JP6724512B2 - Compound, pigment dispersant containing the compound, coloring composition and color filter - Google Patents

Description

The present invention is formed by a printing ink, a paint, a resin colorant, a compound suitably used for ink jet inks and color filter inks, a pigment dispersant, a pigment composition, a coloring composition, and the coloring composition. The present invention relates to a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like.

Pigments used in inks and paints are often fine particles in order to achieve a clearer color tone.To solve such problems, a pigment dispersant is used, and the space between the pigment and the vehicle is reduced. It is known to improve the affinity and stabilize the dispersion, and various pigment dispersants have been disclosed so far. For example, in a system in which highly miniaturized diketopyrrolopyrrole pigment particles such as printing inks, paints, especially ink jet inks and color filter inks are dispersed, in order to loosen the strong cohesive force of the pigment particles and obtain stability over time. In addition, a diketopyrrolopyrrole compound is used as a pigment dispersant (Patent Document 1). However, although this pigment dispersant is excellent in dispersibility, the dispersion has a problem that the sharpness (brightness) is lowered.
It is also known to use a sulfonated derivative of a diketopyrrolopyrrole pigment as a pigment dispersant, which is a sulfonated free diketopyrrolopyrrole pigment or a salt neutralized with an aqueous metal alkali solution or an aqueous amine solution. 2-4).
However, conventional diketopyrrolopyrrole pigment dispersants are used in printing inks, paints, especially ink jet inks, inks for color filters, etc., in which highly finely divided pigment particles are required to achieve high clarity. In the above, the effect of suppressing the crystal growth of the pigment was not sufficient, and satisfactory physical properties could not be obtained.

JP H03-26767 JP 2000-160084 JP 2001-240780 A JP, 2009-299886, A

The object of the present invention is, in addition to the high dispersibility that has been required for pigment dispersants, a compound that exhibits a high pigment crystal growth inhibitory effect on high clarity (brightness) and diketopyrrolopyrrole pigment, and the compound. The present invention provides a pigment composition, a coloring composition, and a color filter containing

That is, the present invention relates to a compound represented by the following general formula (1) or general formula (2).
General formula (1)
[In the general formula (1),
X represents a hydrogen atom, an alkyl group, a phenyl group, a halogen, a thiophenyl group, an N,N-dialkylamino group, a trifluoromethyl group, or a cyano group.
Y ₁ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group which may have a substituent, or a naphthylene group which may have a substituent.
S ₁ represents a sulfonic acid group; its amine salt, its quaternary ammonium salt or its metal salt.
m represents an integer of 0 or 1, n represents an integer of 1 or 2, and m+n represents an integer of 1 or 2. ]

General formula (2)
[In the general formula (2),
X represents a hydrogen atom, an alkyl group, a phenyl group, a halogen, a thiophenyl group, an N,N-dialkylamino group, a trifluoromethyl group, or a cyano group.
Y ₂ represents a group obtained by removing one hydrogen atom from an alkylene group having 1 to 6 carbon atoms, a group obtained by removing one hydrogen atom from a phenylene group of a phenylene group which may have a substituent, or a substituent. The naphthylene group which may be represented is a naphthylene group having one hydrogen atom removed.
S ₂ represents a sulfonic acid group; its amine salt, its quaternary ammonium salt, or its metal salt.
p represents an integer of 0 or 1, q represents an integer of 1 or 2, and p+q represents an integer of 1 or 2. ]

The present invention also relates to the compound represented by the general formula (1).

The present invention also relates to the above compound, wherein in the general formula (1), Y ₁ is a group selected from the group consisting of an alkylene group having 1 to 6 carbon atoms and a phenylene group which may have a substituent.

The present invention also relates to the above compound, wherein in the general formula (1), X is an alkyl group.

The present invention also relates to a pigment dispersant containing the above compound.

The present invention also relates to a pigment composition containing the pigment dispersant and the pigment.

The present invention also relates to the above pigment composition, wherein the pigment is a diketopyrrolopyrrole pigment.

The present invention also relates to a coloring composition containing a colorant and an organic solvent, wherein the colorant contains the pigment dispersant or the pigment composition.

The present invention also relates to the above coloring composition, which further contains at least one of a photopolymerizable monomer and a photopolymerization initiator.

Furthermore, the present invention relates to a color filter formed from the above coloring composition.

With the compound of the present invention, a pigment dispersant capable of finely dispersing a pigment in a wide range of resins, excellent in non-aggregation, non-crystallinity, fluidity, coating gloss, sharpness, and storage stability It is possible to provide good ink and paint. In particular, the compound of the present invention, when used as a pigment dispersant, is excellent in dispersion while exhibiting high clarity in a red pigment group such as a diketopyrrolopyrrole red pigment, a quinacridone red pigment, and an anthraquinone red pigment. It has the effect of exerting the above effect.
Due to the above effects, the coloring composition containing the pigment dispersant of the present invention can be used in various general paints for gravure inks, automobiles, woods, metals, etc., magnetic tape back coat paints, radiation cure inks, inkjet printers. It can be used for applications such as ink and ink for color filters.

The compound of the present invention is a compound represented by the following general formula (1) or general formula (2).
<Compound represented by general formula (1) or general formula (2)>
General formula (1)

[In the general formula (1),
X represents a hydrogen atom, an alkyl group, a phenyl group, a halogen, a thiophenyl group, an N,N-dialkylamino group, a trifluoromethyl group, or a cyano group.
Y ₁ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group which may have a substituent, or a naphthylene group which may have a substituent.
S ₁ represents a sulfonic acid group; its amine salt, its quaternary ammonium salt or its metal salt.
m represents an integer of 0 or 1, n represents an integer of 1 or 2, and m+n represents an integer of 1 or 2. ]

General formula (2)

[In the general formula (2),
X represents a hydrogen atom, an alkyl group, a phenyl group, a halogen, a thiophenyl group, an N,N-dialkylamino group, a trifluoromethyl group, or a cyano group.
Y ₂ represents a group obtained by removing one hydrogen atom from an alkylene group having 1 to 6 carbon atoms, a group obtained by removing one hydrogen atom from a phenylene group of a phenylene group which may have a substituent, or a substituent. The naphthylene group which may be represented is a naphthylene group having one hydrogen atom removed.
S ₂ represents a sulfonic acid group; its amine salt, its quaternary ammonium salt, or its metal salt.
p represents an integer of 0 or 1, q represents an integer of 1 or 2, and p+q represents an integer of 1 or 2. ]

The substituents in the general formulas (1) and (2) will be described below, but the substituents are not limited thereto.

The alkyl group may have a side chain as well as a straight chain. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, Examples thereof include a decyl group and a dodecyl group.

Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the N,N-dialkylamino group include N,N-dimethylamino group, N,N-diethylamino group, N,N-dibutylamino group and the like.

