JP2014136784A - Pigment dispersant, and pigment composition, coloring composition and color filter including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersant that exhibits high clarity (lightness) as well as high dispersion performance, and also provide a pigment composition and a coloring composition having excellent clarity (lightness).SOLUTION: This invention provides a pigment dispersant represented by formula (1), where R-Rindependently represent a hydrogen atom, a specific amino group, or a basic group of a specific piperazine-containing group, and at least one of R-Ris a specific amino group, or a basic group of a specific piperazine-containing group.

Description

The present invention relates to a pigment dispersant, a pigment composition, and a coloring composition that are suitably used for printing inks, paints, resin colorants, inkjet inks, color filter inks, and the like. The present invention also relates to a color filter used for a color liquid crystal display device, a color image pickup tube element and the like.

In printing inks, paints, etc., pigments are dispersed in a fine state to exert a high coloring power, and have appropriate properties such as clear color tone and gloss of printed or coated products. Moreover, the labor and energy at the time of manufacturing printing ink and a coating material can be reduced significantly by dispersing a pigment in a stable state. Furthermore, a dispersion in a stable state is generally excellent in storage stability.

However, pigments used in printing inks and paints are often fine particles in order to achieve a clearer color tone, and as a result, the cohesion between the pigment particles becomes stronger and the above-mentioned suitability is imparted. Is often difficult.

In order to solve such problems, it is known to use a pigment dispersant, improve the affinity between the pigment and the vehicle, and stabilize the dispersion. Agents are disclosed.

For example, a pigment derivative in which a functional group such as an acidic group, a basic group, or a phthalimidomethyl group is introduced into an organic pigment has been developed and has been effective. However, since the pigment derivative has an intrinsic strong color because it uses an organic pigment as a base skeleton, it may be significantly restricted when used for a pigment having a different hue.

For example, in systems that disperse highly refined anthraquinone pigment particles, such as printing inks, paints, especially ink jet inks, color filter inks, etc., in order to relieve the strong cohesive force of the pigment particles and obtain stability over time, anthraquinone A pigment dispersant having a skeleton is used. However, although it has excellent dispersibility, it has a problem that sharpness (lightness) is lowered.

  On the other hand, a color filter is a fine filter segment in which two or more kinds of fine band (striped) filter segments having different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass. Are arranged in a constant vertical and horizontal arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are arranged regularly in a predetermined arrangement for each hue. In general, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning liquid crystal in a certain direction is formed thereon. The process of forming these transparent electrodes and alignment films is generally performed at a high temperature of 200 ° C. or higher, and in some cases 230 ° C. or higher. For this reason, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  However, color filters manufactured by the pigment dispersion method generally have a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. Therefore, the light leaks when the light must be blocked, or the transmitted light attenuates when the light must be transmitted. Therefore, the luminance ratio (contrast) on the display device at the time of blocking and transmitting. The problem is that it is low.

  Of the pigments used for color filters, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments and the like have been conventionally used for the production of red color filters. Among these, in particular, anthraquinone pigments have good contrast characteristics when formed into a coating film, and are often used for this purpose.

In recent years, pigments used for color filters have been required to be further improved in sharpness, and it has been difficult to achieve the object with conventionally used anthraquinone pigments.

  In general, many pigments having high coloring power and clear color tone have fine primary particles. In particular, pigments used for color filters are often further refined than conventional pigments in order to improve the contrast of the coating film.

Examples of methods widely used as a pigmentation method for preparing fine pigment particles include solvent salt milling, acid pasting, and dry milling.

Just adding together with commonly used grinding aids such as pigments, inorganic salts and solvents, pigment particles grow at the same time due to heat generated during grinding, solvents added as dispersion aids, etc. By applying mechanical force for a long time, the state of the pigment particles becomes unstable, so even if it takes time and energy to cause a change such as a crystal transition, it can be sufficiently finely pigmented. May not be obtained.

  On the other hand, when the pigment is made finer, the cohesive force between the pigment particles becomes stronger, and the ink and the paint often have high viscosity. In addition, when this dispersion is produced, not only is it difficult to take out the product from the disperser and transfer the product from the disperser to a tank or the like, but in a worse case, gelation occurs during storage and the use becomes difficult. Sometimes.

  In order to solve such problems, it is known to use a pigment dispersant, improve the affinity between the pigment and the vehicle, and stabilize the dispersion. Agents are disclosed. For example, pigment derivatives in which functional groups such as acidic groups, basic groups, and phthalimidomethyl groups are introduced into organic pigments, and resin-type dispersants in which acidic groups and basic groups are introduced into some acrylic polymers and polyester resins have been developed. It is used alone or in combination, and the effect is obtained.

  However, conventional pigment dispersants are excellent in stabilizing the dispersion of pigment particles used in printing inks, paints, especially inkjet inks and color filter inks, but are not always sufficient to achieve high sharpness. It was.

JP-A-5-331398 JP-A-9-272812 Japanese Patent Laid-Open No. 10-245501 JP-A-10-245502 Japanese Patent No. 4396778

An object of this invention is to provide the pigment dispersant which exhibits high sharpness (lightness) in addition to the high dispersion performance currently requested | required of the pigment dispersant.

Another object of the present invention is to provide a pigment composition which is excellent in sharpness (brightness) and exhibits excellent dispersion performance with respect to a pigment carrier.

Furthermore, the present invention has high sharpness (brightness), excellent fluidity, storage stability, and gloss when made into a dry film, and is suitable as a printing ink, paint, inkjet ink, color filter ink, etc. It aims at provision of the coloring composition used for.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.

That is, the embodiment of the present invention relates to a pigment dispersant represented by the following formula (1).

(In the formula, R _{1 to} R ₇ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, a nitro group, an amino group, a cyano group, a sulfonic acid group, a carboxylic acid group, the following formula (2 Or a basic group represented by formula (3), provided that at least one of R _{1 to} R ₇ is a basic group represented by formula (2) or formula (3).

(Where
X is a direct bond, -S -, - O -, - SO 2 -, - CO -, - SO 2 NR -, - NRSO 2 -, - CONR -, - CH 2 NRCOCH 2 NR- , or - (CH ₂ ) _m represents NH-.
m represents an integer of 1 to 10.
R may have a hydrogen atom, an optionally substituted alkyl group having 20 or less carbon atoms, an optionally substituted alkenyl group having 20 or less carbon atoms, or a substituent. An aryl group having 20 or less carbon atoms.
Y may have a direct bond, an alkylene group having 20 or less carbon atoms which may have a substituent, an alkenylene group having 20 or less carbon atoms which may have a substituent, or a substituent. It represents an arylene group having 20 or less carbon atoms, a divalent heterocyclic group which may have a substituent, or —Y ₁ —Y ₂ —Y ₃ —.
Y ₁ and Y ₃ each independently have an alkylene group having 20 or less carbon atoms which may have a substituent, an alkenylene group having 20 or less carbon atoms which may have a substituent, and a substituent. And an arylene group having a carbon number of 20 or less or a divalent heterocyclic group which may have a substituent.
Y ₂ represents a direct bond, —NR—, —O—, —SO ₂ —, —CONR— or —CO—, but when Y ₁ and Y ₃ are the same group, it is not a direct bond. Absent.
R ₈ and R ₉ each independently represents an alkyl group having 30 or less carbon atoms which may have a substituent or an alkenyl group having 30 or less carbon atoms which may have a substituent, and R ₈ And R ₉ may be connected to each other to form a ring.
Z is a direct _{bond, -CH 2 NR'COCH 2 NR '-} , - CH 2 NR'COCH 2 NR'-G -, - NR' -, - NR'-G-CO -, - NR'-G- CONR '-, - NR'-G -SO 2 -, - NR'-G-SO 2 NR' -, - O-G-CO -, - O-G-CONR '-, - SO 2 -, - O -G-SO ₂ - or represents a -O-G-SO ₂ NR'-.
G is an alkylene group having 20 or less carbon atoms that may have a substituent, an alkenylene group having 20 or less carbon atoms that may have a substituent, or a carbon number that may have a substituent. Represents an arylene group having 20 or less, and R ′ represents a hydrogen atom, an alkyl group having 20 or less carbon atoms which may have a substituent, and an alkenyl group having 20 or less carbon atoms which may have a substituent. Alternatively, it represents an aryl group having 20 or less carbon atoms which may have a substituent.
R _{10 to} R ₁₃ each independently represents a hydrogen atom, an alkyl group having 20 or less carbon atoms that may have a substituent, an alkenyl group or substituent having 20 or less carbon atoms that may have a substituent. Represents an aryl group having 20 or less carbon atoms.
R ₁₄ represents a hydrogen atom, an optionally substituted alkyl group having 20 or less carbon atoms, or an optionally substituted alkenyl group having 20 or less carbon atoms. )

Further, in an embodiment of the present invention, R _{1 to} R ₇ are each independently a hydrogen atom or a basic group represented by formula (2) or formula (3), wherein R _{1 to} R ₇ are , Any one to four relates to the pigment dispersant which is a basic group represented by formula (2) or formula (3).

