JP5402003B2 - Pigment dispersion and ink - Google Patents

Description

  The present invention relates to a pigment dispersion that makes it possible to easily obtain a fine dispersion of pigment particles and to keep it in a stable state. More specifically, the present invention relates to a pigment dispersion suitably used for an ink for a color filter. The present invention relates to a body and an ink using the body.

  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. Further, in offset inks, gravure inks, paints, particularly ink jet inks, color filter inks, etc., it is necessary to highly refine the pigment particles in order to obtain high sharpness. At this time, a solvent salt milling method, a dry pulverization method, and the like are widely used as methods for refining the pigment particles. However, if the pigment is added together with commonly used grinding aids such as inorganic salts and solvents, pigment particles may grow at the same time due to the heat generated during grinding and the solvent added as a dispersion aid. When the mechanical force is applied for a long time, the state of the pigment particles becomes unstable, causing changes such as crystal transition. May not be obtained. In addition, since the pigment particle diameter is likely to vary particularly only by dry pulverization, finer pigment particles are more likely to cause crystal growth when controlled by solvent treatment, and are difficult to control.

  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.
Patent Document 1 discloses that the dispersibility of a pigment is improved by containing a pigment derivative having a pigment as a base skeleton and having a basic group as a substituent in a side chain. However, those containing pigments that are further refined cannot be sufficiently reduced in viscosity and storage stability with the pigment derivatives shown above. In addition, a great amount of energy is required to disperse until high gloss and transparency are obtained when loosely aggregated fine pigment particles are loosened.

  Therefore, a pigment dispersion having high dispersion performance, excellent viscosity suitability, and storage stability is desired also in color filter inks obtained by dispersing highly fine pigment particles.

Japanese Patent Laid-Open No. 3-153780 JP 2002-88269 A The present invention relates to an ink and a pigment dispersion for providing the ink.

An object of the present invention is to provide a pigment composition in which pigment particles are stably highly refined, and is particularly low for applications requiring fine dispersion of pigment particles, such as color filter inks. The object of the present invention is to provide a pigment ink that is vastly excellent in viscosity and stability over time.

The present invention is a pigment composition comprising at least a pigment, a dispersant, a solvent, and an organic dye derivative or heteroaromatic ring derivative (D), wherein the organic dye derivative or heteroaromatic ring derivative (D) is represented by the following general formula ( 1) The organic dye derivative or heteroaromatic ring derivative (D1) represented by the formula (2) and the organic dye derivative or heteroaromatic ring derivative (D2) represented by the following general formula (2), wherein the weight ratio of D1: D2 is It is a pigment dispersion for a color filter characterized by being 5: 95-40: 60.
General formula (1):

General formula (2):

The symbols in the formula have the following meanings.
Q: an organic dye residue, an anthraquinone residue, a heterocyclic ring that may have a substituent, or an aromatic compound X that may have a substituent; a direct bond, —CONH—Y ₁ —, SO ₂ NH—Y ₁ —, or —CH ₃ NHCOCH ₂ NH—Y ₁ —
(Y ₁ ; alkylene group or arylene group which may have a substituent)
R ₁ ;

(Y ₂ ; —NH— or —O—)
(R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group, or R ₂ and R ₃ may form a heterocycle containing at least a nitrogen atom.)
m: integer of 1-6 n: integer of 1-4

The present invention further relates to a color filter pigment dispersion characterized in that the ratio of pigment to organic dye derivative or heteroaromatic ring derivative (D) is from 100: 0.1 to 100: 100.
The present invention further relates to the color filter pigment dispersion according to claim 1 or 2, wherein the dispersant is a compound represented by the following general formula.
General formula (3)

(In the formula, R ₄ represents a polyester residue having a number average molecular weight of 50 0 to 1 0 0 0 0, and y represents 1 to 2)

In the present invention, the dispersant further comprises a polymer having an aromatic carboxyl group (A), an aromatic tricarboxylic acid anhydride (B1) and / or an aromatic tetracarboxylic acid anhydride (B2) and a hydroxyl group (C 3. The pigment dispersion for a color filter according to claim 1, which is a compound obtained by reacting
The present invention further relates to the pigment dispersion for a color filter according to claim 4, wherein the polymer (C) having a hydroxyl group is a polymer (C1) having a hydroxyl group at one end.

The present invention further relates to the pigment dispersion for a color filter according to claim 4, wherein the polymer (C) having a hydroxyl group is a polymer (C2) having a hydroxyl group in a side chain.
The color dispersion pigment dispersion according to claim 4, wherein the polymer (C1) having a hydroxyl group at one end is a polymer (C3) having two hydroxyl groups at one end. About.
The present invention further relates to a pigment ink for a color filter comprising the above pigment dispersion.

The pigment dispersion obtained in the present invention is superior in stability to pigment dispersions using conventional organic dye derivatives or heteroaromatic ring derivatives, and can disperse finer pigments. Therefore, the color filter produced by the pigment dispersion of the present invention can achieve a high contrast ratio.

Organic dye derivative comprising organic dye derivative or heteroaromatic ring derivative (D1) represented by the following general formula (1) and organic dye derivative or heteroaromatic ring derivative (D2) represented by the following general formula (2) Examples of the organic dye residue (Q) of the heteroaromatic ring derivative (D) include, for example, phthalocyanine dyes, azo dyes, quinacridone dyes, dioxazine dyes, anthrapyrimidine dyes, ansanthrone dyes, and indanthones. Examples thereof include pigment skeletons or dye skeletons such as Ron dyes, flavanthrone dyes, perylene dyes, perinone dyes, thioindico dyes, isoindolinone dyes, and triphenylmethane dyes.
Examples of the heterocyclic ring or aromatic ring include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, Naphthalene, anthracene, fluorene, phenanthrene and the like can be mentioned.

  In the pigment composition of the present invention, an organic dye derivative or heteroaromatic ring derivative (D1) represented by the following general formula (1) and an organic dye derivative or heteroaromatic ring derivative represented by the following general formula (2) The weight ratio of (D2) is preferably 5:95 to 40:60, more preferably 10:90 to 25:75. When the ratio of D1 is high, or extremely low or 0, the viscosity becomes high, and further, the long-term storage stability of the target pigment composition cannot be ensured.