Examples of the alkylene group include groups obtained by removing one hydrogen atom from the above alkyl group.

Examples of amines that form amine salts with sulfonic acid groups include (mono-, di- or tri)alkylamines, substituted or unsubstituted alkylenediamines and alkanolamines, and quaternary ammonium salts that form quaternary ammonium salts. Examples thereof include alkyl ammonium chloride and the like. Examples of the metal forming the metal salt include alkali metals such as Li, Na and K, and polyvalent metals such as Ca, Ba, Al, Mn, Sr, Mg, Fe, Zn and Ni.

Examples of the “substituent” which may be included include an alkyl group, an alkoxy group, a halogen, a nitro group and the like. The alkyl group and halogen have the same meanings as the substituents in the general formula (1) and the general formula (2). An alkoxy group is a group in which an oxygen atom is bonded to an alkyl group.

Of these, X is preferably hydrogen, an alkyl group or a phenyl group, more preferably an alkyl group, and particularly preferably a methyl group.
As Y ₁ , a phenylene group or a naphthylene group is preferable.
S ₁ is preferably an amine salt of sulfonic acid, the amine is preferably an alkylamine, more preferably a primary amine having 6 to 36 carbon atoms, and having 8 to 18 carbon atoms. Particularly preferred is a primary amine.
Y ₂ is preferably a group obtained by removing one hydrogen atom from a phenylene group or a group obtained by removing one hydrogen atom from a naphthylene group, and more preferably a group obtained by removing one hydrogen atom from a naphthylene group.
S ₂ is preferably an amine salt of sulfonic acid, the amine is preferably an alkyl amine, more preferably a primary amine having 6 to 36 carbon atoms, and having 8 to 18 carbon atoms. Particularly preferred is a primary amine.

As the compound of the present invention, the compound represented by the general formula (1) is preferable.

<Method for producing compound>
As a method for producing the compound of the present invention, a production method known in the art can be used. An example of a method for producing the compound represented by the following formula (3) is shown below, but the present invention is not limited to this production method.

First, a diketopyrrolopyrrole pigment represented by the following formula (4) is sulfonated by reacting with fuming sulfuric acid to produce a compound represented by the following formula (5). Further, the compound represented by the following formula (6) is produced by reacting the compound represented by the following formula (5) with a chlorinating agent. Next, the compound represented by the following formula (6) is reacted with taurine and heated to produce the compound represented by the above formula (3).

Various compounds of the invention can be formed by using compounds having other amine moieties and sulfonic acid moieties in place of taurine.
For example, N-methyltaurine, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, sulfanilic acid, 4-chloroaniline-3-sulfonic acid, 2-nitroaniline-4-sulfonic acid, 2-methoxysulfoaniline, 4-methoxy-3-sulfoaniline, 3-methylaniline-4-sulfonic acid, 2-amino-1-naphthalenesulfonic acid, 5-amino-1-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid and 5 -Amino-3-naphthalenesulfonic acid, 8-amino-1-naphthalenesulfonic acid, aniline-2,5-disulfonic acid, 4-amino-1,5-naphthalenedisulfonic acid and the like can be mentioned.

<Pigment>
Next, the pigment used in the present invention will be described. The pigment used in the present invention may be a pigment known in the art, and may be an organic pigment or an inorganic pigment.
Organic pigments include azo, anthanthrone, anthrapyrimidine, anthraquinone, isoindolinone, isoindoline, indanthrone, quinacridone, quinophthalone, dioxazine, diketopyrrolopyrrole, thiazine. Examples thereof include indigo type, thioindigo type, pyranthrone type, phthalocyanine type, flavanthron type, perinone type, perylene type, benzimidazolone type and the like. Examples of the inorganic pigments include carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, rouge, iron black, zinc white, navy blue, ultramarine, and the like. These pigments may be used in combination.

When the compound of the present invention is used in combination with a pigment having the same or similar chemical structure as the compound, the non-aggregation property, non-crystallinity, fluidity and the like can be effectively improved. In terms of hue, it is preferably used for yellow to red pigments, and more preferably used for orange to red pigments.

Among these, organic pigments are preferable, red pigments typified by diketopyrrolopyrrole pigments, quinacridone pigments, thiazineindigo pigments, and anthraquinone pigments are more preferable, and diketopyrrolopyrrole pigments are particularly preferable.

Examples of diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 272, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73, brominated diketopyrrolopyrrole and the like. Among them, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264 and brominated diketopyrrolopyrrole are preferred, and C.I. I. Pigment Red 254 is more preferable.

The amount of the compound of the present invention contained in the pigment composition is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the pigment.

The pigment composition can obtain a sufficient dispersing effect even if it is prepared by mixing the pigment and the compound of the present invention. However, if it is prepared by the following method, a better result can be obtained. As a method for preparing a pigment composition other than the mixing method, a dissolver, a high speed mixer, a homomixer, a kneader, a roll mill, an attritor, a sand mill, various pulverizers and the like are used to mechanically prepare the pigment powder and the pigment dispersant powder. , A method of adding a solution containing a pigment dispersant to a suspension system of water or an organic solvent for the pigment, and depositing the pigment dispersant on the surface of the pigment, an organic pigment and a pigment in a solvent having a strong dissolving power such as sulfuric acid. A method in which a dispersant is co-dissolved and co-precipitated with a poor solvent such as water can be used.

(Miniaturization of pigment)
The pigment composition of the present invention, in order to obtain high brightness and high contrast when it is used as a colored composition, by subjecting the pigment particles to finer treatment, such as salt milling or acid pasting treatment, if necessary, to obtain a color filter. It can be preferably used for applications. The average primary particle diameter of the pigment determined by TEM (transmission electron microscope) is preferably 10 nm or more in order to enhance the dispersibility in the pigment carrier. Further, in order to obtain a filter segment having high contrast, it is preferably 50 nm or less.

Salt milling treatment is a process of heating a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or the like while heating. After the kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and it is considered that the pigment is crushed by utilizing the hardness of the inorganic salt during salt milling, which causes an active surface and crystal growth. There is. Therefore, during kneading, crushing of the pigment and crystal growth occur at the same time, and the primary particle size of the obtained pigment differs depending on the kneading conditions.

In order to promote the crystal growth of the pigment by heating, the heating temperature is preferably 35 to 150°C. The kneading time of salt milling is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milled pigment and the cost required for salt milling.

By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution. In particular, it is preferable to use a dye derivative together.

As the water-soluble inorganic salt used for salt milling, sodium chloride, barium chloride, potassium chloride, sodium sulfate or the like can be used, but sodium chloride (salt) is preferable from the viewpoint of cost. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1200 parts by mass, based on the total weight of the pigment (100% by weight).

The water-soluble organic solvent has a function of wetting 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 used. However, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety, because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on the total weight of the pigment (100% by weight).

