JP5099187B2 - Coloring composition for color filter and color filter - Google Patents

Description

The present invention relates to a colored composition for a color filter used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.

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 dispersion of a pigment 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 then an unexposed portion is obtained. The color filter can be manufactured by repeating the same operation for all the filter colors in order after forming a first color pattern by applying a process such as heating if necessary.

In the second method, a dispersion of a pigment 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. Two filter color patterns are exposed 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. A color filter can be manufactured by forming a color pattern and, if necessary, applying a treatment such as heating, and then repeating the same operation for all filter colors. Note that the development of the resist and the etching of the pigment-dispersed coating film can be performed simultaneously.

JP-A-9-176511

In the above method, a colored composition containing a red pigment is used for the production of the red filter segment. I. Pigment Red 179 and the like have been used.
However, in the situation where there is an increasing demand for color characteristics such as transparency, that is, brightness, improvement in color purity, coating uniformity when forming pixels, sensitivity, developability, pattern shape, etc. C. is adopted from I. Pigment Red 179 and the like are becoming difficult to cope with. In particular, in recent years, liquid crystal display devices have been applied for television monitor applications, and bright color filters are required to produce low power consumption panels.

An object of the present invention is to provide a coloring composition that is excellent in color characteristics, has a particularly high transmittance, and can therefore form a color filter with high brightness. Another object of the present invention is to provide a color filter having good color characteristics, that is, high whiteness.

Since the coloring composition for a color filter of the present invention contains a perylene pigment having specific spectral characteristics as a red pigment, the spectral spectrum of the filter segment can be controlled by using the composition, and the lightness and high color purity can be controlled. Can be obtained.

（上記式（１）において、Ａは、それぞれ独立に、水素原子または置換基を有してもよいアルキル基もしくはアリール基を表す。） That is, the present invention has a colorant carrier comprising a transparent resin, a precursor thereof or a mixture thereof, a perylene pigment represented by the following formula (1) dispersed in the colorant carrier, and an acidic group. A composition comprising at least one derivative selected from a dye derivative, an anthraquinone derivative, an acridone derivative or a triazine derivative, or a salt thereof, wherein the perylene pigment is salt milled together with a water-soluble inorganic salt and a water-soluble organic solvent. Spectral transmission at 545 nm of the coating film when the coating film is formed using the red composition obtained by processing and dispersing the pigment in the colorant carrier so that the spectral transmittance at 470 nm is 1%. A color filter coloring group characterized by having spectral characteristics such that the transmittance is 8% or more and the spectral transmittance at 615 nm is 80% or more To provide things.
Formula (1)

(In the above formula (1), each A independently represents a hydrogen atom or an alkyl or aryl group which may have a substituent.)

The colored composition of the present invention contains at least one derivative selected from a dye derivative, an anthraquinone derivative, an acridone derivative or a triazine derivative having an acidic group, or a salt thereof, and particularly an aluminum salt of a derivative having an acidic group. It is preferable.
Moreover, it is preferable that content of the aluminum salt of the derivative | guide_body which has an acidic group is 0.001 to 40 weight% on the basis of the perylene-type pigment represented by Formula (1).

Furthermore, the present invention comprises at least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein the at least one red filter segment is formed from the colored composition of the present invention. A color filter is provided.

A coating film is formed by using a red composition represented by the above formula (1), in which the pigment is dispersed in the colorant carrier so that the spectral transmittance at 470 nm is 1%. A perylene pigment (hereinafter referred to as the perylene pigment of the present invention) having spectral characteristics such that the spectral transmittance at 545 nm of the coating film is 8% or more and the spectral transmittance at 615 nm is 80% or more. When a red filter segment is formed using the coloring composition of the present invention containing at least one derivative selected from a dye derivative, an anthraquinone derivative, an acridone derivative or a triazine derivative having a group, or a salt thereof, a conventional red filter Compared to the segment, the transmission wavelength region with a transmittance of 75% or more at the same hue is shifted to the short wavelength side, and the transmission region is wider. Ri permeability increases, also increases the brightness of the white.