General formula (1):

General formula (2):

The symbols in the formula have the following meanings.
Q: an organic dye residue, an anthraquinone residue, a heterocyclic ring that may have a substituent, or an aromatic compound X that may have a substituent; a direct bond, —CONH—Y ₁ —, SO ₂ NH—Y ₁ —, or —CH ₃ NHCOCH ₂ NH—Y ₁ —
(Y ₁ ; alkylene group or arylene group which may have a substituent)
R ₁ ;

(Y ₂ ; —NH— or —O—)
(R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group, or R ₂ and R ₃ may form a heterocycle containing at least a nitrogen atom.)
m: integer of 1-6 n: integer of 1-4

 The organic dye derivative or heteroaromatic ring derivative (D) composed of the organic dye derivative or heteroaromatic ring derivative (D1) and the organic dye derivative or heteroaromatic ring derivative (D2) is added in an amount of 100 parts by weight of the pigment. The amount is preferably 0.1 to 100 parts by weight, more preferably 1 to 40 parts by weight. If the organic dye derivative or heteroaromatic ring derivative (D) is less than 0.1 parts by weight or more than 100 parts by weight with respect to 100 parts by weight of the pigment, the dispersibility may deteriorate.

Regarding the pigment used in the pigment dispersion of the present invention, for example, the following organic pigments can be used.
Azo, anthanthrone, anthrapyrimidine, anthraquinone, isoindolinone, isoindoline, indanthrone, quinacridone, quinophthalone, dioxazine, diketopyrrolopyrrole, thiazine indigo, thioindigo , Pyranthrone, phthalocyanine, flavanthrone, perinone, perylene, benzimidazolone, etc., preferably Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Violet 19, 23, 29, 30, 37, 40, 50, Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 144, 146, 149, 166, 168, 177, 178, 179, 185, 206 , 207, 209, 220 221, 238, 242, 254, 255, Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138 , 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 199, Pigment Orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74, Pigment Green 7, 10, 36, 37, 58, etc. can be used.

 Examples of the dispersant used in the pigment dispersion of the present invention include the following compounds. For example, a polyester-based, acrylic-based, urethane-based linear or comb-shaped resin or a surfactant can be used.

 As the resin-type pigment dispersant, those having a basic group, an acidic group, an aromatic group or the like in the main chain or terminal of the linear resin or in the main chain or side chain of the comb-shaped resin in a block or randomly are preferable. Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long A chain polyaminoamide phosphate, a hydroxyl group-containing polycarboxylic acid ester, a modified product thereof, an amide formed by reaction of poly (lower alkyleneimine) with a polyester having a free carboxyl group, a salt thereof, or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used. These can be used alone or in admixture of two or more.

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

 Examples of commercially available resin-type pigment dispersants include various Solsperse dispersants such as Solsperse 13240, 20000, 24000, 26000, 28000, 31000, and 76500 (manufactured by Nippon Lubrizol Co., Ltd.), Dispersic 110, 111, 160, 161, 162, 163, 164, 167, 170, 182, 2000, 2001, 2020, 2025, 2050, 2070, 2096, 2150, etc. (disclosed by Big Chemie), Addisper PB711, PB411, PB111, PB814 , PB821, PB822, etc. Ajisper dispersant (manufactured by Ajinomoto Finetechno Co., Ltd.), Fuka dispersants such as Fuka 46, 47, 4300, 4330, 4340 (manufactured by Fuka Additives Co., Ltd.) Etc., and the like.

As the dispersant used in the pigment dispersion in the present invention, a dispersant represented by the following general formula (3) and / or a dispersant (A) having an aromatic carboxyl group is preferable in that stability is further improved.
General formula (3)

(In the formula, R ₄ represents a polyester residue having a number average molecular weight of 500 to 10,000, and y represents 1 to 2.) A more preferable number average molecular weight is 500 to 3000.

The phosphate ester represented by the general formula (3) can be obtained by converting a polyester residue having a hydroxyl group at one end to a phosphate ester. A polyester residue having a hydroxyl group at one end can be obtained by ring-opening addition of ε-caprolactone or the like using monoalcohol as an initiator.
The monoalcohol is not particularly limited as long as it has one hydroxyl group in the molecule, and any of primary, secondary, and tertiary alcohols can be used. For example, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, Stearyl alcohol, oleyl alcohol, hexadecyl alcohol and the like and mixtures thereof are used.

 A polyester residue having a hydroxyl group at one end can be obtained by ring-opening addition of ε-caprolactone or the like using monoalcohol as an initiator. The addition reaction of ε-caprolactone can be carried out in a known manner, for example, by charging monoalcohol, ε-caprolactone and a polymerization catalyst into a reactor connected to a dehydrating tube and a condenser, and under a nitrogen stream. When a monoalcohol having a low boiling point is used, the reaction can be carried out under pressure using an autoclave. In the reaction, a solvent-free or a suitable dehydrating solvent such as toluene or xylene can be used. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.

 The reaction temperature is 120 ° C to 220 ° C, preferably 160 ° C to 210 ° C. If the reaction temperature is less than 120 ° C, the reaction rate is very slow, and if it exceeds 220 ° C, side reactions other than the addition reaction of ε-caprolactone, such as decomposition of ε-caprolactone adduct into ε-caprolactone monomer, cyclic ε-caprolactone dimer Is likely to occur. The number of moles of ε-caprolactone added to 1 mole of monoalcohol is 1 to 50 moles, preferably 3 to 20 moles. When the number of added moles is less than 1 mole, it is difficult to obtain the effect as a dispersant.

Examples of the polymerization catalyst include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium. Quaternary ammonium salts such as iodo, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethyl In addition to quaternary phosphonium salts such as suphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, phosphorus compounds such as triphenylphosphine, organic compounds such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate In addition to alkali metal alcoholates such as carboxylates, sodium alcoholates and potassium alcoholates, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, zinc compounds such as zinc chloride, and the like. The amount of catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 100 ppm. When the amount of the catalyst exceeds 3000 ppm, the resin is vigorously colored and tends to adversely affect the stability of the product. Conversely, if the amount of catalyst used is less than 1 ppm, the rate of ring-opening polymerization of the cyclic ester tends to be extremely slow.

 A polyester residue having a hydroxyl group at one end is subjected to phosphoric esterification by reacting with one or a combination of two or more phosphorylating agents such as phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, and phosphorus oxychloride. Can do. Of these, one or more phosphate esterifying agents selected from the group consisting of orthophosphoric acid, polyphosphoric acid, and phosphorus pentoxide are preferred because there is no by-product such as hydrochloric acid gas and no special equipment is required. Of these, polyphosphoric acid having an orthophosphoric acid content of 116% is preferred.

 The ratio of the phosphoric acid esterifying agent is preferably such that the ratio of the phosphorus atom in the phosphoric acid esterifying agent to the hydroxyl group of the polyester residue having a hydroxyl group at one end is 0.5 to 1.5. It is more preferably 0 to 1.3, and most preferably 1.05 to 1.2. This is because when the ratio of the phosphorus atom to the epoxy group is less than 0.5, phosphoric acid esterification with respect to the hydroxyl group tends to be insufficient, and the amount of by-product of the phosphoric acid diester tends to increase. When it exceeds 5, there is a tendency that the effect of increasing the amount corresponding to the amount added cannot be obtained.