When the pigment composition is subjected to the salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and natural resin, modified natural resin, synthetic resin, synthetic resin modified with natural resin, and the like can be used. The resin used is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the above organic solvent. The amount of the resin used is preferably in the range of 2 to 200% by weight based on the total weight of the pigment (100% by weight).

When the pigment composition is subjected to the salt milling treatment, a dye derivative may be added if necessary. As the dye derivative, a compound in which an organic pigment has a base skeleton and a basic group, an acidic group, or a phthalimidomethyl group is introduced into the organic pigment by a known method can also be used. The organic pigments are specifically quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, etc. Are listed. Further, a light yellow aromatic polycyclic compound such as a phthalimide-based, naphthalene-based, naphthoquinone-based, anthracene-based or anthraquinone-based compound, which is not generally called a dye, is also included. As the dye derivative, JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and JP-A-06- Those described in 306301, JP 2001-220520 A, JP 2003-238842 A, etc. can be used, and these can be used alone or in combination of two or more kinds.

The amount of the dye derivative used is preferably in the range of 2 to 200% by weight based on the total weight of the pigment (100% by weight).

<Coloring composition>
The coloring composition of the present invention contains a coloring agent containing a pigment composition comprising a compound represented by the general formula (1) or (2) of the present invention (including a pigment as necessary), and an organic solvent, and is required. Depending on the requirement, a binder resin, a dispersion aid, and a dye other than the colorant may be included.

<Binder resin>
The binder resin contained in the coloring composition of the present invention disperses the pigment composition, and examples thereof include conventionally known thermoplastic resins and thermosetting resins.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin. , Polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

When used as a color filter, a resin having a spectral 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 is preferable. When used in the form of an alkali-developing colored resist, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. Further, in order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can be used.

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or Examples thereof include isobutylene/(anhydrous) maleic acid copolymer. Above all, at least one resin selected from an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group is preferably used because it has high heat resistance and transparency.

As the energy ray curable resin having an ethylenically unsaturated active double bond, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group is reactively substituted with an isocyanate group, an aldehyde group, an epoxy group or the like. A resin in which a photo-crosslinkable group such as a (meth)acryloyl group or a styryl group is introduced into the polymer by reacting a (meth)acrylic compound having a group or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth)acrylic compound having a hydroxyl group such as hydroxyalkyl (meth)acrylate. It is also used.

A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable for color filter applications.

The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth) (Meth)acrylates such as acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate,
Alternatively, (meth)acrylamide, such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine. Styrenes such as acrylamides, styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether, fatty acid vinyl such as vinyl acetate or vinyl propionate The kind is mentioned.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide. Coumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4- Phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide Examples include N-substituted maleimides such as hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin. Among them, epoxy resin and melamine resin are more preferably used from the viewpoint of improving heat resistance.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, and more preferably in the range of 7,000 to 50,000 in order to disperse the pigment composition preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw/Mn is preferably 10 or less.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are the gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, four separation columns are connected in series, and the packing material is Tosoh stock in order. It is a polystyrene-equivalent molecular weight measured by using "TSK-GEL SUPER H5000", "H4000", "H3000", and "H2000" manufactured by the company and using tetrahydrofuran as a mobile phase.

When the binder resin is used for a color filter, a carboxyl group acting as an alkali-soluble group during adsorption to the pigment composition and development, an aliphatic group and an aromatic group acting as an affinity group for the pigment composition carrier and solvent are used. The balance of the groups is important for the dispersibility, developability and durability of the pigment composition, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH/g. When the acid value is less than 20 mgKOH/g, the solubility in a developing solution is poor and it may be difficult to form a fine pattern. If it exceeds 300 mgKOH/g, the fine pattern may not remain in the development.

The binder resin can be used in an amount of 20 to 500 mass% based on the total mass of the pigment composition. If it is less than 20% by mass, the film-forming property and various resistances are insufficient, and if it is more than 500% by mass, the pigment concentration is low and the color characteristics may not be exhibited.

<Organic solvent>
In the coloring composition of the present invention, the pigment composition is sufficiently dispersed in the pigment composition carrier and coated on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. An organic solvent can be included to facilitate formation. The organic solvent is selected in consideration of good coatability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate and 1,4-dioxane. , 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene , O-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol Monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol Dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl Examples thereof include cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester.

Among them, the solubility of each component of the coloring composition, and good coating properties, such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Aromatic alcohols such as glycol acetates and benzyl alcohol, and ketones such as cyclohexanone are preferably used.

These organic solvents can be used alone or in combination of two or more. In addition, the organic solvent can adjust the viscosity of the coloring composition to an appropriate value and form a filter segment having a desired uniform film thickness. Therefore, based on the total mass of the pigment composition (100 mass %), 500 to 4000 can be used. It is preferably used in an amount of% by weight.

<Dispersion aid>
When the pigment composition is dispersed in the pigment composition carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment composition and has a large effect of preventing re-aggregation of the pigment composition after dispersion. Therefore, the dispersion aid is used to disperse the pigment composition in the pigment composition carrier. When the coloring composition is used, a color filter having high spectral transmittance (luminance) can be obtained.

(Dye derivative)
As the dye derivative used in the present invention, a compound having an organic pigment as a base skeleton and a basic group, an acidic group, or a phthalimidomethyl group introduced into the organic pigment by a known method can also be used. Specific examples of the organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzimidazolone pigments. Are listed. Further, a light yellow aromatic polycyclic compound such as a phthalimide-based, naphthalene-based, naphthoquinone-based, anthracene-based or anthraquinone-based compound, which is not generally called a dye, is also included. As the dye derivative, JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and JP-A-06- Those described in 306301, JP 2001-220520 A, JP 2003-238842 A, etc. can be used, and these can be used alone or in combination of two or more kinds.

From the viewpoint of improving the dispersibility of the pigment composition, the amount of the dye derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably 1% by weight or more, based on the total amount of the pigment composition (100% by weight). It is preferably at least 3% by weight. From the viewpoint of heat resistance and light resistance, the total amount of the pigment composition is 100% by weight as a standard (40% by weight or less), and more preferably 35% by weight or less.

(Resin type dispersant)
The resin-type dispersant has a site having an affinity for the pigment composition, which has a property of adsorbing to the pigment composition, and a site having compatibility with the pigment composition carrier. It serves to stabilize the dispersion in the carrier. Specific examples of the resin-type dispersant 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 alkylamine salts. , Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyester having a free carboxyl group, and salts thereof Water-soluble dispersants such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resins, water-soluble polymer compounds, polyester systems, modified polyacrylate systems, ethylene oxide/propylene oxide addition compounds, phosphoric acid ester systems and the like are used, and these can be used alone or in combination of two or more, It is not necessarily limited to these.