An embodiment of the present invention also relates to a pigment composition comprising the pigment dispersant and a pigment.

In another embodiment of the present invention, the pigment composition is one or more pigments selected from the group consisting of a diketopyrrolopyrrole pigment, a quinacridone pigment, a thiazine indigo pigment, and an anthraquinone pigment. About.

The embodiment of the present invention further relates to the pigment composition further comprising a pigment derivative.

Further, according to an embodiment of the present invention, the pigment derivative has at least one pigment residue selected from the group consisting of diketopyrrolopyrrole, quinacridone, thiazineindigo, benzoisoindole and anthraquinone, a basic group, an acidic group. The pigment composition is a pigment derivative formed by bonding one or more groups selected from the group consisting of a group and a phthalimidomethyl group.

The embodiment of the present invention further relates to the pigment composition further comprising a yellow pigment.

An embodiment of the present invention also relates to a coloring composition comprising the pigment composition and a pigment carrier.

An embodiment of the present invention also relates to a color filter comprising a filter segment formed from the colored composition.

By using the pigment dispersant of the present invention, the pigment can be finely dispersed in a wide range of resins, and non-aggregation, non-crystallinity, fluidity, coating film gloss, sharpness, and storage stability can be achieved. Excellent excellent ink and paint can be easily obtained.

In particular, the pigment dispersant of the present invention has high sharpness (lightness) in red pigment groups such as anthraquinone red pigments, quinacridone red pigments, diketopyrrolopyrrole red pigments, and has an excellent effect on dispersion. Demonstrate.

The pigment dispersant of the present invention is a pigment derivative (Patent Documents 2, 3, and 4) conventionally used in a pigmentation method by a salt milling method of an anthraquinone pigment or a pigmentation method by an acid pasting method of an anthraquinone pigment. It is possible to provide an anthraquinone pigment that is finer than the pigment derivative that has been used (Patent Document 5).

The coloring composition containing the pigment dispersant of the present invention includes gravure inks, various general paints for automobiles, woods, metals, etc., back coat paints for magnetic tapes, radiation cure inks, inks for ink jet printers, and color filters. Can be used for applications such as ink.

First, the pigment dispersant of the present invention will be described.
The pigment dispersant of this invention is represented by Formula (1). In formula (1), R _{1 to} R ₇ are each independently a hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkoxyl group, nitro group, amino group, cyano group, sulfonic acid group, carboxylic acid group, formula ( 2) or a basic group represented by formula (3). However, at least one of R _{1 to} R ₇ is a basic group represented by formula (2) or formula (3).

Here, as a halogen atom in R < ₁ > -R < ₇ > of Formula (1), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

The alkyl group in R _{1 to} R ₇ in the formula (1) is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent, for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group. Group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl Group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methyl Phenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenol Sill group, 3-Nitorofenashiru group.

As an alkoxyl group in R < ₁ > -R < ₇ > of Formula (1), the C1-C30 alkoxyl group which may have a substituent is preferable, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group , Butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group , Octadecyloxy group, ethoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonyl Methyloxy group, N Octylaminocarbonyl methyloxy group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

Examples of the alkyl group having 20 or less carbon atoms which may have a substituent in R in the formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. , Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl Group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl Group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitrophenacyl Etc., and a hydrogen atom is a fluorine atom of these groups, a chlorine atom, a halogen such as bromine atom, a hydroxyl group, a cyano group, a mercapto group, an alkenyl group also include those substituted with an aryl group. Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

Examples of the alkenyl group having 20 or less carbon atoms which may have a substituent in R in the formula (2) include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 1-butenyl group, 2- Examples include butenyl group, 2-pentenyl group, 2-methylallyl group, etc. The hydrogen atom of these groups is halogen such as fluorine atom, chlorine atom, bromine atom, hydroxyl group, cyano group, mercapto group, alkyl group, aryl group, etc. And those substituted by. Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-6.

Examples of the aryl group having 20 or less carbon atoms which may have a substituent in R in the formula (2) include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9- Phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, o-, m- and p-tolyl groups, xylyl group, o-, m -And p-cumenyl group, mesityl group, biphenylyl group, indacenyl group, fluoranthenyl group, acenaphthenyl group, fluorenyl group, anthryl group, phenanthryl group, triphenylenyl group, pyrenyl group, naphthacenyl group, perylenyl group, rubicenyl group, etc. The hydrogen atoms of these groups are halogens such as fluorine atoms, chlorine atoms, bromine atoms, hydroxyl groups, cyano groups, Mercaptoalkyl group, an alkyl group also include those substituted with an alkenyl group. The carbon number is preferably 6 to 10, more preferably 6.

Examples of the alkylene group having 20 or less carbon atoms that may have a substituent in Y in Formula (2) include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, Examples include decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptacamethylene, octadecamethylene, nonadecamethylene, icosamethylene, and the hydrogen atom of these groups is fluorine. Examples include those substituted with halogens such as atoms, chlorine atoms, bromine atoms, hydroxyl groups, cyano groups, mercapto groups, alkyl groups, alkenyl groups, aryl groups, and the like. Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

Examples of the alkenylene group having 20 or less carbon atoms which may have a substituent in Y in the formula (2) include vinylene, propenylene, butenylene, pentenylene, hexenylene, and the hydrogen atom of these groups is a fluorine atom, chlorine Examples thereof include those substituted with halogen such as an atom or bromine atom, a hydroxyl group, a cyano group, a mercapto group, an alkyl group, an alkenyl group, an aryl group. Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-6.

Examples of the arylene group having 20 or less carbon atoms which may have a substituent in Y in the formula (2) include divalent benzene, naphthalene, anthracene, naphthacene, pyrene, phenanthrene, indene, azulene, perylene, and fluorene. Residues are mentioned, and those in which the hydrogen atom of these groups is substituted with halogen such as fluorine atom, chlorine atom, bromine atom, hydroxyl group, cyano group, mercapto group, alkyl group, alkenyl group, aryl group, etc. It is done. The carbon number is preferably 6 to 10, more preferably 6.

The divalent heterocyclic group which may have a substituent in Y in the formula (2) is a divalent heterocyclic ring containing a non-carbon atom such as a nitrogen atom, oxygen atom or sulfur atom as a constituent atom. It means a residue, which may or may not have aromaticity, and may be a single ring or a condensed ring.
Specifically, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indole, indazole, Examples include divalent residues such as purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, furazane, and phenoxazine. In which the hydrogen atom of the group is substituted by halogen such as fluorine atom, chlorine atom, bromine atom, hydroxyl group, cyano group, mercapto group, alkyl group, alkenyl group, aryl group, etc. It is below.