The red coloring composition for color filters of the present invention comprises a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and a perylene pigment represented by the above general formula (1). Examples of perylene pigments represented by the general formula (1) include C.I. I. Pigment Red 123, 149, 178, 179, 190, and the like. I. Pigment Red 179 is preferred.

The perylene pigment of the present invention is a salt milling system in which the perylene pigment represented by the above formula (1) is kneaded for 8 hours or more with heating together with a water-soluble inorganic salt and a small amount of a water-soluble organic solvent to control the pigment particle size. It can manufacture by processing. The kneading time of the perylene pigment, the water-soluble inorganic salt and the water-soluble organic solvent is preferably 24 hours or less from the viewpoint of the balance between the color characteristics of the obtained salt milled pigment and the cost required for the salt milling treatment.
The salt milling treatment time of a general pigment is 2 to 4 hours. With this treatment time, even when the obtained salt milling pigment is dispersed in a colorant carrier, the spectral transmittance at 470 nm is 1%. When the coating film is formed in such a manner, the spectral transmittance at 545 nm of the coating film is not more than 8% and the spectral transmittance at 615 nm is not more than 80%, and the transmission region does not widen, so the transmittance does not increase.

Specifically, the salt milling treatment is performed by kneading a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, and then washing with water to wash the water-soluble inorganic salt and the water-soluble salt. This is a process for removing the organic solvent. The water-soluble inorganic salt works as a crushing aid, and it is thought that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Therefore, the crushing of the pigment and the crystal growth occur simultaneously during the kneading, and the primary particle diameter of the pigment obtained varies depending on the kneading conditions. When salt milling the pigment, it is necessary to promote crystal growth by heating, and the heating temperature is preferably 70 to 150 ° C. When the heating temperature is less than 70 ° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes undesirably close to amorphous. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds excessively and the primary particle diameter of the pigment becomes large, which is not preferable as a colorant for the color filter coloring composition.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The amount of the inorganic salt used for salt milling is preferably 0.5 to 20 times by weight, particularly 1 to 10 times by weight of the pigment from the viewpoint of both processing efficiency and production efficiency.
The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates.

Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol. , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Is used.

At the time of salt milling, a resin can be used in combination in order to prevent strong agglomeration when the treated pigment obtained after the salt milling treatment is dried and to be easily dispersed in the colorant carrier. A soft powder-treated pigment can be obtained by using a resin together during salt milling. The resin used for salt milling is preferably a resin that is solid at room temperature, insoluble in water, and at least partially soluble in the above organic solvent, natural resin, modified natural resin, synthetic resin, synthetic resin modified with natural resin Resin or the like is used. As the natural resin, rosin is representative, and as the modified natural resin, rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof are used. Examples of the synthetic resin include epoxy resin, acrylic resin, maleic acid resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, and polyamide resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic resin, rosin-modified fumaric acid resin, and rosin-modified phenol resin. The amount of resin used is preferably in the range of 5 to 100% by weight based on the total pigment.

At the time of salt milling, in addition to the above resins, additives such as pigment dispersion aids and plasticizers, or inorganic pigments such as calcium carbonate, barium sulfate, and silica, which are generally known as extender pigments, may be used in combination. Moreover, in order to adjust a hue, you may mix and process with another pigment.
The perylene pigment of the present invention can also be produced by dry milling the perylene pigment represented by the above formula (1). Specifically, the dry milling process is a method of finely pulverizing primary particles of a pigment by dry pulverization with a ball mill, an attritor, a vibration mill or the like.

As described above, the colorant carrier in which the perylene pigment of the present invention is dispersed 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 a precursor thereof includes a monomer or an oligomer that is cured by radiation irradiation to form a transparent resin, which are used alone or in combination. 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 for a color filter 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 phenol resin. , Polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubbers, celluloses, polybutadiene, polyimide resins, and the like. Moreover, as a thermosetting resin, an epoxy resin, a benzoguanamine resin, a melamine resin, a urea resin etc. are mentioned, for example.

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. In addition, 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.