In the phosphoric acid ester represented by the general formula (3), it is preferable that the abundance ratio of y = 1 and y = 2 is 100: 0 to 100: 30 because the pigment dispersibility is good.
In addition, in the phosphate ester represented by the general formula (3), it is preferable that R ₄ is a polycaprolactone residue because pigment dispersibility, dry solubility, and substrate adhesion are improved. A polycaprolactone residue having a number average molecular weight of 500 to 3000 is more preferred.

Dispersant (A) having aromatic carboxyl group
The dispersant (A) having an aromatic carboxyl group of the present invention preferably has a number average molecular weight of 500 to 30,000. If it is less than 500 or more than 30,000, the viscosity and viscosity stability of the pigment dispersion may deteriorate, which is not preferable.
Moreover, it is preferable that the dispersing agent (A) which has an aromatic carboxyl group of this invention has an acid value of 10-200 mgKOH / g.

  The dispersant (A) having an aromatic carboxyl group of the present invention has an aromatic carboxyl group in the molecule. The production method includes, for example, production method 1 in which aromatic tricarboxylic acid anhydride (B1) and / or aromatic tetracarboxylic acid dianhydride (B2) is reacted with a polymer (C) having a hydroxyl group, aromatic carboxyl Production method 2 for producing a polymer using a monomer having a group, aromatic tricarboxylic acid anhydride (B1) and / or aromatic tetracarboxylic dianhydride (B2) while polymerizing a monomer having a hydroxyl group Any one of production methods 3 in which is reacted. Among these, from the viewpoint of pigment dispersibility, those produced by the production method 1 in which the number of aromatic carboxyl groups in the dispersant (A) can be more easily controlled are preferable.

<Polymer (C)>
As a polymer (C) having a hydroxyl group used as a precursor of a dispersant having an aromatic carboxyl group of the present invention, a polymer (C1) having a hydroxyl group at one end and a polymer having a hydroxyl group at a side chain ( C2). Furthermore, as the polymer (C1) having a hydroxyl group at one end, a polymer (C3) having two hydroxyl groups at one end is preferable.

[Polymer (C1)]
First, the polymer (C1) having a hydroxyl group at one end will be described. The polymer (C1) having a hydroxyl group at one end used in the present invention includes a polyester and / or polyether polymer (C1-1) having a hydroxyl group at one end and a vinyl polymer having a hydroxyl group at one end. (C1-2).
[Polyester and / or polyether polymer (C1-1)]
As the polyester and / or polyether polymer (C1-1) having a hydroxyl group at one end, those represented by the following general formula (4) are preferable.
General formula (4):

[In general formula (4),
Z ₁ is a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms,
Z ₂ is —O—, —S—, or —N (Rb) — (wherein Rb is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms),
Z ₃ is —OH;
G ₁ is a repeating unit represented by —R ₆ O—,
G ₂ is a repeating unit represented by —C (═O) R ₇ O—,
G ₃ is a repeating unit represented by —C (═O) R ₈ C (═O) —OR ₉ O—,
R ₆ is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms,
R ₇ is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
R ₈ is a linear or branched alkylene group having 2 to 6 carbon atoms, a linear or branched alkenylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or An arylene group having 6 to 20 carbon atoms,
R ₉ is —CH (R ₁₀ ) —CH (R ₁₁ ) —,
One of R ₁₀ and R ₁₁ is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group The alkyloxymethylene group having 1 to 20 carbon atoms in the moiety, the alkenyloxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, the aryl moiety having 6 to 20 carbon atoms in the aryl moiety, and optionally substituted with a halogen atom An aryloxymethylene group which may be present, an N-methylene-phthalimide group,
R ₅ is R ₆ , —C (═O) R ₇ —, or —C (═O) R ₈ C (═O) —OR ₉ —,
m ₁ is an integer from 0 to 100;
m ₂ is an integer of 0 to 60,
m ₃ is an integer from 0 to 30,
However, m ₁ + m ₂ + m ₃ is 1 or more and 100 or less,
The arrangement of the repeating units G _{1 to} G _{3 in} the general formula (4) does not limit the order, and in the polymer represented by the general formula (4), between the group Z ₂ and the group R _5. Indicates that the repeating units G _{1 to} G ₃ are included in an arbitrary order, and the repeating units G _{1 to} G ₃ may be either random type or block type. ]

In the general formula (4), Z ₁ is preferably a linear or branched alkyl group having 1 to 18 carbon atoms from the viewpoint of lowering the viscosity of the pigment dispersion and storage stability.

As another embodiment, Z ₁ in the general formula (4) preferably having an ethylenically unsaturated double bond. In this case, active energy ray curability can be imparted to the dispersant having an aromatic carboxyl group.
Further, in the above general formula (4), it m ₂ is an integer of 3 to 15 is preferable from the viewpoint of low viscosity and storage stability of the pigment dispersion.
In the general formula (4), when m ₂ = 0 and m ₃ = 0, Z ₁ is a linear or branched alkyl group having 1 to 7 carbon atoms, or an ethylenic group. It preferably has a saturated double bond.

  The polyester and / or polyether-based polymer (C1-1) having a hydroxyl group at one end represented by the general formula (4) can be produced by a known method, monoalcohol, primary monoamine, secondary It can be easily obtained by ring-opening polymerization of a cyclic compound selected from the group of alkylene oxide, lactone, lactide, dicarboxylic anhydride, and epoxide using a compound selected from the group of monoamine and monothiol as an initiator.

  The monoalcohol may be any compound as long as it is a compound having one hydroxyl group. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1 -Heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldeca Aliphatic monoalcohols such as nor, 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, or oleyl alcohol;

Monoalcohols having an aromatic ring such as benzyl alcohol, phenoxyethyl alcohol, paracumylphenoxyethyl alcohol; or
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, Ethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol Mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, Tripropylene glycol monomer Ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl Ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl A And alkylene glycol monoalkyl ethers such as tetra-propylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether.

  A monoalcohol having an ethylenically unsaturated double bond may be used as the monoalcohol. In this case, active energy ray-curing performance can be imparted to the produced dispersant having an aromatic carboxyl group.

  Examples of the group having an ethylenically unsaturated double bond include a vinyl group or a (meth) acryloyl group (hereinafter referred to as “(meth) acryloyl” or “(meth) acrylate”). Each represents “acryloyl and / or methacryloyl” or “methacrylate and / or acrylate”, with a (meth) acryloyl group being preferred. The type of the group having a double bond may be one type or a plurality of types.

