.

Next, the yellow resist material obtained in Example 11 and the green resist material obtained in Example 18 were mixed to prepare a green resist, and the film thicknesses of chromaticities (x, y) shown in Table 20 were obtained. It was applied as follows. After drying, a striped pattern adjacent to the red filter segment was exposed with an exposure machine to form a striped green filter segment.
Furthermore, the blue resist material obtained in Example 24 was applied so as to have a film thickness of chromaticity (x, y) shown in Table 20, and striped blue filter segments adjacent to the red and green filter segments were formed. Formed.

The shape of each color filter segment was good, and the resolution was also good. Finally, the obtained color filter is heated in an oven at 230 ° C. for 30 minutes to completely react with the remaining polymerizable functional groups, and a red, green, and blue stripe-shaped stripe shape is formed on the transparent substrate. A color filter comprising filter segments was obtained.
Y of each color of the color filter obtained in Example 38 was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). In addition, when light is transmitted through all three colors, white light is obtained. The x, y, Y, color temperature K, duv of the white light was calculated from x, y, Y of each color. The results are shown in Table 20.

[Example 39]
A color filter including a cyan color filter segment, a magenta color filter segment, and a yellow color filter segment was produced by the following method.
Table 21 shows the cyan resist material obtained in Example 37, the magenta resist material obtained in Example 36, and the yellow resist material obtained in Example 11, as in Example 39. The film was applied so as to have a film thickness of chromaticity (x, y), and a color filter having a stripe-shaped filter segment of three colors of cyan, magenta, and yellow on a transparent substrate was obtained.
Y of each color of the color filter obtained in Example 39 was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). When light is transmitted through all three colors, white light is obtained. The x, y, Y and color temperature K, duv of the white light were calculated from x, y, Y of each color. The results are shown in Table 21.

Claims (7)

A coloring composition for a color filter , comprising: a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof; an organic pigment dispersed in the pigment carrier; and an aluminum salt of a sulfonated dye derivative. The dyes constituting the aluminum salts of sulfonated dye derivatives are diketopyrrolopyrrole dyes, azo dyes, phthalocyanine dyes, anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes 2. The coloring composition for a color filter according to claim 1, wherein the coloring composition is any one of a dye, an isoindoline dye, an isoindolinone dye, a quinophthalone dye, a selenium dye, and a metal complex dye. The coloring composition for a color filter according to claim 1 or 2 , wherein the dye constituting the aluminum salt of the sulfonated dye derivative is CI Pigment Yellow 138. The coloring composition for color filters according to any one of claims 1 to 3, further comprising a resin-type dispersant. The colored composition for a color filter according to claim 4, wherein the resin-type dispersant is a basic resin-type dispersant. A compound represented by the following general formula (1) (a) with other ethylenically unsaturated compounds having a double bond (b) and the characterized in that it contains a copolymerization comprising a resin according to claim 1 The coloring composition for color filters in any one of 5 .
General formula (1)
(R ₁ is H or CH ₃ , R ₂ is an alkylene group, R ₃ is H or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring) A color filter comprising a filter segment formed from the colored composition for a color filter according to any one of claims 1 to 6 .