As photopolymerization initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy Acetophenone photopolymerization initiators such as cyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin photopolymerization initiators such as benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-ben Benzophenone photopolymerization initiators such as yl-4′-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (tri (Loromethyl) -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 combination of two or more. As sensitizers, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanthrenequinone are used. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.

The coloring composition for a color filter of the present invention is obtained by mixing the perylene pigment of the present invention with other pigments as necessary, and then, if necessary, together with the photopolymerization initiator in a colorant carrier, a three-roll mill. It can be produced by finely dispersing using various dispersing means such as a two-roll mill, a sand mill, and a kneader.
When the pigment is dispersed in the colorant carrier, a dispersion aid such as a resin-type pigment dispersant, a surfactant, a dye derivative, or a triazine derivative can be appropriately contained. The dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition is used in which the pigment is dispersed in the colorant carrier using the dispersion aid. In this case, a color filter having excellent transparency can be obtained. In particular, a pigment derivative, anthraquinone derivative, acridone derivative, triazine derivative or salt thereof having a basic group or an acidic group is preferably used because of a large pigment dispersion effect. An aluminum salt of a triazine derivative having a basic group or a derivative having an acidic group is preferable.

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 colorant carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment into the colorant carrier. It works to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Oil-based dispersants such as salts; water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

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

A 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. These can be used alone or in combination of two or more.

式（３）

式（４）

式（５）

Specific examples of the basic group that the dye derivative and the triazine derivative have include substituents represented by the following general formulas (2), (3), (4), and (5).
Formula (2)

Formula (3)

Formula (4)

Formula (5)

X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ₁ and R ₂ Represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R _{3 represents} an alkyl group which may be substituted, an alkenyl group which may be substituted or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
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. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.
Z: represents an alkylene group that may be substituted, an alkenylene group that may be substituted, or a phenylene group that may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-8 are preferable.
P: The substituent shown by Formula (6) or the substituent shown by Formula (7) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (6) or a substituent represented by the formula (7).

式（７）

Formula (6)

Formula (7)

Examples of the organic dye constituting the dye derivative having a basic group include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, and ant 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 Dyes, metal complex dyes, and the like. Moreover, the pigment used for the coloring composition for color filters mentioned later may be used.

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.

A pigment derivative having a basic group can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the following formula (8) to formula (11) into an organic dye, the substituent represented by formula (2) to formula (5) is reacted with the substituent. Amine component to be formed, for example, 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.
Equation (8) -SO ₂ Cl
Formula (9) -COCl
Equation (10) -CH ₂ NHCOCH ₂ Cl
Equation (11) -CH ₂ Cl

When the organic dye is an azo dye, the basic group is introduced by introducing a substituent represented by the general formulas (2) to (5) into the diazo component or the coupling component in advance and then performing a coupling reaction. It is also possible to produce an azo dye derivative having the same.
Triazine derivatives having a basic group 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 (2) to (5) 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 (2) to (7) 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, di-sec-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-dimethylamino Amylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N , N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylamino The Pyramine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4 -Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isnicopetinate, Ethyl isonicopetic acid, 2-Piperidinethanol, Pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecholine, N-amino Examples thereof include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

Examples of the acidic group of the derivative obtained by forming an aluminum salt of an acidic group include a sulfonic acid group and a terephthalic acid monoamidomethyl group. Sulfonic acid groups can be introduced by allowing sulfuric acid to act on organic pigments, and terephthalic acid monoamidomethyl groups can be chloromethylated and then aminomethylated with primary amines and then monoamidated with terephthalic acid. Can be introduced.

As the pigment derivative, those shown in Tables 1 to 15 can be used, but are not limited thereto. The pigment derivatives can be used alone or in admixture of two or more.

The coloring composition of the present invention can contain other organic or inorganic colorants together with the perylene pigment of the present invention, depending on the hue of the filter segment to be formed. Examples of the organic colorant include dyes, organic pigments, natural pigments, and the like, and examples of the inorganic colorant include inorganic pigments. The inorganic pigment includes extender pigments. As the colorant, a colorant having high color developability and high heat resistance, particularly a colorant having high heat decomposition resistance is preferable, and an organic colorant is usually used, and an organic pigment is particularly preferable. An organic or inorganic coloring agent can be used individually or in mixture of 2 or more types.
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, 81: 3, 81: 4, 146, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, CI Pigment Orange 43, 71, 73, etc. A red pigment can be used in combination.
In this case, the content of the perylene pigment of the present invention based on the total amount of the colorant (the total amount of the perylene pigment and the red pigment of the present invention) varies depending on the required color characteristics, but sufficient brightness. From the viewpoint of obtaining, it is preferably 0.01 to 90% by weight, particularly 10 to 50% by weight.