  As the monoalcohol having an ethylenically unsaturated double bond, a compound containing one, two, and three or more ethylenically unsaturated double bonds can be used. Examples of the monoalcohol having one ethylenically unsaturated double bond include 2-hydroxyethyl (meth) acrylate (in the case of “(meth) acrylate”, acrylate and / or methacrylate). The same shall apply hereinafter.), 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl Ether, or 4-hydroxybutyl vinyl ether. Examples of the monoalcohol having two ethylenically unsaturated double bonds include 2-hydroxy-3-acryloyloxypropyl methacrylate, glycerin di (meth) acrylate, and the like. Examples of the monoalcohol having 3 ethylenically unsaturated double bonds include pentaerythritol triacrylate, and examples of the monoalcohol having 5 ethylenically unsaturated double bonds include dipentaerythritol pentaacrylate. Is mentioned.

Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are obtained as a mixture of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, respectively. Therefore, in order to control the molecular weight of the produced dispersant, HPLC (high speed It is necessary to determine the ratio of monoalcohols by liquid chromatography) method or hydroxyl value measurement. This is because the molecular weight of the dispersant is determined by the number of monoalcohols and the ratio of raw materials forming G _{1 to} G ₃ .

  Among the above-mentioned monoalcohols, those having two or more ethylenically unsaturated double bonds are preferable in the case of use in an active energy ray-curable pigment composition in terms of curability.

Examples of primary monoamines include:
Methylamine, ethylamine, 1-propylamine, isopropylamine, 1-butylamine, isobutylamine, tert-butylamine, 1-pentylamine, isopentylamine, 3-pentylamine, 1-hexylamine, cyclohexylamine, 4-methyl- 2-pentylamine, 1-heptylamine, 1-octylamine, isooctylamine, 2-ethylhexylamine, 1-nonylamine, isononylamine, 1-decylamine, 1-dodecylamine, 1-myristylamine, cetylamine, 1- Aliphatic primary monoamines such as stearylamine, isostearylamine, 2-octyldecylamine, 2-octyldodecylamine, 2-hexyldecylamine, behenylamine, or oleylamine;
3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 2-ethylhexyloxypropylamine, 3-isobutyroxypropylamine, 3-decyloxypropylamine, or 3- Alkoxyalkyl primary monoamines such as myristyloxypropylamine; or
Aromatic primary monoamines such as benzylamine are listed.
Examples of secondary monoamines include dimethylamine, diethylamine, di-1-propylamine, diisopropylamine, di-1-butylamine, diisobutylamine, di-1-pentylamine, diisopentylamine, and di-1-hexylamine. , Dicyclohexylamine, di- (4-methyl-2-pentyl) amine, di-1-heptylamine, di-1-octylamine, isooctylamine, di- (2-ethylhexyl) amine, di-1-nonylamine, Diisononylamine, di-1-decylamine, di-1-dodecylamine, di-1-myristylamine, dicetylamine, di-1-stearylamine, diisostearylamine, di- (2-octyldecyl) amine, di- (2 -Octyldodecyl) amine, di- (2-hexyldecyl) a Emissions, N- methylethylamine, N- methylbutylamine, N- methyl isobutyl amine, N- methyl-propylamine, N- methyl hexylamine, piperazine or secondary aliphatic monoamines such as alkyl-substituted piperazine,.

  Examples of the monothiol include methylthiol, ethylthiol, 1-propylthiol, isopropylthiol, 1-butylthiol, isobutylthiol, tert-butylthiol, 1-pentylthiol, isopentylthiol, 3-pentylthiol, 1- Hexylthiol, cyclohexylthiol, 4-methyl-2-pentylthiol, 1-heptylthiol, 1-octylthiol, isooctylthiol, 2-ethylhexylthiol, 1-nonylthiol, isononylthiol, 1-decylthiol, 1- Dodecylthiol, 1-myristylthiol, cetylthiol, 1-stearylthiol, isostearylthiol, 2-octyldecylthiol, 2-octyldodecylthiol, 2-hexyldecylthiol Aliphatic monothiols such as behenyl thiol or oleyl thiol; or alkyl thioglycolates such as methyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, methyl mercaptopropionate, octyl mercaptopropionate, mercapto And mercaptopropionic acid alkyl esters such as methoxybutyl propionate or tridecyl mercaptopropionate.

The compound selected from the group consisting of monoalcohol, primary monoamine, secondary monoamine, and monothiol as referred to in the present invention is not limited to the above examples, but is a hydroxyl group, primary amino group, secondary amino group, or thiol. Any compound can be used as long as it is a compound having one group, and it may be used alone or in combination of two or more.
Here, the portion of the monoalcohol, primary monoamine, secondary monoamine, or monothiol, excluding the hydroxyl group, primary amino group, secondary amino group, or thiol group, represents Z ₁ in the general formula (4). Configure.

From the above-exemplified monoalcohol, primary monoamine, secondary monoamine, and a compound selected from the group consisting of monothiols as an initiator, alkylene oxide, lactone, lactide, and a group consisting of a combination of dicarboxylic anhydride and epoxide The selected cyclic compound can be subjected to ring-opening polymerization to produce a polymer represented by the general formula (4) in which Z ₃ is —OH. However, the combination of the dicarboxylic acid anhydride and the epoxide is always used at the same time and is alternately polymerized.

Here, the reaction order of the cyclic compound selected from the group consisting of alkylene oxide, lactone, lactide, and a combination of dicarboxylic anhydride and epoxide may be any, for example, as the first step, the initiator After the alkylene oxide is polymerized, the lactone can be polymerized in the second stage, and the dicarboxylic acid anhydride and the epoxide can be alternately polymerized in the third stage. In this example, the initiator for polymerizing the lactone in the second stage is an alkylene oxide polymer having a hydroxyl group at one end polymerized in the first stage. The initiator for alternately polymerizing dicarboxylic acid anhydrides and epoxides in the third stage is a block copolymer of an alkylene oxide polymer having a hydroxyl group at one end and a lactone polymer polymerized by the second stage. It becomes a polymer. In the production method of the present invention, Z ₃ among the polymers represented by the general formula (4) is used as an initiator in the production of the polymer represented by the general formula (4) described below. A polymer represented by general formula (6) described later can be used as the initiator.

  The reaction sequence of the cyclic compound is not limited to the combination of the first-stage alkylene oxide, the second-stage lactone, and the third-stage dicarboxylic anhydride and epoxide, but the alkylene oxide, lactone (and / or lactide). , And a combination of a dicarboxylic acid anhydride and an epoxide can be carried out in any order one to several times. Alternatively, for any combination of alkylene oxide, lactone (and / or lactide), and dicarboxylic anhydride and epoxide, without performing any ring-opening polymerization, any cyclic compound may be selected from them, Ring-opening polymerization can also be carried out.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide, and the like. Or it can use in combination of 2 or more types. When two or more types of alkylene oxide are used in combination, the bond form may be random and / or block. As for the polymerization mole number of the alkylene oxide with respect to 1 mol of initiators, 0-100 are preferable.