In Y ₁ and Y ₃ , an optionally substituted alkylene group having 20 or less carbon atoms, an optionally substituted alkenylene group having 20 or less carbon atoms, or a substituent may be present. The arylene group having a good carbon number of 20 or less or the divalent heterocyclic group which may have a substituent has the same meaning as in Y.

The alkyl group having 30 or less carbon atoms which may have a substituent in R ₈ and R ₉ in formula (2) is an alkyl group having 20 or less carbon atoms which may have a substituent in R. In addition, an alkyl group having 21 to 30 carbon atoms which may have a substituent is mentioned. Carbon number becomes like this. Preferably it is 1-25, More preferably, it is 1-20.

The alkenyl group having 30 or less carbon atoms which may have a substituent in R ₈ and R ₉ in Formula (2) is an alkenyl group having 20 or less carbon atoms which may have a substituent in R. In addition, the C21-30 alkenyl group which may have a substituent is mentioned. Carbon number becomes like this. Preferably it is 2-25, More preferably, it is 2-20.

R ₈ and R _{9 in} the formula (2) may be connected to each other to form a ring (a heterocycle containing a nitrogen atom), but may or may not have aromaticity.
Specific examples include phenoxazine, pyrrole, imidazole, pyrazole, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, piperidine, piperazine, morpholine, indole, indazole, purine, carbazole, carboline, perimidine, phenoxazine and the like. And those in which the hydrogen atom of these groups is substituted with a halogen such as a fluorine atom, a chlorine atom or a bromine atom, a hydroxyl group, a cyano group, a mercapto group, an alkyl group, an alkenyl group or an aryl group.

The alkylene group having 20 or less carbon atoms that may have a substituent in G in Formula (1) has the same meaning as the alkylene group that has 20 or less carbon atoms that may have a substituent in Y. . Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

The alkenylene group having 20 or less carbon atoms which may have a substituent in G in formula (1) has the same meaning as the alkenylene group having 20 or less carbon atoms which may have a substituent in Y. Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-6.

The arylene group having 20 or less carbon atoms which may have a substituent in G in Formula (1) has the same definition as the arylene group having 20 or less carbon atoms which may have a substituent in Y. The carbon number is preferably 6 to 10, more preferably 6.

The alkyl group having 20 or less carbon atoms which may have a substituent in R ′ in formula (1) has the same meaning as the alkyl group having 20 or less carbon atoms which may have a substituent in R. is there. Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

The alkenyl group having 20 or less carbon atoms which may have a substituent in R ′ in formula (1) has the same meaning as the alkenyl group having 20 or less carbon atoms which may have a substituent in R. . Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-6.

The aryl group having 20 or less carbon atoms that may have a substituent in R ′ in formula (1) has the same meaning as the aryl group that has 20 or less carbon atoms that may have a substituent in R. is there. The carbon number is preferably 6 to 10, more preferably 6.

As the alkyl group having 20 or less carbon atoms which may have a substituent in R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in the formula (3), the carbon number which may have a substituent in R is It is synonymous with 20 or less alkyl groups. Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

The alkenyl group having 20 or less carbon atoms which may have a substituent in R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in Formula (3) has 20 carbon atoms which may have a substituent in R. It is synonymous with the following alkenyl groups. Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-6.

As the aryl group having 20 or less carbon atoms which may have a substituent in R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in formula (3), the number of carbons which may have a substituent in R Is synonymous with 20 or less aryl groups. The carbon number is preferably 6 to 10, more preferably 6.

The alkyl group having 20 or less carbon atoms which may have a substituent in R ₁₄ in Formula (3) has the same meaning as the alkyl group having 20 or less carbon atoms which may have a substituent in R. is there. Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

The alkenyl group having 20 or less carbon atoms which may have a substituent in R ₁₄ in formula (3) has the same meaning as the alkenyl group having 20 or less carbon atoms which may have a substituent in R. . Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-6.

In an embodiment of the present invention, the preferred pigment dispersant, R ₁ to R ₇ are each independently a basic group represented by hydrogen or the formula (2) or formula (3), R ₁ ~ Any one to four of R ₇ are the basic groups represented by formula (2) or formula (3).

As a particularly preferred embodiment of the pigment dispersant of the present invention, R _{1 to} R ₇ in formula (1) are a hydrogen atom, a basic group represented by formula (2) or formula (3), Any one of R _{1 to} R ₇ is a basic group represented by the formula (2), and in the formula (2), X is —S—, —SO ₂ NR—, —CONR— or —CH _2. NRCOCH ₂ NR—, R is a hydrogen atom, Y is an alkylene group having 20 or less carbon atoms, or —Y ₁ —Y ₂ —Y ₃ —, and Y ₁ and Y ₃ are An alkylene group having 20 or less carbon atoms or an arylene group having 20 or less carbon atoms, Y ₂ is —CONR—, R ₈ and R ₉ are alkyl groups having 30 or less carbon atoms, and in formula (3) , Z is —CH ₂ NR′COCH ₂ NR′—G—, and G is an alkylene group having 20 or less carbon atoms. And R ′ is a hydrogen atom, R _{10 to} R ₁₃ are hydrogen atoms, and R ₁₄ is a hydrogen atom.

The aminoanthraquinone pigment dispersant of the present invention can be synthesized through several synthetic routes.

For example, the aminoanthraquinone pigment dispersant in which X in the formula (2) is —SO ₂ — or —SO ₂ NH— and Y is — (CH ₂ ) _m1 — is, for example, an aminoanthraquinone represented by the formula (4). In the usual manner, chlorosulfonation with chlorosulfuric acid was carried out to obtain aminoanthraquinonesulfonyl chloride in which 1 to 4 chlorosulfonyl groups were bonded on the benzene ring of aminoanthraquinone, and this was converted to HN (R ₈ ) (R ₉ ) or NH ₂ — (CH ₂ ) _m1 —N (R ₈ ) (R ₉ ) can be produced by reacting with an amine and heating (where m1 is an integer of 1 to 20). Represent).

The aminoanthraquinone pigment dispersant in which X in Formula (2) is —SO ₂ NH— and Y is —C ₆ H ₄ —CO— is obtained, for example, by reacting the aminoanthraquinonesulfonyl chloride with an aminobenzoic acid ester. The product can be produced by reacting (amidating) with an amine represented by HN (R ₈ ) (R ₉ ) and heating.

The aminoanthraquinone pigment dispersant in which X in the formula (2) is —S— and Y is — (CH ₂ ) _m2 — is, for example, an aminobromoanthraquinone represented by the formula (5) is HS— (CH ₂ ) _m2 —. It can be produced by reacting with an amine represented by N (R ₈ ) (R ₉ ) (where m2 represents an integer of 1 to 20).

The aminoanthraquinone pigment dispersant in which X in the formula (2) is —CH ₂ NHCOCH ₂ NH— and Y is — (CH ₂ ) _m3 — reacts the aminoanthraquinone represented by the formula (4) with chloroacetamide and paraformaldehyde. To obtain chloroacetamidomethyltrans-type aminoanthraquinone having 1 to 4 chloroacetamidomethyl groups bonded on the benzene ring of aminoanthraquinone, which is NH ₂ — (CH ₂ ) _{m 3} —N (R ₈ ) (R ₉ ) can be produced by reacting with an amine represented by the formula (3) (wherein m3 represents an integer of 1 to 20).

In the formula (2), an aminoanthraquinone pigment dispersant in which X is a direct bond or — (CH ₂ ) _m4 NH— and Y is — (CH ₂ ) _m5 — is obtained by _converting an aminoanthraquinone represented by the formula (4) into aluminum chloride. in the presence of a Lewis acid _{like, Hal- (CH 2) m4 -N} (R 8) (R 9) or _{Hal- (CH 2) m4 NH- (} CH 2) m5 -N (R 8) (R 9 ) (Wherein m4 represents an integer of 1 to 10, m5 represents an integer of 1 to 20, and Hal represents a halogen).