In addition, the coloring composition of the present invention has titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, etc. in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness. Inorganic colorants such as zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be contained.

When the coloring composition of the present invention contains two or more kinds of coloring agents, the coloring composition of the invention mixes two or more kinds of coloring agents, and then the obtained coloring agent mixture is used as necessary. Along with the photopolymerization initiator, it can be produced by finely dispersing in a colorant carrier by a known method. In addition, the coloring composition of the present invention can be produced by mixing each colorant separately finely dispersed in a colorant carrier.

Further, in the coloring composition of the present invention, the colorant is sufficiently dispersed in the colorant carrier, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easier to form, a solvent can be included. 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, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

In addition, the colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.

The coloring composition of the present invention can be prepared in the form of inkjet ink, 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 the perylene pigment of the present invention and, if necessary, other colorants in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, and a photopolymerization initiator. Is.

The perylene pigment of the present invention and other colorants used as needed are added in a ratio of 1.5 to 7% by weight in the total color composition when the filter segment is formed by photolithography. It is preferable to contain. Moreover, when forming a filter segment by a printing method, it is preferable to contain in a ratio of 1.5 to 40 weight% in total in a coloring composition. In any case, the colorant is preferably contained in the final filter segment in a proportion of 10 to 40% by weight, more preferably 20 to 40% by weight, the remainder from the resinous binder provided by the colorant carrier. Become substantial.

The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

As mentioned above, the color filter of the present invention comprises at least one red filter segment, at least one blue filter segment, at least one green filter segment, wherein at least one red filter segment It is formed using a coloring composition.
The blue filter segment can be formed using a normal blue coloring composition. Instead of the perylene pigment of the present invention, the blue coloring composition may be, for example, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, and the like. Blue coloring compositions include C.I. I. Purple violet pigments such as Pigment Violet 1, 19, 23, 27, 32, and 42 can be used in combination.

Moreover, a green filter segment can be formed using a normal green coloring composition. Instead of the perylene pigment of the present invention, the green coloring composition may be, for example, C.I. I. This is a composition obtained using a green pigment such as Pigment Green 7, 10, 36, 37. Green coloring compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 It can be used in combination with the yellow pigments such as 181,182,185,187,188,193,194,198,199,213,214.

The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate using the coloring composition of this invention by the printing method or the photolithographic method.
As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate 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 developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, 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 alkaline 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.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.
First, the acrylic resin solution and red pigment used in Examples and Comparative Examples will be described.

(Preparation of acrylic resin solution)
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A photosensitive transparent resin solution was obtained.
After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-photosensitive transparent resin solution synthesized earlier had a non-volatile content of 20% by weight. Cyclohexanone was added so that The obtained non-photosensitive transparent resin had a weight average molecular weight of 40,000.

Next, the perylene pigment represented by the formula (1) was subjected to a salt milling treatment by the following method to produce a red treated pigment.
[Red pigment 1]
C. I. Pigment Red 179 pigment (“Pariogen Maroon L-3920” manufactured by Bayer): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. for 8 hours. Kneaded. 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, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of red pigment 1 were obtained.

[Red pigment 2]
C. I. Pigment Red 179 pigment ("Pariogen Maroon L-3920" manufactured by Bayer): 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 for 4 hours. Kneaded. 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, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of red pigment 2 were obtained.

[Red pigment 3]
C. I. Pigment Red 179 pigment ("Pariogen Maroon L-3920" manufactured by Bayer): 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 for 2 hours. Kneaded. 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, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of red pigment 3 were obtained.