Among the above dispersants, the acid-base interaction with the pigment dispersant of the present invention is utilized to the maximum, the viscosity of the coloring composition becomes low with a small addition amount, and a high spectral transmittance is exhibited, A polymer dispersant having a basic functional group is more preferable. In particular, a graft copolymer containing an amino group, a basic functional group-containing acrylic block copolymer having an amino group in a side chain, and a urethane polymer dispersant are preferable.

Examples of commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 6919, or Anti-Terra-U, 203, 204,. Alternatively, BYK-P104, P104S, 220S, 21116, or Lactimon, Lactimon-WS, Bykumen, or the like, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000 manufactured by Nippon Lubrizol Co., Ltd. , 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, BASF EFKA-46, 47, 47, etc. 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Azino PA111, PB711, PB821, PB822 manufactured by Ajinomoto Fine-Techno. , PB824 and the like.

(Surfactant)
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate. Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, styrene-acrylic acid copolymer monoethanolamine, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkyl betaines such as alkyldimethylaminoacetic acid betaine and alkyl imidazolines, and these may be used alone or in combination of two or more. Although they can be used as a mixture, they are not necessarily limited thereto.

The amount of the resin-type dispersant and the surfactant to be added is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the pigment composition (100% by weight). %. If the content of the resin type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the effect of the addition, and if the content is more than 55% by weight, the excess dispersant adversely affects the dispersion. May be affected.

<Colorants (other pigments)>
In the coloring composition of the present invention, the following pigments or dyes may be used in combination as colorants within the range that does not impair the effects of the present invention, for example, for adjusting chromaticity.

For example, C.I. I. Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, Mention may be made of red pigments such as 280, 281, 282, 283, 284, 285, 286, 287 or brominated diketopyrrolopyrrole pigments. Examples of red dyes include xanthene-based, azo-based (pyridone-based, barbituric acid-based, metal complex-based, etc.), disazo-based, anthraquinone-based, cyanine-based, and the like. A xanthene dye is particularly preferable. Specifically, the xanthene-based oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, and CI Solvent. Red 44, CI Solvent Red 45, CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72 , CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, C I Solvent Violet 2, CI Solvent Violet 10, etc.
Examples of the xanthene-based acid dye include C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B, Acid Rhodamine G, C.I. I. Acid Violet 9 etc.
Examples of the xanthene-based basic dye include C.I. I. Basic Red 1, C.I. I. Basic Red 8, C.I. I. Basic Violet 10 and the like.

Also, C.I. I. Pigment Orange 38, 43, 71, or 73 or an orange pigment such as C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination. Examples of orange or yellow dyes include quinoline-based, azo-based (pyridone-based, barbituric acid-based, metal complex-based, etc.), disazo-based, and methine-based dyes.

Preferred dyes to be used in combination include azo dyes, naphtholazo dyes, diketopyrrolopyrrole dyes, anthraquinone dyes, quinophthalone dyes, and perylene dyes from the viewpoint of color characteristics. Specifically, C.I. I. Pigment Red 254, brominated diketopyrrolopyrrole pigment, C.I. I. Pigment Yellow 138, 139, 150, 185.

<Method for producing colored composition>
The coloring composition of the present invention is obtained by mixing the pigment composition with an organic solvent and, if necessary, a binder resin, a dispersion aid, or other dyes, and then kneader, two-roll mill, three-roll mill, ball mill, It can be finely dispersed and manufactured using various dispersing means such as a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. In the coloring composition of the present invention, the pigment composition and other dyes may be simultaneously dispersed in the pigment composition carrier, or the pigment composition carrier may be separately dispersed and mixed.

<Photosensitive coloring composition>
The coloring composition of the present invention can be used as a photosensitive coloring composition by further adding a photopolymerizable monomer.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be added to the photosensitive coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays or heat to produce a transparent resin. A mixture of two or more species can be used.

Examples of the monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. , Cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di( (Meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di (Meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, methylolated melamine Various (meth)acrylic acid esters, epoxy (meth)acrylates, urethane acrylates and other acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol triester Examples thereof include, but are not limited to, vinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.
These photopolymerizable compounds may be used alone or in combination of two or more at an arbitrary ratio as needed.

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight, more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability, with respect to 100 parts by weight of the pigment composition. preferable.

<Photopolymerization initiator>
The photosensitive coloring composition of the present invention may be solvent-developed or alkali-developed by adding a photopolymerization initiator if necessary in order to cure the composition by ultraviolet irradiation and to form a filter segment by a photolithography method. Mold-type photosensitive coloring composition can be prepared.

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 Acetophenone compounds such as -[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′. -Methyldiphenyl sulfide, or a benzophenone compound such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 A thioxanthone compound such as diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-( p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6- Bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4- Triazine-based compounds such as trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime) ], or oxime ester compounds such as O-(acetyl)-N-(1-phenyl-2-oxo-2-(4′-methoxy-naphthyl)ethylidene)hydroxylamine; bis(2,4,6-trimethyl) Benzoyl)phenylphosphine oxide, phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds Compounds; imidazole compounds, or titanocene compounds are used.
These photopolymerization initiators can be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

The content of the photopolymerization initiator is preferably 2 to 200 parts by weight, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability, with respect to 100 parts by weight of the pigment composition.

<Sensitizer>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, etc., 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives. , Polymethine dyes such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonole derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester , Acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3′, or 4,4′. -Tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned.
These sensitizers may be used alone or in a mixture of two or more at an arbitrary ratio, if necessary.

More specifically, Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Tadaburo Ikemori et al. Examples of the sensitizer include those described in "Special Function Material" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may be contained.

The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the photosensitive coloring composition, and 5 to 50 from the viewpoint of photocurability and developability. More preferably, it is parts by weight.

<Amine compound>
Further, the photosensitive coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine and the like can be mentioned.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the photosensitive coloring composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used together. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight, based on the total weight of the photosensitive coloring composition (100% by weight).

Particularly preferred as a leveling agent is one of so-called surfactants having a hydrophobic group and a hydrophilic group in the molecule, which has low hydrophilicity even though it has a hydrophilic group, and when added to a photosensitive coloring composition. , Whose surface tension lowering ability is low, and which has good wettability to a glass plate in spite of its low surface tension lowering ability, is useful, and does not cause defects in the coating film due to foaming. Those that can sufficiently suppress the charging property in the amount can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. It may be of a linear block copolymer type in which alternately and repeatedly bonded. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -207, but not limited thereto.

Anionic, cationic, nonionic or amphoteric surfactants can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Examples of anionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, and alkyldiphenyletherdisulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples thereof include esters.

Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate. Examples thereof include polyethylene glycol monolaurate and the like; alkylbetaine such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based or silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the photosensitive coloring composition of the present invention may contain a curing agent, a curing accelerator, etc., if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited to these, and thermosetting resins Any curing agent may be used as long as it can react with. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferable. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl). -N,N-dimethylbenzylamine etc.), quaternary ammonium salt compound (eg triethylbenzylammonium chloride etc.), blocked isocyanate compound (eg dimethylamine etc.), imidazole derivative bicyclic amidine compound and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- Ethyl-4-methylimidazole etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S-triazine derivatives (eg 2,4-diamino-6). -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine/isocyanuric acid adduct) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other additive components>
The photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time. Further, an adhesion improver such as a silane coupling agent may be contained in order to improve the adhesion to the transparent substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the colorant.

Examples of the adhesion improver include vinyl silanes such as vinyl tris(β-methoxyethoxy)silane, vinyl ethoxy silane and vinyl trimethoxy silane, (meth)acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β-(3, 4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(amino Ethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples of the silane coupling agent include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the photosensitive coloring composition.

<Removal of coarse particles>
The colored composition and the photosensitive colored composition of the present invention are coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0. It is preferable to remove coarse particles of 5 μm or more and dust mixed therein. As described above, it is preferable that the coloring composition and the photosensitive coloring composition do not substantially contain particles of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, in which the red filter segment contains a coloring composition or a photosensitive coloring composition containing the compound of the present invention. Formed from.

The green filter segment can be formed by using an ordinary green coloring composition containing a green pigment and a pigment carrier or a green photosensitive coloring composition. Examples of green pigments include C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like are used. A blue pigment such as aluminum phthalocyanine can also be used.

Further, a yellow pigment can be used in combination with the green coloring composition or the green photosensitive coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, There may be mentioned yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Further, a salt-forming compound of a basic dye or an acid dye which exhibits a yellow color can be used in combination.

The blue filter segment can be formed by using an ordinary blue coloring composition or a blue photosensitive coloring composition containing a blue pigment and a pigment carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64 and the like are used. Further, a purple pigment can be used in combination with the blue coloring composition or the blue photosensitive coloring composition. Examples of purple pigments that can be used in combination include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments. Further, a salt-forming compound of a basic dye or an acid dye that exhibits blue or purple can also be used. When a dye is used, a xanthene dye is preferable in terms of heat resistance and brightness.

(Color filter manufacturing method)
The color filter of the present invention can be manufactured by a printing method or a photolithography method.
Since the formation of the filter segment by the printing method can be patterned by simply printing and drying the coloring composition prepared as the printing ink, the manufacturing method of the color filter is low cost and excellent in mass productivity. Furthermore, the development of printing technology enables printing of fine patterns having high dimensional accuracy and smoothness. For printing, it is preferable that the composition is such that the ink does not dry and solidify on the printing plate or on the blanket. In addition, it is important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When the filter segment is formed by a photolithography method, the coloring composition prepared as the solvent-developing or alkali-developing colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, it is applied 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, which is provided in contact or non-contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying a 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 carried out if necessary. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above printing method.

Upon development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the ultraviolet exposure sensitivity, after coating and drying the above-mentioned colored resist, a water-soluble or alkali water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated and dried to form a film which prevents polymerization inhibition by oxygen. After that, it is possible to perform ultraviolet exposure.

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, and the coloring composition or the photosensitive coloring composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by utilizing a transparent conductive film formed on a substrate to form each color filter segment on the transparent conductive film by electrophoretic deposition of colloidal particles. .. The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet and the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on the transparent substrate or the reflective substrate. The black matrix may be, but is not limited to, chromium, a chromium/chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed. It is also possible to previously form a thin film transistor (TFT) on the transparent substrate or the reflective substrate, and then form each color filter segment. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as needed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the examples,% and parts mean% by mass and parts by mass.

(Weight average molecular weight of binder resin)
In the gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, four separation columns were connected in series, and the packing material was "TSK-GEL SUPER H5000", "H4000", "H3000" manufactured by Tosoh Corporation in order. , And “H2000”, and the polystyrene-equivalent molecular weight was measured by using tetrahydrofuran as a mobile phase.

(LC-MASS (mass spectrometry))
Device: Nippon Waters Co., Ltd. UPLC H-Class/XevoTQD
Column: Symmetry C18 5micron (Japan Waters Co., Ltd.)
Eluent:
(A) 0.05 mol/l CH ₃ COONH ₄ aqueous solution (B) DMF
Gradient condition: (A):(B)=87:13 (volume ratio) and hold for 1 minute, then (A):(B)=87:13 to (A):(B)=5 over 5 minutes. :95 (volume ratio), and then hold for 3 minutes at (A):(B)=5:95 (volume ratio).
Flow rate: 0.400 ml/min Injection volume: 1 μl
Column temperature: 35°C

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer in a separable four-necked flask, the temperature was raised to 80° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) 20.7. Part, and a mixture of 1.1 parts of 2,2′-azobisisobutyronitrile were added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, dried by heating at 180° C. for 20 minutes to measure the nonvolatile content, and the resin solution synthesized above was adjusted so that the nonvolatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction container equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device in a separable four-necked flask, heated to 80° C., the inside of the reaction container was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis. A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped, and after stirring while injecting dry air for 1 hour, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenzu manufactured by Showa Denko KK) A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropping was completed, the reaction was continued for another hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts 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. Then, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18,000.

<Synthesis of compound>
[Example 1]
(Synthesis of Compound (a-1))
In 36 parts of 30% fuming sulfuric acid, 4.5 parts of C.I. I. Pigment Red 255 was charged at 15° C. or lower. After stirring at 30° C. for 3 hours, 32 parts of chlorosulfonic acid was charged and stirred for 10 minutes, 44.5 parts of thionyl chloride was slowly added dropwise, and the mixture was stirred at 55° C. for 30 minutes. The reaction liquid cooled to room temperature was poured into 750 parts of water and 400 parts of ice, the precipitate was filtered and washed twice with 1000 parts of ice water to obtain a chlorosulfonyldiketopyrrolopyrrole presscake. 5 parts of triethylamine was put into 200 parts of water and 15 parts of taurine, and then this presscake was put. The mixture was warmed to 80° C., allowed to stir for 3 hours, allowed to cool to room temperature and then added dropwise to 500 parts cold methyl ethyl ketone (MEK) over 30 minutes. The precipitated compound was filtered, washed with 450 parts of cold MEK and dried at 80° C. to obtain 9.9 parts of compound (a-1) represented by A1. When the obtained compound was subjected to mass spectrometry, it was identified as a compound having a structure represented by A1.