The polymerization of the alkylene oxide can be carried out in a known manner, for example, in the presence of an alkali catalyst at a temperature of 100 to 200 ° C. under a pressurized state. An alkylene oxide polymer having a hydroxyl group at one end obtained by polymerizing an alkylene oxide to a hydroxyl group of a monoalcohol is commercially available, for example, a NOOX series manufactured by NOF Corporation, a BLEMMER series manufactured by NOF Corporation, Among the polymers represented by the general formula (4), Z ₃ is —OH, and G _{1 to} G ₃ having only G ₁ as a raw material for the dispersant having an aromatic carboxyl group of the present invention. It can also be used as it is. Specific examples of commercially available products include UNIOX M-400, M-550, M-2000, BLEMMER PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP- 1000, PP-500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 55PET-400, 30PET-800, 55PET-800, AET Series, 30PPT-800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, 10APB-500B, etc.

Here, the alkylene group of the alkylene oxide constitutes R ₆ in the repeating unit G ₁ in the general formula (4).

  Specific examples of lactones include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone. From the viewpoint of ring-opening polymerization, it is preferable to use δ-valerolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone.

  In the production method of the present invention, the lactone can be used without being limited to the above examples, and may be used alone or in combination of two or more. Use of two or more types in combination is preferable in terms of workability and compatibility with other resins, since the crystallinity may decrease and become liquid at room temperature.

As the lactide, those represented by the following general formula (5) are preferable (including glycolide).
General formula (5):

[In general formula (5),
R ₁₂ and R ₁₃ are each independently a hydrogen atom, a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms,
R ₁₄ and R ₁₅ are each independently a hydrogen atom, a halogen atom, or a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms. ]
As a raw material for the dispersant having an aromatic carboxyl group of the present invention, lactide particularly suitable is lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide (1,4-dioxane). -2,5-dione). Moreover, it is preferable that lactone is used among the said lactone or lactide as a raw material of the dispersing agent which has an aromatic carboxyl group of this invention.

  The ring-opening polymerization of lactone and / or lactide can be carried out in a known manner, for example, by introducing an initiator, lactone and / or lactide, and a polymerization catalyst into a reactor connected to a dehydrating tube or a condenser, and under a nitrogen stream. . When a monoalcohol having a low boiling point is used, the reaction can be carried out under pressure using an autoclave. Moreover, when using what has an ethylenically unsaturated double bond in monoalcohol, it is preferable to add a polymerization inhibitor and to react under a dry air flow.

  The number of moles of lactone and / or lactide polymerized relative to 1 mole of initiator is preferably in the range of 1 to 60 moles, more preferably 2 to 20 moles, and most preferably 3 to 15 moles.

As the polymerization catalyst for lactone and / or lactide, known ones can be used without limitation.
Quaternary ammonium such as tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, or benzyltrimethylammonium iodide salt;
Tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, Quaternary phosphonium salts such as tetraphenylphosphonium bromide or tetraphenylphosphonium iodide;
Phosphorus compounds such as triphenylphosphine;
Organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, or sodium benzoate;
Alkali metal alcoholates such as sodium alcoholate or potassium alcoholate; tertiary amines;
An organometallic compound such as an organotin compound, an organoaluminum compound, or an organotitanate compound; or
Examples thereof include zinc compounds such as zinc chloride.
The catalyst is used in an amount of 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. When the amount of the catalyst exceeds 3000 ppm, the resin may be intensely colored. On the contrary, if the amount of the catalyst used is less than 0.1 ppm, the rate of ring-opening polymerization of lactone and / or lactide becomes extremely slow, which is not preferable.

  The polymerization temperature of the lactone and / or lactide is 100 ° C to 220 ° C, preferably 110 ° C to 210 ° C. If the reaction temperature is less than 100 ° C, the reaction rate is very slow. If it exceeds 220 ° C, side reactions other than the addition reaction of lactone and / or lactide, for example, depolymerization of lactone adducts to lactone monomers, cyclic lactone dimers and trimers Generation is likely to occur.

Here, a portion other than the ester group of lactone or lactide constitutes R ₇ in the repeating unit G ₂ in the general formula (4).

  Examples of the dicarboxylic acid anhydride include succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, itaconic acid anhydride, glutaric acid anhydride, dodecenyl succinic acid anhydride, and chlorendec acid anhydride.

  Examples of the epoxide include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, phenyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, 2,4-dibromophenyl glycidyl ether, Examples include 3-methyl-dibromophenyl glycidyl ether (wherein the bromo substitution position is arbitrary), allyl glycidyl ether, ethoxyphenyl glycidyl ether, glycidyl (meth) acrylate, glycidyl phthalimide, or styrene oxide.

  Dicarboxylic anhydride and epoxide are used simultaneously for the initiator and react alternately. At this time, the hydroxyl group, primary amino group, secondary amino group, or thiol group of the initiator first reacts with the acid anhydride group of the dicarboxylic acid anhydride to form a carboxyl group, and then the epoxide is added to the carboxyl group. The epoxy group reacts to form a hydroxyl group. Further, the reaction similar to the above can be sequentially proceeded so that the acid anhydride group of the dicarboxylic acid anhydride reacts with this hydroxyl group. The number of moles of polymerization of dicarboxylic anhydride and epoxide with respect to 1 mole of initiator is preferably 0 to 30 moles. Moreover, the reaction ratio ([D] / [E]) of dicarboxylic acid anhydride and epoxide is:

0.8 ≦ [D] / [E] ≦ 1.0
([D] is the number of moles of dicarboxylic anhydride, and [E] is the number of moles of epoxide)
It is preferable that If it is less than 0.8, the epoxide remains undesirably, and if it exceeds 1.0, a polymer having a hydroxyl group at one end cannot be obtained, and a polymer having a carboxyl group at one end is formed, which is not preferable.

  The alternating polymerization of the dicarboxylic acid anhydride and the epoxide is preferably performed in the range of 50 ° C to 180 ° C, more preferably 60 ° C to 150 ° C. When the reaction temperature is less than 50 ° C or exceeds 180 ° C, the reaction rate is extremely slow.

Here, the portion other than the dicarboxylic anhydride group of the dicarboxylic anhydride constitutes R ₈ in the repeating unit G ₃ in the general formula (5), and the portion other than the oxygen atom that forms the cyclic ether of the epoxide It constitutes R ₉ in the repeating unit G ₃ in the formula (4).