[Production Example 1]
A mixture having the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a perylene red pigment dispersion.
Red pigment 1 9.0 parts Dye derivative (Compound A-44) 1.0 part Acrylic resin solution 50.0 parts Cyclohexanone 40.0 parts Then, the mixture having the following composition was stirred and mixed to be uniform, Filtration through a filter gave an alkali developing red resist material.
Perylene red pigment dispersion 60.0 parts Acrylic resin solution 11.0 parts Trimethylolpropane triacrylate 4.2 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Geigy) 1.2 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Cyclohexanone 23.2 parts

[Example 1]
An alkali-developable red resist material was produced in the same manner as in Production Example 1 except that the dye derivative (A-44) was changed to the dye derivative (B-10).

[Comparative Example 1]
An alkali development type red resist material was prepared in the same manner as in Production Example 1 except that the red pigment 1 was changed to the red pigment 2.
[Comparative Example 2]
An alkali development type red resist material was produced in the same manner as in Production Example 1 except that the red pigment 1 was changed to the red pigment 3.
[Comparative Example 3]
Red pigment 1 is treated with untreated C.I. I. An alkali-developable orange resist material was produced in the same manner as in Production Example 1 except that Pigment Red 179 pigment (“Pariogen Maroon L-3920” manufactured by Bayer) was used.

The resist materials obtained in Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were placed on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater at 500 rpm, 1000 rpm, 1500 rpm, and 2000 rpm. Coating was performed at the number of rotations to obtain four types of coated substrates having different film thicknesses. Next, after drying at 70 ° C. for 20 minutes, ultraviolet exposure was performed with an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp. The coated substrate was heated at 230 ° C. for 1 hour and allowed to cool, and then the chromaticity (Y, x, y) of the obtained red coating film with a C light source was measured by a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It measured using. From the four sets of chromaticity / spectral measurement results, spectral transmittances at 545 nm and 615 nm when the spectral transmittance at 470 nm was 1%, x, y, and Y were obtained. Furthermore, the surface state of the coated substrate at 1000 rpm was observed with an optical microscope (“BX60” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 16.

As shown in Table 16, the red coating film formed using the resist materials of Comparative Example 1, Comparative Example 2 and Comparative Example 3 had a transmittance of less than 80% at 615 nm, whereas that of Example 1 was small. The 615 nm transmittance of the red coating film formed using the resist material is as high as 80% or more, and the red coating film formed using the colored composition (resist material) of the present invention has a wider transmission region and is excellent. ing. Further, the lightness Y is increased due to the high transmittance, and the color characteristics are improved.

[Example 2]
In order to produce a color filter comprising a red filter segment, a blue filter segment, and a green filter segment, blue and green resist materials were produced by the following method.

(Blue resist material)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a copper phthalocyanine dispersion.
ε-type copper phthalocyanine pigment C.I. I. Pigment Blue 15: 6 8.6 parts ("Heliogen Blue L-6700F" manufactured by BASF)
Dioxazine pigments C.I. I. Pigment Violet 0.4 part (“Rionogen Violet R-6200” manufactured by Toyo Ink Co., Ltd.)
Dye derivative (A-47) 0.9 part Dye derivative (A-51) 0.1 part Acrylic resin solution 50.0 parts Cyclohexanone 40.0 parts Next, after stirring and mixing the mixture having the following composition to be uniform It filtered with a 1 micrometer filter and obtained the blue resist material.
Copper phthalocyanine dispersion 60.0 parts Acrylic resin solution 11.0 parts Trimethylolpropane triacrylate 4.2 parts (Shin Nakamura Chemical Co., Ltd. “NK ester ATMPT”)
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Geigy) 1.2 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Cyclohexanone 23.2 parts

(Green resist material)
8.6 parts of ε-type copper phthalocyanine pigment and 0.4 parts of dioxazine pigment were added to copper phthalocyanine green pigment C.I. I. Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.) 5.7 parts, metal complex yellow pigment C.I. I. Pigment Yellow 150 (“E-4GN” manufactured by Bayer Co.) is changed to 3.3 parts, and the dye derivative (A-47) and the dye derivative (A-51) are changed to the dye derivative (A-44). A green resist material was prepared in the same manner as the resist material.