[Example 2]
(Synthesis of Compound (a-2))
In 36 parts of 30% fuming sulfuric acid, 4.5 parts of C.I. I. Pigment Red 255 was charged at 15° C. or lower. After stirring at 30° C. for 3 hours, 32 parts of chlorosulfonic acid was charged and stirred for 10 minutes, 44.5 parts of thionyl chloride was slowly added dropwise, and the mixture was stirred at 55° C. for 30 minutes. The reaction liquid allowed to cool to room temperature was poured into 750 parts of water and 400 parts of ice, the precipitate was filtered and washed twice with 1000 parts of ice water to obtain a chlorosulfonyldiketopyrrolopyrrole presscake. 5 parts of triethylamine was put into 200 parts of water and 15 parts of taurine, and then this presscake was put. The mixture was warmed to 80° C., allowed to stir for 3 hours, allowed to cool to room temperature, then 93 parts of acetamine 24 (10% aqueous solution) was added, the product was filtered, washed with water and dried at 80° C. .. As a result, 15.5 parts of the amine salt (a-2) of A1 was obtained.

[Example 3]
(Synthesis of Compound (a-3))
4.5 parts of C.I. I. Pigment Red 255, 4.94 parts of C.I. I. Pigment Red 272 was replaced by the same procedure as in Example 2 to obtain 15.9 parts of the amine salt (a-3) of compound A2. Mass spectrometry identified A2 as a mixture as shown in the formula.

[Example 4]
(Synthesis of Compound (a-4))
4.5 parts of C.I. I. Pigment Red 255, 6.88 parts of C.I. I. Pigment Red 264 was performed in the same manner as in Example 2 to obtain 17.7 parts of amine salt (a-4) of compound A3. Mass spectrometry identified A3 as a mixture as shown in the formula.

[Example 5]
(Synthesis of Compound (a-5))
4.5 parts of C.I. I. Pigment Red 255 was changed to 6.96 parts of the diketopyrrolopyrrole pigment of the formula (7), and the same procedure as in Example 2 was carried out to obtain 17.8 parts of the amine salt (a-5) of the compound A4. .. Mass spectrometry identified A4 as a mixture as shown in the formula.

Formula (7)

[Example 6]
(Synthesis of Compound (a-6))
4.5 parts of C.I. I. Pigment Red 255, 5.28 parts of C.I. I. Pigment Orange 71 was replaced by the same procedure as in Example 2 to obtain 16.2 parts of the amine salt of compound A5 (a-6). Mass spectrometry identified A5 as a mixture as shown in the formula.

[Example 7]
(Synthesis of compound (a-7))
4.5 parts of C.I. I. Pigment Red 255 was changed to 7.88 parts of the diketopyrrolopyrrole compound of the formula (8) and carried out in the same manner as in Example 2 to obtain 18.7 parts of the amine salt (a-7) of the compound A6. .. Mass spectrometry identified A6 as a mixture as shown in the formula.

Formula (8)

[Example 8]
(Synthesis of Compound (a-8))
4.5 parts of C.I. I. Pigment Red 255 was changed to 5.84 parts of the diketopyrrolopyrrole compound of the formula (9) in the same manner as in Example 2 to obtain 16.8 parts of the amine salt (a-8) of the compound A7. .. Mass spectrometry identified A7 as a mixture as shown in the formula.

Formula (9)

[Example 9]
(Synthesis of Compound (a-9))
4.5 parts of C.I. I. Pigment Red 255 was changed to 6.62 parts of the diketopyrrolopyrrole compound of the formula (10) and carried out in the same manner as in Example 2 to obtain 17.5 parts of the amine salt (a-9) of the compound A8. .. Mass spectrometry identified A8 as a mixture as shown in the formula.

Formula (10)

[Example 10]
(Synthesis of compound (a-10))
In 36 parts of 5% fuming sulfuric acid, 4.5 parts of C.I. I. Pigment Red 255 was charged at 15° C. or lower. After stirring at 15°C for 3 hours, 16 parts of chlorosulfonic acid was charged and stirred for 10 minutes, and further, 23 parts of thionyl chloride was slowly added dropwise, and the mixture was stirred at 55°C for 30 minutes. The reaction liquid cooled to room temperature was poured into 750 parts of ice and 400 parts of water, the precipitate was filtered and washed twice with 1000 parts of ice water to obtain a chlorosulfonyldiketopyrrolopyrrole presscake. 5 parts of triethylamine was put into 200 parts of water and 7.5 parts of taurine, and then this presscake was put. The mixture was warmed to 80° C., allowed to stir for 3 hours, allowed to cool to room temperature, then 93 parts of acetamine 24 (10% aqueous solution) was added, the product was filtered, washed with water and dried at 80° C. .. As a result, 9.9 parts of the amine salt of A9 (a-10) was obtained. Mass spectrometric analysis of A9 identified A9 as a compound of formula.

[Example 11]
(Synthesis of compound (a-11))
The procedure of Example 3 was repeated except that 93 parts of acetamine 24 (10% aqueous solution) was replaced with 12.5 parts of acetamine 86 to obtain 18.4 parts of the amine salt (a-11) of compound A2.

[Example 12]
(Synthesis of compound (a-12))
The same procedure as in Example 3 was repeated except that 93 parts of acetamine 24 (10% aqueous solution) was replaced with 299 parts of 8% aqueous aluminum sulfate solution (liquid sulfuric acid band), and 10 parts of the aluminum salt of compound A2 (a-12) was used. I got 2 copies.

[Example 13]
(Synthesis of compound (a-13))
17.6 parts of the ammonium salt (a-13) of A2 was obtained in the same manner as in Example 3 except that 93 parts of acetamine 24 (10% aqueous solution) was changed to 12.2 parts of tetrabutylammonium bromide. It was

[Examples 14 to 21]
(Synthesis of Compounds (a-14) to (a-21))
The same procedure as in Example 3 was carried out except that 15 parts of taurine were changed to the compounds and amounts shown in Table 1 to obtain amine salts A10 to A17 (a-14) to (a-21). The mixture was identified by mass spectrometry as shown in A10 to A17.
However, Examples 1, 12, and 13 are reference examples.

[Comparative Example 1]
(Synthesis of Compound (b-1))
In 36 parts of 30% fuming sulfuric acid, 4.5 parts of C.I. I. Pigment Red 255 was charged at 15° C. or lower. After stirring at 30° C. for 3 hours, the reaction liquid cooled to room temperature was added dropwise to 1150 parts of cold methyl ethyl ketone (MEK) over 30 minutes. The precipitated compound was filtered, washed twice with 1000 parts of cold MEK, and dried at 80° C. to obtain 7.1 parts of compound (b-1) that was a disulfonate-free form of diketopyrrolopyrrole pigment.