The aminoanthraquinone in which Z in the formula (3) is —SO ₂ — is, for example, chlorosulfonated from the aminoanthraquinone represented by the formula (4) using chlorosulfuric acid by a conventional method to obtain 1 to 4 chlorosulfonates. An aminoanthraquinonesulfonyl chloride having a sulfonyl group bonded on the benzene ring of aminoanthraquinone can be obtained, and this can be produced by reacting with an unsubstituted or substituted piperazine.

The aminoanthraquinone pigment dispersant in which the —Z— group in the formula (3) is —CH ₂ NHCOCH ₂ NH— (CH ₂ ) _m6 — or —CH ₂ NHCOCH ₂ NH— is an aminoanthraquinone represented by the formula (4) The pigment is reacted with chloroacetamide and paraformaldehyde to give chloroacetamidomethylaminoanthraquinone having 1-4 chloroacetamidomethyl groups attached on the benzene ring of aminoanthraquinone, which is NH _2- (CH ₂ ) _m6- (unsubstituted or substituted piperazino group) or NH ₂ - (substituted or unsubstituted piperazino group) is reacted with an amine represented can be produced by in (here, m6 represents an integer of 1 to 20).

The aminoanthraquinone pigment dispersant in which the —Z— group in the formula (3) is —NH— (CH ₂ ) _m7 —SO ₂ — is an aminobromoanthraquinone represented by the formula (5) in the presence of a catalyst such as palladium acetate. Can be prepared by reacting with an amine represented by NH ₂ — (CH ₂ ) _m7 —SO ₂ — (unsubstituted or substituted piperazino group) (where m7 represents an integer of 1 to 20). .

Examples of amines used in the above reaction are shown below. For example, dimethylamine, diethylamine, N-ethylisopropylamine, N-methylbutylamine, N-methylisobutylamine, N-butylethylamine, N-tert-butylethylamine, diisopropylamine, dipropylamine, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N-methyloctadecylamine, didecylamine, diallylamine N-ethyl-1,2-dimethylpropylamine, N-methylhexylamine, 2-hydroxymethylaminoethanol, dioleylamine, distearylamine, , N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N , N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-dimethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N , N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-di Stearylaminoethylamine, N, -Dioleoylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidine Methanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-pyridinemethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N -Aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopent Rupiperajin, 1-amino-4-methylpiperazine, 1-cyclopentyl piperazine is diethylaminoethanethiol etc.

Specific examples of the pigment dispersant of the present invention include the following, but the present invention is not limited to these (where Me represents a methyl group and Et represents an ethyl group).

Next, the pigment composition of the present invention will be described.
The pigment composition of the present invention contains a pigment and the pigment dispersant of the present invention.

As the pigment contained in the pigment composition of the present invention, various commercially available organic pigments or inorganic pigments can be used.

Examples of organic pigments include azo, anthanthrone, anthrapyrimidine, anthraquinone, isoindolinone, isoindoline, indanthrone, quinacridone, quinophthalone, dioxazine, diketopyrrolopyrrole, Organic pigments such as thiazine indigo, thioindigo, pyranthrone, phthalocyanine, flavanthrone, perinone, perylene, benzimidazolone and the like can be mentioned. Examples of the inorganic pigment include carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, dial, iron black, zinc white, bitumen, and ultramarine blue. These pigments may be used in combination.

Among pigments, non-aggregation, non-crystallinity, fluidity, and the like are significant for pigments having the same or similar chemical structure as the pigment dispersant of the present invention. In terms of hue, it is preferably used for yellow to red pigments, and more preferably for orange to red pigments.

In particular, the pigment dispersant of the present invention is preferably used for red pigments represented by anthraquinone red pigments, diketopyrrolopyrrole red pigments, quinacridone red pigments, and thiazine indigo red pigments.

0.1-30 weight part is preferable with respect to 100 weight part of pigments, and, as for the quantity of the pigment dispersant of this invention contained in a pigment composition, 1-20 weight part is more preferable. When the content of the pigment dispersant of the present invention is less than 0.1 parts by weight, it is difficult to obtain the effect of the added pigment dispersant, and when it is more than 30 parts by weight, the effect of the added amount is obtained. In addition, the difference between the physical properties of the obtained pigment composition and the physical properties of the pigment alone increases, and there may be problems in practical quality when used in inks and paints.

When the pigment composition of the present invention is mechanically kneaded with the mixture of the pigment and the pigment dispersant of the present invention in the presence of a water-soluble inorganic salt or a water-soluble inorganic salt and a solvent, pigment crystal growth prevention and particle stability are achieved. Due to the effect, fine and sized particles can be easily obtained. As a kneading machine used at this time, a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or the like can be used, but is not limited thereto. Further, coarse pigments may be used as the pigment. The proportion of the pigment and the pigment dispersant of the present invention is preferably 0.1 to 30 parts by weight of the pigment dispersant of the present invention with respect to 100 parts by weight of the pigment, more preferably 0.5 to 25 parts by weight. .

Examples of water-soluble inorganic salts used for mechanical kneading include, but are not limited to, sodium chloride, potassium chloride, mirabilite, and the like. The water-soluble inorganic salt is preferably used in an amount of 100 to 2000 parts by weight, more preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment. Further, the solvent used for mechanical kneading is not particularly limited, but a solvent having a high boiling point is preferable from the viewpoint of safety because the temperature rises during the kneading and the solvent is easily evaporated. Examples include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tri Ethylene 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, low molecular weight polypropylene A glycol etc. can be mentioned. The solvent is preferably used in an amount of 10 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

In addition, the pigment dispersant of the present invention can be used to reduce the viscosity even when it is added when the pigment particles are refined. However, the pigment dispersant of the present invention is added to the refined pigment later and mixed with powder. Then, a higher effect can be obtained. Furthermore, in order to effectively reduce the viscosity, the pigment dispersant of the present invention is mechanically mixed using a dissolver, a high speed mixer, a homomixer, a kneader, a roll mill, an attritor, a sand mill, various pulverizers, and the like. Or by adding a solution containing the pigment dispersant of the present invention to a suspension system of pigment water or an organic solvent and depositing the pigment dispersant on the surface of the pigment, or organic pigment and pigment in a solvent having strong dissolving power such as sulfuric acid The method of co-dissolving a dispersing agent and coprecipitating with poor solvents, such as water, is mentioned. The structure of the pigment dispersant of the present invention to be added after the refining of the pigment may be different from that added at the time of refining the pigment.

Further, the pigment dispersant of the present invention contained in the pigment composition of the present invention has a wide structure, crystal growth, particle stability effect, and viscosity reduction effect, and in particular, anthraquinone red pigment, diketopyrrolopyrrole Red pigments represented by red pigments, quinacridone red pigments, and thiazine indigo red pigments are highly effective.

Next, the coloring composition of this invention is demonstrated. The coloring composition of the present invention contains the pigment composition of the present invention and a pigment carrier. The pigment carrier is constituted by a resin, its precursor or a mixture thereof. Moreover, you may use together coloring agents other than the pigment composition of this invention.

The coloring composition of the present invention may be used in combination with a pigment or dye other than the pigment composition of the present invention as long as the effect of the present invention is not impaired in order to adjust the 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, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Mention may be made of red pigments such as 279, 280, 281, 282, 283, 284, 285, 286 or 287. Examples of red dyes include xanthene series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and anthraquinone series. Specifically, C.I. I. Examples include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289, and 338.

In addition, C.I. I. Pigment Orange 43, 71, or 73 and / or 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, Yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination. Examples of the orange dye and / or yellow dye include quinoline series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and methine series.

Preferred colorants to be used in combination are C.I. I. Pigment red 177, 254, 242 and C.I. I. Pigment yellow 139, 150, and 185.

When using together colorants other than the pigment composition of this invention, it is preferable that the pigment composition of this invention is the range of 40 mass%-100 mass% in the coloring agent whole quantity (100 mass%). More preferably, it is the range of 60 mass%-100 mass%. When the pigment composition of this invention is 40 mass% or less, the effect which was excellent in the brightness cannot fully be exhibited.