When the monoalcohol, dicarboxylic acid anhydride, or epoxide having an ethylenically unsaturated double bond is used when producing the polymer represented by the general formula (4), a polymerization inhibitor may be used. preferable. As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, phenothiazine and the like are preferable, and these may be used alone or in combination from 0.01% to 6%. %, Preferably in the range of 0.05% to 1.0%.
Vinyl polymer having a hydroxyl group at one end (C1-2)
As the vinyl polymer (C1-2) having a hydroxyl group at one end, a polymer represented by the following general formula (6) is preferable.
General formula (6):

[In General Formula (6), Z ₄ is a polymerization termination group of a vinyl polymer, Z ₆ is —OH or —R ₂₀ (OH) ₂ , and R ₂₀ has 1 to 18 carbon atoms. R ₁₆ and R ₁₇ are each independently a hydrogen atom or a methyl group, one of R ₁₈ and R ₁₉ is a hydrogen atom, and the other is an aromatic group, Or —C (═O) —Z ₇ —R ₂₁ (wherein Z ₇ is —O— or —N (R ₂₂ ) —, R ₂₁ and R ₂₂ are each a hydrogen atom or a carbon atom number of 1 to 18) Or a linear or branched alkyl group having 1 to 18 carbon atoms having an aromatic group as a substituent, and Z ₅ is —O—R ₂₃ —, or _{-S-R 23} - a _{and, R 23} is a direct bond, or straight-chain having 1 to 18 carbon atoms Or a branched alkylene group, _{n 1} is 2-50.]
The polymer represented by the general formula (6) is a vinyl polymer obtained by polymerizing an ethylenically unsaturated monomer.

The portion of the repeating unit of the polymer represented by the general formula (6), that is, {-[C (R ₁₆ ) (R ₁₈ ) -C (R ₁₇ ) (R ₁₉ )] n _1- } is mutually They may be the same (homopolymer) or different (copolymer). In a preferred form of the polymer represented by the general formula (5), R ₁₆ and R ₁₇ are either a hydrogen atom, the other is a hydrogen atom or a methyl group, and R ₁₈ and R ₁₉ are either One is a hydrogen atom and the other is —C (═O) —O—R ₂₄ (R ₂₄ is a linear or branched alkyl group having 1 to 8 carbon atoms and has an aromatic group as a substituent. And —Z ₅ —Z ₆ is —S—CH ₂ CH ₂ —OH or S—CH ₂ CH (OH) CH ₂ —OH.

Z ₄ in the general formula (6), that is, the polymerization termination group of the vinyl polymer is any known polymerization termination introduced when the usual ethylenically unsaturated monomer is polymerized in the usual manner. And is obvious to those skilled in the art. Specifically, for example, it can be a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Even Z ₄ are have any chemical structure of these, the dispersants of this invention, without being affected by the polymerization terminating group Z _4, can exert its effect.

Among the polymers represented by the general formula (6), those in which Z ₆ is —OH can be produced by a known method, for example, a compound having a hydroxyl group and a thiol group and an ethylenically unsaturated monomer. Can be obtained by mixing and heating.
Examples of the compound having a hydroxyl group and a thiol group in the molecule include mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol, and 2-mercapto-3-butanol. Can be mentioned.

Among the polymers represented by the general formula (6), those in which Z ₆ is —R ₂₀ (OH) ₂ can be produced by a known method, for example, a compound having two hydroxyl groups and one thiol group It can be obtained by mixing and heating an ethylenically unsaturated monomer. In this case, among the polymers (C) having a hydroxyl group at one end, the polymer (C3) having two hydroxyl groups at one end, which is the most preferable mode, is obtained.

  Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-1,2-propanediol. (Thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto- Examples include 2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

  Preferably, bulk polymerization or solution polymerization is performed using a compound having 1 to 30 parts by weight of a hydroxyl group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours. If the compound having a hydroxyl group and a thiol group is less than 1 part by weight, the molecular weight is increased, and the viscosity of the dispersion is sometimes increased, which is not preferable. If it exceeds 30 parts by weight, the molecular weight is decreased, and the steric repulsion effect due to the solvent-affinity vinyl polymer portion is decreased, which may be undesirable.

  Since the thiol group becomes a radical generating group for polymerizing the ethylenically unsaturated monomer, another polymerization initiator is not necessarily required for the polymerization, but it can also be used. When using this polymerization initiator, 0.001-5 weight part is preferable with respect to 100 weight part of ethylenically unsaturated monomers.

 As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer include acrylic monomers and monomers other than acrylic monomers. Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate Or (meth) acrylates such as ethoxypolyethylene glycol (meth) acrylate, or (meth) acrylamide (in addition, “(meth) acrylamide” indicates acrylamide and / or methacrylamide) The same shall apply hereinafter), (meth) such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine. Examples include acrylamides.

  Examples of the monomer other than the acrylic monomer include styrenes such as styrene and α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether. Examples thereof include vinyl ethers, and fatty acid vinyls such as vinyl acetate and vinyl propionate. The monomer other than the acrylic monomer can be used in combination with the acrylic monomer.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used alone or in combination with the monomer. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-couplerlactone-added acrylic acid, ε-couplerlactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, or croton. An acid etc. are mentioned and 1 type (s) or 2 or more types can be selected.

  In the step of producing the polymer represented by the general formula (6), no solvent or a solvent can be used in some cases. Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used, but is not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used.

  The amount of the solvent used is preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. The solvent used can be removed by an operation such as distillation after completion of the reaction, or can be used as it is as a part of the product of the dispersant.

Polymer having hydroxyl group in side chain (C2)
The polymer (C2) having a hydroxyl group in the side chain of the present invention can be obtained by polymerizing an ethylenically unsaturated monomer having a hydroxyl group and, if necessary, another ethylenically unsaturated monomer. As an ethylenically unsaturated monomer having a hydroxyl group,
(Meth) acrylate monomers having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate Or a hydroxyalkyl (meth) acrylate such as cyclohexanedimethanol mono (meth) acrylate, or an alkyl-α-hydroxyalkyl acrylate such as ethyl-α-hydroxymethyl acrylate, or
A (meth) acrylamide monomer having a hydroxyl group, for example, N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, or N- (2-hydroxybutyl) ( N- (hydroxyalkyl) (meth) acrylamide such as (meth) acrylamide, or
A vinyl ether monomer having a hydroxyl group, for example, a hydroxyalkyl vinyl ether such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, or 2- (or 3- or 4-) hydroxybutyl vinyl ether, or
Allyl ether monomers having a hydroxyl group, for example, hydroxyalkyl such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, or 2- (or 3- or 4-) hydroxybutyl allyl ether Examples include allyl ether.
Moreover, the monomer which has two hydroxyl groups, such as glycerol mono (meth) acrylate, is also mentioned. Further, a product obtained by reacting an ethylenically unsaturated monomer having a cyclic ether group such as an epoxy group with a carboxyl group-containing ethylenically unsaturated monomer such as (meth) acrylic acid, or (meth) acrylic acid Examples include those obtained by reacting a carboxyl group-containing ethylenically unsaturated monomer such as a monofunctional cyclic ether compound such as a monofunctional epoxy compound.