[Comparative example 2]
(Synthesis of compound (b-2))
7.1 parts of the compound obtained in Comparative Example 1 was put into 200 parts of water, 93 parts of acetamine 24 (10% aqueous solution) was added, and the product was filtered, washed with hot water, and dried at 80°C. .. As a result, 12.6 parts of compound (b-2), which is an acetamine salt of a disulfonated diketopyrrolopyrrole pigment, was obtained.

The abbreviations in the table are described.
Acetamine 24: (coconut amine acetate, manufactured by Kao Corporation, alkylamine)
Acetamine 86: (Stearylamine acetate, Kao Corporation, alkylamine)

<Method for producing pigment composition>
[Example 22]
(Production of Pigment Composition R-1)
135 parts of C.I. I. Pigment Red 254, a mixture of 15 parts of the compound (a-3), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were kneaded at 60° C. for 10 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this kneaded product was put into 5000 parts of warm water and stirred for 1 hour while heating at 70° C. to obtain a slurry form. Filtration and washing with water were repeated to remove sodium chloride and diethylene glycol, followed by drying and pulverization to obtain 134 parts of pigment composition R-1.

[Example 23]
(Production of Pigment Composition R-2)
135 parts of C.I. I. Pigment Red 254, except that 15 parts of the compound (a-3) are replaced with 135 parts of the diketopyrrolopyrrole pigment of the formula (7) and 15 parts of the compound (a-5), Pigment Composition R- In the same manner as in 1, 132 parts of Pigment Composition R-2 was obtained.

<Other fine pigment manufacturing methods>
(Production of fine pigment PR254-1)
150 parts of C.I. I. Pigment Red 254, 1500 parts of sodium chloride, and 250 parts of diethylene glycol were kneaded at 60° C. for 10 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this kneaded product was put into 5000 parts of warm water and stirred for 1 hour while heating at 70° C. to obtain a slurry form. Filtration and washing with water were repeated to remove sodium chloride and diethylene glycol, followed by drying and pulverization to obtain 135 parts of fine pigment PR254-1.

(Production of fine pigment PR177-1)
150 parts of dianthraquinone pigment (CI Pigment Red 177), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, the kneaded mixture is poured into warm water, stirred for 1 hour while heating to about 70° C. to form a slurry, which is filtered and washed with water to remove salt and diethylene glycol, and then dried at 80° C. for one day and pulverized. By doing so, 138 parts of anthraquinone-based fine pigment PR177-1 was obtained.

<Method for producing colored composition>
[Example 24]
(Preparation of coloring composition (RP-1))
The mixture having the composition shown below was uniformly stirred and mixed, and was dispersed with Picomill (manufactured by Asada Iron Works Co., Ltd.) for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered with a 5 μm filter to give a colored composition ( RP-1) was prepared.
Fine pigment (PR254-1): 11.0 parts Compound (a-1): 1.0 parts Disperbyk-2000 (NV40%): 20.0 parts Propylene glycol monomethyl ether acetate: 68.0 parts

[Examples 25 to 47, Comparative Examples 3 to 4]
(Preparation of colored composition (RP-2 to 24, 26, 27))
Coloring compositions (RP-2 to RP-2) were obtained in the same manner as the coloring composition (RP-1), except that the fine pigment (PR254-1) and the compound (a-1) were changed to the materials shown in Table 3. 24, 26, 27) were produced.
However, Examples 24, 35 and 36 are reference examples.

[Example 48]
(Preparation of Colored Composition (RP-25))
The mixture having the composition shown below was uniformly stirred and mixed, and was dispersed with Picomill (manufactured by Asada Iron Works Co., Ltd.) for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered with a 5 μm filter to give a colored composition RP-25) was prepared.
Fine pigment (R-1): 12.0 parts Disperbyk-2000 (NV40%): 20.0 parts Propylene glycol monomethyl ether acetate: 68.0 parts

<Evaluation of coloring composition>
The obtained coloring composition was evaluated by the following methods. The results are shown in Table 3.
(Dispersibility: viscosity characteristic)
Regarding the viscosity of the coloring composition, the initial viscosity at 25° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the coloring composition was allowed to stand in a glass container in a hermetically sealed state at 40° C. for 24 hours, and then the viscosity was measured by the same method as above to obtain the viscosity with time.
◯: When the rate of change in viscosity was within ±10% and no sediment was formed.
Δ: When the rate of change in viscosity is within ±10% to 20% and no sediment is formed.
X: When the rate of change in viscosity exceeds ±20%, or when a precipitate is formed even if the rate of change in viscosity is within ±20%.

<Method for producing other colored composition>
(Preparation of other coloring composition (PR177-1P))
A mixture having the composition shown below is uniformly stirred and mixed, and dispersed using a zirconia bead having a diameter of 0.1 mm for 8 hours with a pico mill, and then filtered with a 5 μm filter to prepare a colored composition (PR177-1P). did.
Fine pigment (PR177-1): 12.0 parts Disperbyk-2000 (NV40%): 20.0 parts Propylene glycol monomethyl ether acetate: 68.0 parts

<Method for producing photosensitive coloring composition>
[Example 49]
(Preparation of Photosensitive Coloring Composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a 1 μm filter to prepare a photosensitive coloring composition (RR-1).
Coloring composition (RP-1): 37.8 parts Coloring composition (PR177-1P): 4.2 parts Acrylic resin solution 2: 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) ): 2.8 parts Photoinitiator ("IRGACURE 907" manufactured by BASF): 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Ethylene glycol monomethyl ether Acetate: 39.6 parts

[Examples 50 to 73, Comparative Examples 5 to 6]
(Preparation of Photosensitive Coloring Compositions (RR-2 to 27))
Photosensitization was performed in the same manner as the photosensitive coloring composition (RR-1) except that the coloring composition (RP-1) and the coloring composition (PR177-1P) were changed to the coloring compositions shown in Table 4. Coloring compositions (RR-2) to (RR-27) were prepared.
The blending amounts of the two kinds of coloring compositions were fixed at 42 parts in total, and the ratio was changed so that the chromaticity of x=0.640 and y=0.328 with the C light source when the coating film was formed. did.
However, Examples 49, 60 and 61 are reference examples.

<Evaluation of photosensitive coloring composition>
The obtained photosensitive colored compositions (RR-1 to 27) were evaluated for brightness, contrast ratio, and heat resistance by the following methods. The results are shown in Table 4.

(Brightness Y (C) evaluation)
A 100 mm×100 mm, 0.7 mm thick glass substrate is coated with a photosensitive coloring composition having a film thickness such that x=0.640, y=0.328 in a C light source, dried, and then super-high pressure mercury. UV light of 300 mJ/cm ² was irradiated using a lamp. Furthermore, a red coating film was obtained by heating at 230° C. for 60 minutes. Then, the brightness Y(C) of the obtained coating film was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Regarding the lightness Y(C), it can be said that there is a clear difference if it is 0.2 points or more.