Examples of the resin include thermoplastic resins, thermosetting resins, and photosensitive resins. Examples of the resin precursor include monomers or oligomers that are cured by irradiation with radiation to form a resin, and these can be used alone or in combination of two or more.

  The pigment carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the pigment composition in the coloring composition. When a mixture of a resin and its precursor is used as a pigment carrier, the resin is 20 to 400 parts by weight, preferably 50 to 250 parts by weight with respect to 100 parts by weight of the pigment composition in the colored composition. Can be used. The resin precursor can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment composition in the colored composition.

  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, and polyurethane resin. Polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene, polybutadiene, polyimide resin, and the like.

Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

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

  As monomers and oligomers that are precursors of resins, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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, 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, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) Various acrylates and methacrylates such as acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl ( Examples include meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

  In order to improve the dispersibility of the pigment in the pigment carrier, the coloring composition according to the present invention may appropriately contain a dispersion aid such as a surfactant or a resin-type pigment dispersant. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the pigment composition in the coloring composition.

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

  Resin-type pigment dispersant is a resin that has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier. It works to do. Examples of the resin-type pigment dispersant include those made of a polyester-based, acrylic-based, or urethane-based linear or comb-like resin. The main chain or terminal of the linear resin, the main chain or side of the comb-shaped resin, and the like. Those having a basic group, acidic group, aromatic group or the like in the chain in a block or randomly are preferable.

Examples of commercially available resin-type pigment dispersants include, for example, Polyflow No. 75, NO. 90, NO. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), MegaFuck F171, F172, F173 (manufactured by Dainippon Ink and Chemicals), and Fluorard FC430. , FC431 (manufactured by Sumitomo 3M), various Solsperse dispersants (manufactured by Avicia) such as Solsperse 13240, 20000, 24000, 26000, 28000, Dispersic 111, 160, 161, 162, 163, 164, 170, 182, 2000, 2001 Dispersic dispersants (made by BYK Chemie), etc., Ajisper PB711, PB411, PB111, PB814, PB821, PB822, and other various adipar dispersants (manufactured by Ajinomoto Fine-Techno), Fuka dispersants such as Fuka 46 and 47 Chemicals Co., Ltd.), and the like.

  When the colored composition of the present invention is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator is added.

  Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-T-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone-based photopolymerization initiators such as zoyl-4′-methyldiphenyl sulfide, thioxanthone-based light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (P-methoxyphenyl) -4,6-bis (trichloro) Methyl) -S-triazine, 2- (P-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -S-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-S-triazine, 2- (naphth-1-yl) -4,6-bis Trichloromethyl) -S-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine and other triazine photopolymerization initiators, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators and the like are used. It is done. A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigment compositions in a coloring composition, Preferably it is 10-150 weight part.

  The above photopolymerization initiators can be used alone or in combination of two or more. As the sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10- Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (T-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone These compounds can also be used in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  The coloring composition of the present invention can contain a solvent in order to facilitate the dispersion of the pigment in the pigment carrier and the formation of a uniform coating film. Examples of the solvent include cyclohexanone, propylene glycol diacetate, propylene glycol monomethyl ether, diethylene glycol diethyl ether, methyl isobutyl ketone, N-butyl alcohol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene. Glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl butyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether acetate, 1,3-butylene glycol diacetate, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 3-methoxybutanol, 1,3-butylene glycol, triacetin, 3,3,5-trimethyl-2-cyclohexen-1-one, ethylene glycol monoethyl ether , Γ-butyrolactone, isoamyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, toluene, O-xylene, M-xylene, P-xylene, methyl 3-methoxypropionate, butyl acetate, isobutyl acetate, propyl acetate Etc. These solvents can be used alone or in combination.

The solvent can be used in a total amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, based on 100 parts by weight of the pigment composition in the coloring composition.

The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a base material, adhesion improving agents, such as a silane coupling agent, can also be contained.

In addition, the coloring composition of the present invention, if necessary, within a range not impairing the effects of the present invention, a thermal polymerization inhibitor, a plasticizer, a surface protective agent, a smoothing agent, a coating aid, an adhesion improver, a coating Additives such as property improvers or development improvers can be added.

  The coloring composition of the present invention comprises a three-roll mill, a two-roll mill, a horizontal sand mill in the pigment carrier and an organic solvent, together with the dispersion aid and the photopolymerization initiator as necessary. It can be produced by finely dispersing using various dispersing means such as a vertical sand mill, an annular bead mill, a kneader, and an attritor. In addition, a coloring composition containing two or more kinds of pigments can also be produced by mixing each pigment separately finely dispersed in a pigment carrier and an organic solvent using the pigment dispersant of the present invention.

The coloring composition of the present invention may be dispersed after mixing all the components constituting the coloring composition. First, the pigment and the pigment dispersant of the present invention are mixed with a part of the resin and / or organic solvent. It is preferable to disperse and then add the remaining components and disperse. If necessary, a pigment dispersant other than the present invention can also be used.

Also, before dispersing with horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc., pre-dispersion using knitted meat mixer such as kneader, three roll mill, solid dispersion with two roll mill, etc., or pigment The diketopyrrolopyrrole pigment dispersant may be treated. In addition, after being dispersed by a bead mill or the like, a post-treatment called aging which is stored at a temperature of 30 to 80 ° C. for several hours to one week, or a post-treatment using an ultrasonic disperser or a collision type beadless disperser is performed. When done, it is effective for the stability of the colored composition. In addition, any disperser or mixer such as a microfluidizer, high speed mixer, homomixer, ball mill, roll mill, stone mill, or ultrasonic disperser can be used to produce the colored composition of the present invention.

  When the colored composition of the present invention is used for the production of a color filter, the coarse particles of 5 μM or more, preferably 1 μM or more, more preferably, by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove coarse particles of 0.5 μM or more and mixed dust.

The coloring composition of the present invention can be prepared as gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material.
The solvent development type or alkali development type colored resist material contains a thermoplastic resin, thermosetting resin or photosensitive resin as a pigment carrier, a monomer, a photopolymerization initiator, and a solvent. The pigment composition of the invention is dispersed.

Furthermore, the colored composition of the present invention is excellent in dispersion effect and stability over time even in the coloring of a wide range of printing inks, paints, inkjet inks, and plastics, and a colored product having coloring power can be obtained.

In that case, without using a monomer or photopolymerization initiator, in addition to the resin and solvent described above, resins such as petroleum resin, casein, shellac, drying oil, synthetic drying oil, and ethyl cellosolve acetate, butyl cellosolve acetate, ethylbenzene, acetic acid Using a solvent such as ethyl, methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, glycerin, dimethylformamide, Solvesso 100 (Exxon Chemical Co., Ltd.), Swazol 1000, petroleum-based solvent, etc., if necessary, a surfactant and / or A colored composition can be produced by the above-described method using a resin-type pigment dispersant.

Next, the color filter will be described.
In the color filter of the present invention, a red filter segment, a green filter segment, and a blue filter segment are formed on a transparent or reflective substrate, and the red filter segment therein contains the pigment composition of the present invention. Formed from a coloring composition or a photosensitive coloring composition. Each color filter segment can be formed by using the coloring composition of the present invention by a printing method or a photolithography method.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

As the reflective substrate, silicon or a substrate obtained by forming an aluminum, silver, silver / copper / palladium alloy thin film on the transparent substrate is used.

  The green filter segment can be formed using a conventional green coloring composition comprising a green pigment and a colorant carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used.

A yellow pigment can be used in combination with the green 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, 82,185,187,188,193,194,198,199,213,214,218,219,220, or it can be given a yellow pigment 221, and the like. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant 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, etc. are used. A purple pigment can be used in combination with the blue coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When using a dye, a xanthene dye is preferable in terms of heat resistance and lightness.

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

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

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

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

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

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

In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.