  In addition, the above-mentioned hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether hydroxyalkyl allyl ether, or glycerol mono (meth) acrylate, alkylene oxide and An ethylenically unsaturated monomer obtained by adding lactone can also be used as an ethylenically unsaturated monomer having a hydroxyl group in the method of the present invention. Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, or 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide. Can be used. When two or more types of alkylene oxide are used in combination, the bond form may be random and / or block. Examples of the lactone to be added include δ-valerolactone, ε-caprolactone, or ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these can also be used. . What added both alkylene oxide and lactone may be used.

The copolymerization ratio between the ethylenically unsaturated monomer having a hydroxyl group and another ethylenically unsaturated monomer is determined so that an average of at least 0.3 to 177 hydroxyl groups per molecule after polymerization. Is preferred.
Examples of other ethylenically unsaturated monomers include the acrylic monomers described in the process for producing the polymer represented by the general formula (6) and monomers other than the acrylic monomers. Can be used arbitrarily.

  As the polymerization initiator, for example, an azo compound or an organic peroxide described in the process for producing the polymer represented by the general formula (6) can be used. When using this polymerization initiator, 0.01-20 weight part is preferable with respect to 100 weight part of ethylenically unsaturated monomers.

 As the polymerization solvent, for example, the solvent described in the process for producing the polymer represented by the general formula (6) can be used in the same manner.

Reaction of OH Resin with Acid Anhydride Next, a polymer having a hydroxyl group at one end (C1) or a polymer having a hydroxyl group at the side chain (C2) and a tricarboxylic acid anhydride (B1) “and / or a tetracarboxylic acid diacid” The step of reacting the anhydride (B2) will be described.

  The hydroxyl group of the polymer (C1) having a hydroxyl group at one end or the polymer (C2) having a hydroxyl group in the side chain, an aromatic tricarboxylic acid anhydride (B1) and / or an aromatic tetracarboxylic dianhydride ( By reacting with the anhydride group of B2), the dispersant having an aromatic carboxyl group of the present invention can be obtained.

  Examples of the aromatic tricarboxylic acid anhydride (B1) include benzene tricarboxylic acid anhydride (1,2,3-benzene tricarboxylic acid anhydride, trimellitic acid anhydride (1,2,4-benzene tricarboxylic acid anhydride). Etc.), naphthalene tricarboxylic acid anhydride (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,8 -Naphthalene tricarboxylic acid anhydride), 3,4,4'-benzophenone tricarboxylic acid anhydride, 3,4,4'-biphenyl ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydride, 2 , 3,2′-biphenyltricarboxylic anhydride, 3,4,4′-biphenylmethanetricarboxylic anhydride, or 3 And the like 4,4'-biphenyl sulfonic tricarboxylic anhydride.

  Examples of the aromatic tetracarboxylic dianhydride (B2) include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetra Carboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyl Rudiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4 ′ -Bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-di Carboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis ( Phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, M-phenylene-bis (triphenylphthalic acid) Anhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-di Carboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, and the like.

  The aromatic tricarboxylic acid anhydride (B1) and aromatic tetracarboxylic acid dianhydride (B2) used in the present invention are not limited to the compounds exemplified above, and may have any structure. These may be used alone or in combination. Those used in the present invention are preferably trimellitic anhydride and pyromellitic dianhydride.

  The number of moles of the hydroxyl group of the polymer (C) is <H>, and the number of moles of the carboxylic acid anhydride group of the aromatic tricarboxylic acid anhydride (B1) or aromatic tetracarboxylic dianhydride (B2) is <N>. The reaction ratio is preferably 0.3 ≦ <H> / <N> ≦ 3, and more preferably 0.5 ≦ <H> / <N> ≦ 2. In particular, when the polymer (C3) is used as the polymer (C1), it is preferable that 1 <H> / <N> ≦ 2. If the reaction is carried out with <H> / <N> <1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water or alcoholicized with a monofunctional alcohol.

  When the polymer (C2) is used, it is preferable to introduce 0.3 to 3 aromatic tricarboxylic acids and / or aromatic tetracarboxylic acids into one molecule. Specifically, the number average molecular weight of the polymer (C2) was measured, and when the measured value was [X], when using the aromatic tricarboxylic acid anhydride (B1), the resin [X] g And 0.3 to 3 mol of aromatic tricarboxylic acid anhydride may be reacted. On the other hand, when aromatic tetracarboxylic dianhydride (B2) is used, 0.15 mol or more and 1.5 mol or less of aromatic tetracarboxylic dianhydride is reacted with resin [X] g. good. This is because the aromatic tetracarboxylic dianhydride has two acid anhydride groups, so that it is half the amount when the aromatic tricarboxylic acid anhydride (B1) is used to bridge the polymer (C2) molecule. This is because it is good.

  A catalyst may be used for the reaction of the polymer (C) with the aromatic tricarboxylic acid anhydride (B1) or the aromatic tetracarboxylic acid dianhydride (B2). As the catalyst, for example, a tertiary amine compound can be used, for example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-. Examples include undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene.

  The reaction of the polymer (C) with the aromatic tricarboxylic acid anhydride (B1) or the aromatic tetracarboxylic acid dianhydride (B2) may be carried out without a solvent or using a suitable dehydrated organic solvent. Also good. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a part of the product of the dispersant. Although the solvent to be used is not particularly limited, the solvent described in the process for producing the polymer represented by the general formula (6) can be used in the same manner.

  The reaction temperature between the polymer (C) and the aromatic tricarboxylic acid anhydride (B1) or aromatic tetracarboxylic dianhydride (B2) is preferably 50 ° C to 180 ° C, more preferably 60 ° C to 160 ° C. Perform in the range. When the reaction temperature is less than 50 ° C., the reaction rate is slow. When the reaction temperature exceeds 180 ° C., the acid anhydride that has reacted and opened the ring forms a cyclic anhydride again, which may make it difficult to complete the reaction.

 Solvents used in the pigment dispersion of the present invention include, for example, propylene glycol diacetate, propylene glycol monomethyl ether, diethylene glycol diethyl ether, methyl isobutyl ketone, n-butyl alcohol and its isomer, n-pentyl alcohol and its isomer, n -Hexyl alcohol and its isomers, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether , Dipropylene glycol monobutyl ether, tripropylene glycol monomethyl 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, propylene Glycol monoethyl ether acetate, 3-methoxybutyl acetate And cyclopentanone, cyclohexanone, methylcyclohexanone, toluene, o-xylene, m-xylene, p-xylene, methyl 3-methoxypropionate, butyl acetate, isobutyl acetate, propyl acetate and the like. These solvents can be used alone or in combination.