(Evaluation of contrast ratio of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dry coating film of the coloring composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing plate and the polarizing surface of the polarizing plate are parallel to each other, light passes through the polarizing plate, but if the polarizing surface is orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the coloring composition, scattering occurs due to the pigment particles and a part of the plane of polarization is displaced, and when the polarizing plate is parallel, the polarized light is The amount of light that passes through the plate decreases, and when the polarizing plate is orthogonal, some light passes through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plates were parallel and the luminance when the polarizing plates were orthogonal was calculated. When the pigment in the coating film scatters, the brightness in the parallel direction decreases and the brightness in the orthogonal direction increases, so that the contrast ratio decreases.
(Contrast ratio)=(Brightness when parallel)/(Brightness when orthogonal)
A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. At the time of measurement, a black mask having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light. For the contrast ratio measurement, a red coating film obtained by the same method as when evaluating the lightness Y(C) was used.

(Heat resistance evaluation: Observation of foreign matter generation during heating process)
The red coated film substrate obtained by the same method as the evaluation of the brightness Y(C) was reheated at 250° C. for 1 hour, observed with an electron microscope at a magnification of 500, and evaluated according to the following criteria.
◯: Generation of foreign matter has not been confirmed (very good)
Δ: Foreign matter slightly generated (somewhat good)
×: Foreign matter (defective)

From the results of Table 4, it was found that in the formation of color filters, the photosensitive composition using the compound of the present invention was excellent in lightness and contrast, and further excellent in dispersibility and heat resistance. Furthermore, in Examples 70 to 73, it was found that by adding the compound of the present invention during wet pulverization, it was effective in increasing the contrast.

<Production of color filter>
A green photosensitive coloring composition and a blue photosensitive coloring composition used for producing the color filter were produced. For the red color, the photosensitive coloring composition (RR-3) of the present invention was used.

(Preparation of Green Coloring Composition 1 (GP-1))
The mixture having the composition shown below was uniformly stirred and mixed, and was dispersed with a zirconia bead having a diameter of 0.1 mm for 8 hours with a pico mill, and then filtered with a 5 μm filter to give a green colored composition (GP-1). It was made.
Green pigment (CI Pigment Green 36): 6.8 parts Yellow pigment (CI Pigment Yellow 150): 5.2 parts Resin type dispersant ("EFKA4300" manufactured by BASF): 1.0 part Acrylic Resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate: 52.0 parts

(Preparation of Green Photosensitive Coloring Composition (GR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a 1 μm filter to prepare a green photosensitive coloring composition (GR-1).
Green coloring composition (GP-1): 42.0 parts Acrylic resin solution 2: 13.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.): 2.8 parts Photopolymerization initiator (BASF) "Irgacure 907" manufactured by the company): 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Ethylene glycol monomethyl ether acetate: 39.6 parts

(Preparation of Blue Coloring Composition 1 (BP-1))
The mixture having the composition shown below was uniformly stirred and mixed, and using zirconia beads having a diameter of 0.1 mm, the mixture was dispersed for 8 hours with a picomill, and then filtered with a 5 μm filter to obtain a blue colored composition (BP-1). It was made.
Blue pigment (CI pigment blue 15:6): 7.2 parts Purple pigment (CI pigment violet 23): 4.8 parts Resin type dispersant ("EFKA4300" manufactured by BASF): 1.0 Parts Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate: 52.0 parts

(Preparation of Blue Photosensitive Coloring Composition 1 (BR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a 1 μm filter to prepare a blue photosensitive coloring composition (BR-1).
Blue coloring composition (BP-1): 34.0 parts Acrylic resin solution 2: 15.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.): 3.3 parts Photopolymerization initiator (BASF) "Irgacure 907" manufactured by the company): 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Ethylene glycol monomethyl ether acetate: 45.1 parts

A black matrix is patterned on a glass substrate, and the photosensitive coloring composition (RR-3) of the present invention is formed on the substrate with a spin coater to a film thickness such that x=0.640 and y=0.328. It was applied to form a colored film. The coating was irradiated with 300 mJ/cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, after spray-developing with an alkali developing solution consisting of 0.2 wt% sodium carbonate aqueous solution to remove the unexposed portion, it was washed with ion-exchanged water, and this substrate was heated at 230° C. for 20 minutes to obtain a red filter segment. Formed. By the same method, the green photosensitive coloring composition (GR-1) was used to a film thickness such that x=0.300 and y=0.600, and the blue photosensitive coloring composition (BR-1) was used. The color filters were obtained by applying the respective components to a film thickness such that x=0.150 and y=0.060 to form green filter segments and blue filter segments.

By using the photosensitive coloring composition (RR-3) of the present invention, a color filter having high brightness and high contrast could be produced.

Claims (10)

A compound represented by the following general formula (1) or general formula (2).
General formula (1)
[In the general formula (1),
X represents a hydrogen atom, an alkyl group, a phenyl group, a halogen, a thiophenyl group, an N,N-dialkylamino group, a trifluoromethyl group, or a cyano group.
Y ₁ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group which may have a substituent, or a naphthylene group which may have a substituent.
S ₁ represents an alkylamine salt of sulfonic acid.
m represents an integer of 0 or 1, n represents an integer of 1 or 2, and m+n represents an integer of 1 or 2. ]

General formula (2)
[In the general formula (2),
X represents a hydrogen atom, an alkyl group, a phenyl group, a halogen, a thiophenyl group, an N,N-dialkylamino group, a trifluoromethyl group, or a cyano group.
Y ₂ represents a group obtained by removing one hydrogen atom from an alkylene group having 1 to 6 carbon atoms, a group obtained by removing one hydrogen atom from a phenylene group of a phenylene group which may have a substituent, or a substituent. The naphthylene group which may be represented is a naphthylene group having one hydrogen atom removed.
S ₂ represents an alkylamine salt of sulfonic acid.
p represents an integer of 0 or 1, q represents an integer of 1 or 2, and p+q represents an integer of 1 or 2. ]
The compound according to claim 1, which is represented by the general formula (1). The compound according to claim 1, wherein in the general formula (1), Y ₁ is a group selected from the group consisting of an alkylene group having 1 to 6 carbon atoms and a phenylene group which may have a substituent. In the said General formula (1), X is an alkyl group, The compound as described in any one of Claims 1-3. A pigment dispersant containing the compound according to claim 1. A pigment composition containing the pigment dispersant according to claim 5 and a pigment. The pigment composition according to claim 6, wherein the pigment is a diketopyrrolopyrrole pigment. A coloring composition containing a colorant and an organic solvent, wherein the colorant contains the pigment dispersant according to claim 5 or the pigment composition according to claim 6 or 7. The coloring composition according to claim 8, further containing at least one of a photopolymerizable monomer and a photopolymerization initiator. A color filter formed of the coloring composition according to claim 8.