The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, in the examples, “part” represents “part by weight”. P.P. R. 177 represents “CI Pigment Red 177”.

[Example 1]
(Production of Pigment Dispersant 1 (D-1))
To 325 parts of 98% sulfuric acid cooled to 0 ° C., 30 parts of 1-aminoanthraquinone was slowly added over 30 minutes while maintaining the temperature at 20 ° C. or lower. Further, 19 parts of α-chloroacetamide was added over 20 minutes, 8 parts of paraformaldehyde was added over 20 minutes, stirred at 15 to 20 ° C. for 4 hours, and left overnight. The reaction solution was poured into 750 parts of ice and 1500 parts of water, and the precipitate was filtered and washed 3 times with 1000 parts of ice water to obtain a press cake of chloroacetamidomethylaminoanthraquinone. Next, 500 parts of ice, 500 parts of water, and 36 parts of 1- (2-aminoethyl) piperazine were added to a 3 L beaker, and a chloracetamidomethylaminoanthraquinone presscake was added at 0 to 5 ° C. The mixture was then warmed to 60 ° C. and stirred for 2 hours. The product was filtered, washed with water and dried at 80 ° C. This obtained 36 parts of pigment dispersant 1 (D-1) represented by following formula (6).

[Example 2]
(Production of Pigment Dispersant 2 (D-2))
In 100 parts of dimethylformamide, 30 parts of 1-amino-4-bromoanthraquinone and 20 parts of 2-diethylaminoethanethiol were charged at room temperature and stirred with heating at 150 degrees for 5 hours. The product was filtered, washed with water and dried at 80 ° C. This obtained 21 parts of pigment dispersant 2 (D-2) represented by following formula (7).

[Example 3]
(Production of Pigment Dispersant 3 (D-3))
In 300 parts of chlorosulfonic acid, 30 parts of 1-aminoanthraquinone was charged at room temperature. After stirring at room temperature for 5 hours, it was added dropwise to 1500 parts of ice water over 15 minutes. The precipitated sulfonyl chloride was filtered and washed with 3000 parts of ice water to obtain a sulfonyl chloride aminoanthraquinone press cake. Next, 500 parts of ice, 500 parts of water, and 62.4 parts of diethylaminoethylamine were charged into a 3 L beaker, and a press cake of sulfonyl chloride was charged at 2 to 5 ° C. The mixture was then warmed to 60 ° C. and stirred for 90 minutes. The product was filtered, washed with water and dried at 80 ° C. This obtained 27 parts of pigment dispersant 3 (D-3) represented by following formula (8).

[Example 4]
(Production of Pigment Dispersant 4 (D-4))
In 300 parts of chlorosulfonic acid, 30 parts of 1-aminoanthraquinone was charged at room temperature. After stirring at room temperature for 5 hours, it was added dropwise to 1500 parts of ice water over 15 minutes. The precipitated sulfonyl chloride was filtered and washed with 3000 parts of ice water to obtain a sulfonyl chloride aminoanthraquinone press cake. Next, in a 3 L beaker, 500 parts of ice, 500 parts of acetone, 67 parts of 4-amino-N- [3- (diethylamino) propyl] benzamide were added, and a sulfonyl chloride presscake was added at 2-5 ° C. did. The mixture was then warmed to 60 ° C. and stirred for 2 hours. The product was filtered, washed with water and dried at 80 ° C. This obtained 21 parts of pigment dispersant 4 (D-4) represented by following formula (9).

<Method for producing pigment composition>
[Example 5]
(Production of Pigment Composition 1 (R-1))
135 parts of anthraquinone red pigment (CI Pigment Red 177, CINIC “Cinilex Red SR3C”), 15 parts of pigment dispersant 1 (D-1) obtained in Example 1, 1500 parts of sodium chloride, The mixture of 180 parts of diethylene glycol was kneaded at 60 ° C. for 6 hours using a stainless 1 gallon kneader (manufactured by Inoue Seisakusho). Next, this kneaded material was put into 5 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing with water were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C. to obtain 135 parts of pigment composition 1 (R-1).

[Example 6]
(Production of Pigment Composition 2 (R-2))
In Example 1, 135 parts of pigment composition 2 (R-2) was used in the same manner as in Example 1 except that pigment dispersant 2 (D-2) was used instead of pigment dispersant 1 (D-1). )

[Example 7]
(Production of Pigment Composition 3 (R-3))
In Example 1, 135 parts of pigment composition 3 (R-3) was used in the same manner as in Example 1 except that pigment dispersant 3 (D-3) was used instead of pigment dispersant 1 (D-1). )

[Example 8]
(Production of Pigment Composition 4 (R-4))
In Example 1, 135 parts of pigment composition 4 (R-4) was used in the same manner as in Example 1 except that pigment dispersant 4 (D-4) was used instead of pigment dispersant 1 (D-1). )

[Comparative Example 1]
(Production of Pigment Composition 5 (R-5))
In Example 1, 135 parts of pigment composition was used in the same manner as in Example 1 except that Pigment Dispersant 5 (D-5) shown in Table 1 was used instead of Pigment Dispersant 1 (D-1). 5 (R-5) was obtained.

[Comparative Example 2]
(Production of Pigment Composition 6 (R-6))
In Example 1, 135 parts of a pigment composition was used in the same manner as in Example 1 except that pigment dispersant 6 (D-6) shown in Table 1 was used instead of pigment dispersant 1 (D-1). 6 (R-6) was obtained.

[Comparative Example 3]
(Production of Pigment Composition 7 (R-7))
In Example 1, 135 parts of pigment composition was used in the same manner as in Example 1 except that Pigment Dispersant 5 (D-7) shown in Table 1 was used instead of Pigment Dispersant 1 (D-1). 7 (R-7) was obtained.

[Example 9]
While stirring 5,000 parts of 98% sulfuric acid weighed in a stirring vessel at room temperature, 460 parts of CI Pigment Red 177 (“Cinilex Red SR3C” manufactured by CINIC) and Pigment Dispersant 1 obtained in Example 1 ( D-1) 40 parts were gradually added, and the mixture was stirred as it was for 1 hour at room temperature for complete dissolution to obtain a sulfuric acid solution. In another stirring vessel, 2500 parts of water and 2500 parts of ice were mixed, and the above-mentioned sulfuric acid solution was gradually poured while stirring to obtain a slurry. The liquid temperature of the slurry after pouring was 8 ° C. The resulting slurry was filtered and washed with water until the pH of the filtrate reached 7 or higher. This was dried and pulverized to obtain 465 parts of Pigment Composition 8 (R-8).

[Example 10]
(Production of Pigment Composition 9 (R-9))
In Example 9, instead of Pigment Dispersant 1 (D-1), Pigment Dispersant 2 (D-2) was used, and 465 parts of Pigment Composition 9 (R-9) were otherwise obtained in the same manner as in Example 9. )

[Example 11]
(Production of Pigment Composition 10 (R-10))
In Example 9, Pigment Dispersant 3 (D-3) was used instead of Pigment Dispersant 1 (D-1), and 465 parts of Pigment Composition 10 (R-10) were otherwise obtained in the same manner as in Example 9. )

[Example 12]
(Production of Pigment Composition 11 (R-11))
In Example 9, Pigment Dispersant 4 (D-4) was used in place of Pigment Dispersant 1 (D-1), and 465 parts of Pigment Composition 11 (R-11) were otherwise obtained in the same manner as in Example 9. )

[Comparative Example 4]
(Production of Pigment Composition 12 (R-12))
In Example 9, Pigment Dispersant 5 (D-5) was used instead of Pigment Dispersant 1 (D-1), and 465 parts of Pigment Composition 12 (R-12) were otherwise obtained in the same manner as in Example 9. )

[Comparative Example 5]
(Production of Pigment Composition 13 (R-13))
In Example 9, Pigment Dispersant 6 (D-6) was used instead of Pigment Dispersant 1 (D-1), and 465 parts of Pigment Composition 13 (R-13) were otherwise obtained in the same manner as in Example 9. )

[Comparative Example 6]
(Production of Pigment Composition 14 (R-14))
In Example 9, Pigment Dispersant 7 (D-7) was used instead of Pigment Dispersant 1 (D-1), and 465 parts of Pigment Composition 14 (R-14) were otherwise obtained in the same manner as in Example 9. )

(Evaluation of average primary particle diameter of pigment composition)
The average primary particle diameter of the produced pigment composition was measured (calculated) by the following method.