The red resist material obtained in Example 1 was applied to a glass substrate by spin coating so that x = 0.5789 and y = 0.343. 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 sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, anionic surfactant (“Perilex NBL” manufactured by Kao Corporation) 8.0% by weight and water 90% by weight. .

Next, in the same manner as the red resist material, a green resist material was applied to a film thickness such that x = 0.283 and y = 0.60. 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, in the same manner as the red resist material, a blue resist material was applied to a film thickness such that x = 0.144 and y = 0.079. After drying, striped blue filter segments adjacent to the red and green filter segments were 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.

[Comparative Example 4]
Of 9.0 parts of red pigment 1, 8.6 parts are red pigment 2 and 0.4 parts are isoindoline yellow pigment C.I. I. An alkali-developable red resist material was obtained in the same manner as in Production Example 1 except that Pigment Yellow 139 (“Irgaphor Yellow 2R-CF” manufactured by Ciba) was used.
A color filter was produced in the same manner as in Example 2, using the produced red resist material, the green resist material produced in Example 2, and the blue resist material produced in Example 2.
[Comparative Example 5]
Of 9.0 parts of red pigment 1, 8.4 parts are red pigment 3 and 0.6 parts are isoindoline yellow pigment C.I. I. An alkali-developable red resist material was obtained in the same manner as in Production Example 1 except that Pigment Yellow 139 (“Irgaphor Yellow 2R-CF” manufactured by Ciba) was used.
A color filter was produced in the same manner as in Example 2, using the produced red resist material, the green resist material produced in Example 2, and the blue resist material produced in Example 2.
[Comparative Example 6]
Out of 9.0 parts of red pigment 1, 8.2 parts of untreated C.I. I. Pigment Red 179 pigment (“Pariogen Maroon L-3920” manufactured by Bayer) and 0.8 part of isoindoline yellow pigment C.I. I. An alkali-developable red resist material was obtained in the same manner as in Production Example 1 except that Pigment Yellow 139 (“Irgaphor Yellow 2R-CF” manufactured by Ciba) was used.
A color filter was produced in the same manner as in Example 2, using the produced red resist material, the green resist material produced in Example 2, and the blue resist material produced in Example 2.

Y of each color of the color filters obtained in Example 2, Comparative Example 4, Comparative Example 5, and Comparative Example 6 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, and x, y, Y of the white light is calculated from x, y, Y of each color. The results are shown in Tables 17 and 18. As shown in Table 18, the Y value of the color filter obtained in Example 2 is higher than those obtained in Comparative Example 4, Comparative Example 5 and Comparative Example 6. When the Y value is high, a white color filter becomes bright.

Claims (4)

A colorant carrier comprising a transparent resin, a precursor thereof or a mixture thereof, a perylene pigment represented by the following formula (1) dispersed in the colorant carrier, a dye derivative having an acidic group, an anthraquinone derivative, A composition comprising at least one derivative selected from an acridone derivative and a triazine derivative, or a salt thereof,
The perylene pigment is C.I. I. Any one selected from the group consisting of Pigment Red 123, 149, 179, and 190,
The perylene pigment is salt milled together with a water-soluble inorganic salt and a water-soluble organic solvent, and a spectral transmittance at 470 nm is 1% using a red composition obtained by dispersing the pigment in the colorant carrier. When the coating film is formed in such a manner, it has a spectral characteristic that the spectral transmittance at 545 nm of the coating film is 8% or more and the spectral transmittance at 615 nm is 80% or more. .
Formula (1)

(In the above formula (1), each A independently represents a hydrogen atom or an alkyl or aryl group which may have a substituent.)   The coloring composition according to claim 1, wherein the derivative is an aluminum salt of a derivative having an acidic group.   The coloring composition according to claim 2, wherein the content of the aluminum salt of the derivative having an acidic group is 0.001 to 40% by weight based on the perylene pigment represented by the formula (1). It comprises at least one red filter segment, at least one blue filter segment, and at least one green filter segment, and the at least one red filter segment is formed from the colored composition according to claim 1. A color filter characterized by having