Propylene glycol monomethyl ether acetate was added to the powder of the pigment composition, a small amount of Disperbyk-161 was added as a resin type dispersant, and the sample for measurement was prepared by ultrasonic treatment for 1 minute. Three samples (for three fields of view) of the primary particles of 100 or more pigment compositions were taken with this sample using an H-7650 transmission electron microscope manufactured by Hitachi High-Technologies Corporation. The size of each primary particle was measured. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment composition are measured in nm units, the average is the primary particle diameter of the pigment composition particles, and a total of 300 distributions in 5 nm increments. Approximate the median value in 5 nm increments (for example, 8 nm for 6 nm or more and 10 nm or less) as the particle diameter of these particles, and calculate the number average particle diameter by calculating based on each particle diameter and the number thereof. Calculated.

  As shown in Table 2 and Table 3, the pigment dispersant of the present invention showed the effect of preventing crystal growth of conventional pigment dispersants 5 to 7 (D-5 to 7) or more.

<Method for producing other pigments>
(Adjustment of red processed pigment 1)
Using a mixture of 150 parts of anthraquinone red pigment (CI Pigment Red 177, CINIC “Cinilex Red SR3C”), 1500 parts of sodium chloride, and 180 parts of diethylene glycol using a stainless steel 1 gallon kneader (Inoue Seisakusho) And kneading at 60 ° C. for 6 hours. Next, this kneaded material was put into 5 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying and pulverization to obtain 135 parts of red treated pigment 1.

(Adjustment of red yellow pigment 1)
Diketopyrrolopyrrole red pigment (CI Pigment Red 254, “IRGAPHOR RED B-CF” manufactured by Ciba Specialty Chemicals Co., Ltd.), anthraquinone red pigment (CI Pigment Red 177, Ciba Specialty Red) "CHROMOPHTAL RED A2B" manufactured by Chemicals Co., Ltd.) and azo yellow pigment (CI Pigment Yellow 150, "YELLOW PIGMENT E4GN-GT" manufactured by LANXESS Co., Ltd.) are mixed at a weight ratio of 3: 5: 2, respectively. 150 parts of sodium chloride, 1500 parts of sodium chloride, and 200 parts of diethylene glycol were kneaded at 60 ° C. for 10 hours using a stainless steel 1 gallon kneader (Inoue Seisakusho). Next, this kneaded material was put into 5 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying and pulverization to obtain 135 parts of red-yellow pigment 1.

(Production of diketopyrrolopyrrole pigment 1 (PR254-1))
A mixture of 150 parts of diketopyrrolopyrrole red pigment (CI Pigment Red 254, “IRGAPHOR RED B-CF” manufactured by Ciba Specialty Chemicals Co., Ltd.), 1500 parts of sodium chloride, and 200 parts of diethylene glycol is made of stainless steel. A 1 gallon kneader (Inoue Seisakusho) was used and kneaded at 60 ° C. for 10 hours. Next, this kneaded material was put into 5 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing with water were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C. and pulverization to obtain 135 parts of diketopyrrolopyrrole pigment 1 (R254-1).

<Method for producing acrylic resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. 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 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, 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, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution 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 vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. 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 completion of dropping, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

  The weight average molecular weight of the acrylic resin is a polystyrene equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

<The preparation method of the coloring composition which uses a pigment composition>
Examples 13-90 and Comparative Examples 7-18
After blending various pigment compositions, pigment dispersants 1 to 5 (D1 to D5), acrylic resin solution 1 and solvent (propylene glycol monomethyl ether acetate) as shown in Tables 3 and 4, respectively, and stirring and mixing uniformly, Using zirconia beads having a diameter of 0.5 mm, the mixture was dispersed for 6 hours in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan). This was filtered with a 5 μm filter to prepare colored compositions 1-90 (RP1-90).

(Evaluation of coloring composition)
<Viscosity>
The viscosity at 25 ° C. of the coloring compositions for color filters obtained in Examples 13 to 90 was measured with a cone plate type viscometer (“TVE-20L type” manufactured by Toki Sangyo Co., Ltd.). Furthermore, after the coloring composition was stored at 40 ° C. for 1 week, the viscosity at 25 ° C. was measured.

  Viscosity stability over time, ◎ (almost no thickening), ○ (slightly thickening can be used, usable range), △ (thickening is not possible), × (noticeable due to significant thickening) It was expressed in four stages.

  As shown in Tables 4 and 5, the pigment dispersant of the present invention showed good dispersibility.

<Method for producing other colored composition>
(Preparation of colored composition 91 (RP-91))
A mixture having the composition shown below was uniformly stirred and mixed, and dispersed for 6 hours in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. This was filtered with a 5-micrometer filter, and the coloring composition 91 (RP-91) was produced.
Diketopyrrolopyrrole pigment (PR254-1) 10.8 parts Dye derivative of formula (10) 1.2 parts Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

<Production method of photosensitive coloring composition>
[Example 91]
(Preparation of photosensitive coloring composition 1 (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare photosensitive coloring composition 1 (RR-1).
Coloring composition 1 (RP-1) 20.0 parts Coloring composition 91 (RP-91) 22.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 2.8 parts photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan) 2.0 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 39 .6 parts

[Examples 92 to 164]
(Photosensitive coloring composition 2-5, 7-30, 32-35, 37-40, 42-45, 47-51, 53-76, 78-81, 83-86 (RR-2-5, 7- 30, 32 to 35, 37 to 40, 42 to 45, 47 to 51, 53 to 76, 78 to 81, 83 to 86)
Coloring composition 1 (RP-1) is colored composition 2-5, 8-31, 33-36, 38-41, 43-46, 49-53, 56-79, 81-84, 86-89 ( RP-2 to 5, 8 to 31, 33 to 36, 38 to 41, 43 to 46, 49 to 53, 56 to 79, 81 to 84, 86 to 89), and further colored compositions 2 to 5, 8-31, 33-36, 38-41, 43-46, 49-53, 56-79, 81-84, 86-89 (RP-2-5, 8-31, 33-36, 38-41, 43-46, 49-53, 56-79, 81-84, 86-89) and the ratio of the colored composition 91 (RP-91) is changed (ratio change within 42 parts of the total amount of the colored composition) In the same manner as in Example 91, photosensitive coloring compositions 2 to 5, 7 to 30, 32 to 35, 37 to 40, 42 to 45 47-51, 53-76, 78-81, 83-86 (RR-2-5, 7-30, 32-35, 37-40, 42-45, 47-51, 53-76, 78-81, 83-86). In addition, about a ratio change, coloring composition 2-5, 8-31, 33-36, so that it may suit chromaticity of x = 0.640, y = 0.328 with a C light source in the case of coating-film evaluation, 38-41, 43-46, 49-53, 56-79, 81-84, 86-89 (RP-2-5, 8-31, 33-36, 38-41, 43-46, 49-53, 56-79, 81-84, 86-89) and the ratio of the colored composition 91 (RP-91) were changed.

[Comparative Examples 19-27]
(Preparation of photosensitive coloring composition 6, 31, 36, 41, 46, 52, 77, 82, 87 (RR-6, 31, 36, 41, 46, 52, 77, 82, 87))
Coloring composition 1 (RP-1) is colored composition 6, 32, 37, 42, 47, 54, 80, 85, 90 (RP-6, 32, 37, 42, 47, 54, 80, 85, 90 ), And coloring composition 6, 32, 37, 42, 47, 54, 80, 85, 90 (RP-6, 32, 37, 42, 47, 54, 80, 85, 90) and coloring composition Photosensitive colored composition 6, 31, 36, 41, 46, 52 in the same manner as in Example 91 except that the ratio of the product 91 (RP-91) was changed (the ratio was changed within 42 parts of the total amount of the colored composition). , 77, 82, 87 (RR-6, 31, 36, 41, 46, 52, 77, 82, 87). In addition, about the ratio change, the coloring composition 6, 32, 37, 42, 47, 54, so that it may match chromaticity of x = 0.640, y = 0.328 with a C light source at the time of coating film evaluation. The ratio of 80, 85, 90 (RP-6, 32, 37, 42, 47, 54, 80, 85, 90) and the colored composition 91 (RP-91) was changed.

<Preparation and evaluation of coating film using photosensitive coloring composition>
The color characteristics and contrast ratio of the red coating film produced using the obtained photosensitive coloring composition (RR-1 to 87) were evaluated by the following methods. Tables 6 to 22 show the types and evaluation results of the coloring compositions in the photosensitive coloring composition.

(Evaluation of color characteristics (lightness) of coating film)
On a glass substrate of 100 mm × 100 mm and 0.7 mm thickness, a photosensitive coloring composition is applied to a film thickness such that x = 0.640 and y = 0.328 with a C light source, and after drying, ultrahigh pressure mercury An ultraviolet ray of 300 mJ / cm ² was irradiated using a lamp. Furthermore, the red coating film was obtained by heating at 230 degreeC for 60 minutes. Then, the brightness (Y) of the obtained coating film was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Evaluation of contrast ratio of coating film)
A method for measuring the contrast ratio of the coating film will be described. The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, 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 colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted 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 plate was parallel and the luminance when it was orthogonal was calculated.

(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)

  Accordingly, when scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.

  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. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light. In contrast ratio measurement, a red coating film obtained by the same method as that used for color characteristic evaluation was used.

  As shown in Tables 6 and 7, better results were obtained in terms of brightness (Y) than when the conventional pigment dispersant 5 (D-5) was used. The contrast ratio of the coated substrate was also good.

<Production of color filter>
The green photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced. In addition, the photosensitive coloring composition 64 (RR-64) of this invention was used about red.

(Preparation of green coloring composition 1 (GP-1))
The mixture having the composition shown below was stirred and mixed uniformly, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and green colored composition 1 (GP-1) 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 Ciba Japan) 1.0 part Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of green photosensitive coloring composition 1 (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare green photosensitive coloring composition 1 (GR-1).
Green coloring composition 1 (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 (Ciba Japan) "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 stirred and mixed uniformly, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and blue colored composition 1 (BP-1) 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 Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition 1 (BR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition 1 (BR-1).
Blue coloring composition 1 (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 (Ciba Japan) "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 7 (RR-7) of the present invention is formed on the substrate with a spin coater so that x = 0.640 and y = 0.328. 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, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green photosensitive coloring composition 1 (GR-1) was formed to a thickness such that x = 0.300 and y = 0.600, and the blue photosensitive coloring composition 1 (BR-1) was added. The film was applied to a thickness of x = 0.150 and y = 0.060, respectively, to form a green filter segment and a blue filter segment to obtain a color filter.

By using the photosensitive coloring composition 64 (RR-64) of the present invention, it was possible to produce a color filter with high brightness and high contrast.

Claims (9)

A pigment dispersant represented by the following formula (1).

(In the formula, R _{1 to} R ₇ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, a nitro group, an amino group, a cyano group, a sulfonic acid group, a carboxylic acid group, the following formula (2 Or a basic group represented by formula (3), provided that at least one of R _{1 to} R ₇ is a basic group represented by formula (2) or formula (3).

(Where
X is a direct bond, -S -, - O -, - SO 2 -, - CO -, - SO 2 NR -, - NRSO 2 -, - CONR -, - CH 2 NRCOCH 2 NR- , or - (CH ₂ ) _m represents NH-.
m represents an integer of 1 to 10.
R may have a hydrogen atom, an optionally substituted alkyl group having 20 or less carbon atoms, an optionally substituted alkenyl group having 20 or less carbon atoms, or a substituent. An aryl group having 20 or less carbon atoms.
Y may have a direct bond, an alkylene group having 20 or less carbon atoms which may have a substituent, an alkenylene group having 20 or less carbon atoms which may have a substituent, or a substituent. It represents an arylene group having 20 or less carbon atoms, a divalent heterocyclic group which may have a substituent, or —Y ₁ —Y ₂ —Y ₃ —.
Y ₁ and Y ₃ each independently have an alkylene group having 20 or less carbon atoms which may have a substituent, an alkenylene group having 20 or less carbon atoms which may have a substituent, and a substituent. And an arylene group having a carbon number of 20 or less or a divalent heterocyclic group which may have a substituent.
Y ₂ represents a direct bond, —NR—, —O—, —SO ₂ —, —CONR— or —CO—, but when Y ₁ and Y ₃ are the same group, it is not a direct bond. Absent.
R ₈ and R ₉ each independently represents an alkyl group having 30 or less carbon atoms which may have a substituent or an alkenyl group having 30 or less carbon atoms which may have a substituent, and R ₈ And R ₉ may be connected to each other to form a ring.
Z is a direct _{bond, -CH 2 NR'COCH 2 NR '-} , - CH 2 NR'COCH 2 NR'-G -, - NR' -, - NR'-G-CO -, - NR'-G- CONR '-, - NR'-G -SO 2 -, - NR'-G-SO 2 NR' -, - O-G-CO -, - O-G-CONR '-, - SO 2 -, - O -G-SO ₂ - or represents a -O-G-SO ₂ NR'-.
G is an alkylene group having 20 or less carbon atoms that may have a substituent, an alkenylene group having 20 or less carbon atoms that may have a substituent, or a carbon number that may have a substituent. Represents an arylene group having 20 or less, and R ′ represents a hydrogen atom, an alkyl group having 20 or less carbon atoms which may have a substituent, and an alkenyl group having 20 or less carbon atoms which may have a substituent. Alternatively, it represents an aryl group having 20 or less carbon atoms which may have a substituent.
R _{10 to} R ₁₃ each independently represents a hydrogen atom, an alkyl group having 20 or less carbon atoms that may have a substituent, an alkenyl group or substituent having 20 or less carbon atoms that may have a substituent. Represents an aryl group having 20 or less carbon atoms.
R ₁₄ represents a hydrogen atom, an optionally substituted alkyl group having 20 or less carbon atoms, or an optionally substituted alkenyl group having 20 or less carbon atoms. ) R _{1 to} R ₇ are each independently a hydrogen atom or a basic group represented by formula (2) or formula (3), and any one to four of R _{1 to} R ₇ are The pigment dispersant according to claim 1, which is a basic group represented by formula (2) or formula (3).   A pigment composition comprising the pigment dispersant according to claim 1 or 2 and a pigment.   The pigment composition according to claim 3, wherein the pigment is one or more pigments selected from the group consisting of diketopyrrolopyrrole pigments, quinacridone pigments, thiazine indigo pigments and anthraquinone pigments.   Furthermore, the pigment composition in any one of Claim 3 or 4 which comprises a pigment derivative.   The pigment derivative is one or more pigment residues selected from the group consisting of diketopyrrolopyrrole, quinacridone, thiazineindigo, benzoisoindole and anthraquinone, and from the group consisting of a basic group, an acidic group and a phthalimidomethyl group 6. The pigment composition according to claim 5, which is a pigment derivative formed by bonding one or more selected groups.   The pigment composition according to any one of claims 3 to 6, further comprising a yellow pigment.   A coloring composition comprising the pigment composition according to any one of claims 3 to 7 and a pigment carrier.   A color filter comprising a filter segment formed from the colored composition according to claim 8.