  The solvent can be used in an amount of 100 to 4000 parts by weight, preferably 150 to 1000 parts by weight, based on 100 parts by weight of the solid content in the pigment dispersion.

  Next, an ink using the pigment dispersion of the present invention contains the pigment dispersion of the present invention and a pigment carrier.

  The pigment carrier is constituted by a resin, its precursor or a mixture thereof. In the case of producing a color filter using the ink of the present invention, it is preferable to use a transparent resin having a transmittance of 80% or more, particularly 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. .

  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 pigment dispersion. 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 pigment dispersion. 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, based on 100 parts by weight of the pigment composition in the pigment dispersion.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like.

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

  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.

  When the ink of the present invention is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator is added. Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone-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 ink of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time of the dispersion. 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 ink of the present invention can be applied to the ink of the present invention, as 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, and an improved coating property. Additives such as agents or development improvers can be added.

  As a method for producing a pigment dispersion in the present invention, a production process using a conventionally known kneader or disperser can be used. Examples of dispersers used include 2-roll mill, 3-roll mill, kneader, pressure kneader, continuous kneader, extruder, continuous extruder, ball mill, attritor, sand mill, coball mill, agitator mill, super mill, and shot mill. , Pin mills, jet mills, disk mills, homogenizers, basket mills, pebble mills, Henschel mixers, super mixers, planetary mixers, dissolvers, ultrasonic dispersers and the like can be used alone or in combination of two or more.

Various materials such as glass, steel, and ceramic can be used for dispersion. However, in order to avoid the influence of foreign matters due to wear or breakage, ceramic is preferable, and zirconia or the like having high hardness is particularly preferable.
The bead size is selected according to the pigment to be used and the target performance, but fine beads are preferable to achieve a high contrast by dispersing the finely divided pigment, and the effect of the present invention is maximized. Therefore, 0.5 μm or less is desirable.

  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 pigment dispersion.

Examples using the organic dye derivative of the present invention will be shown and described below. In each example, unless otherwise specified, “parts” represents parts by weight, and “%” represents percent by weight.
Examples of manufacturing dispersants

<Production example of general formula (3)>
Production Example 1
In a reaction vessel equipped with a nitrogen gas introduction tube, a condenser and a stirrer, 186 g of lauryl alcohol, 571 g of ε-caprolactone monomer, tetrabutyl titanate 0. After charging 6 g and replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 3 hours. The disappearance of the caprolactone monomer was confirmed by a GPC (gel permeation chromatography) RI detector using tetrahydrofuran as an eluent. After cooling to 40 ° C. or lower, mixed with 84.5 g of polyphosphoric acid having an orthophosphoric acid content of 116%, gradually heated, heated with stirring at 80 ° C. for 6 hours, and the number average molecular weight of R ₄ 760 Dispersant K1 having an abundance ratio of y = 1 and 2 of 100: 12 was obtained. The acid value of the reaction product was 166.

<Production Example of Dispersant (A) Having Aromatic Carboxyl Group>
Production Example 2
A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added here, and it was made to react at 120 degreeC for 2 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was completed to obtain a dispersant. Thus, Dispersant A1 having an aromatic carboxyl group having an acid value of 49 mgKOH / g per solid and a number average molecular weight (Mn) of 2,500 was obtained.

Production Example 3
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of methoxypropyl acetate were charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2′-azobisisobutyronitrile is divided into 20 portions. It was added every minute and reacted for 12 hours at 80 ° C., and it was confirmed by solid content measurement that 95% had reacted. Next, 30 parts of pyromellitic anhydride, 190 parts of methoxypropyl acetate and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. I let you. It was confirmed by titration that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. An aromatic carboxyl group having an acid value per solid content of 42 mgKOH / g and a number average molecular weight (Mn) of 4,100 was obtained. Dispersant A2 was obtained.

Production Example 4
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 2 parts of a mixed solution in which 28 parts of benzyl methacrylate, 20 parts of butyl acrylate, 12 parts of 2-hydroxyethyl methacrylate, 40 parts of methoxypropyl acetate and 6 parts of dimethyl-2,2′-azobisdiisobutyrate are uniformly mixed in advance. The solution was added dropwise over a period of time, and then stirred at the same temperature for 3 hours to complete the reaction. In this way, an intermediate having a number average molecular weight of 3,800 and an average number of hydroxyl groups in one molecule of 3.5 was obtained. The intermediate was charged with 100 parts of solid, 5.1 parts of trimellitic anhydride, and 0.1 part of dimethylbenzylamine, and reacted at 100 ° C. for 6 hours. Thus, dispersant A3 having an aromatic carboxyl group having an average number of trimellitic acids per molecule of 1, an acid value of 30 mgKOH / g per solid content, and a number average molecular weight (Mn) of 4,000 is obtained. Obtained.

[Example 1]
Pigment Green 36 (Lionol Green 6YK: manufactured by Toyo Ink Co., Ltd.) 11 parts, organic dye derivative (D3) 0.2 part, organic dye derivative (D4) 0.8 part, dispersant A1 4.0 parts, acrylic resin (acid 4.0, Mw 17000) 4.0 parts and 80.0 parts of propylene glycol methyl ether acetate were mixed and dispersed for 5 hours using a sand mill filled with zirconia beads having a diameter of 0.5 mm.

Organic dye derivative (D3)

Organic dye derivative (D4)

[Example 2]
A pigment dispersion was obtained in the same manner as in Example 1 except that Pigment Green 36 was changed to Pigment RED254 (Irga Fore Red B-CF: manufactured by Ciba Specialty Chemicals).
[Example 3]
A pigment dispersion was obtained in the same manner as in Example 1 except that Pigment Green 36 was changed to Pigment Yellow 150 (E4GN: manufactured by LANXESS).
[Example 4]
A pigment dispersion was obtained in the same manner as in Example 1, except that the organic dye derivative (D3) was changed to 0.1 part and the organic dye derivative (D4) was changed to 0.9 part.
[Example 6]
A pigment dispersion was obtained in the same manner as in Example 2, except that the organic dye derivative (D3) was changed to 0.1 part and the organic dye derivative (D4) was changed to 0.9 part.
[Example 8]
A pigment dispersion was obtained in the same manner as in Example 1 except that the dispersant A1 was changed to K1.

[Example 9]
A pigment dispersion was obtained in the same manner as in Example 4 except that the dispersant A1 was changed to K1.
[Example 11]
A pigment dispersion was obtained in the same manner as in Example 1, except that the dispersant A1 was changed to A2.
[Example 12]
A pigment dispersion was obtained in the same manner as in Example 4, except that the dispersant A1 was changed to A2.
[Example 14]
A pigment dispersion was obtained in the same manner as in Example 1, except that the dispersant A1 was changed to A3.
[Example 15]
A pigment dispersion was obtained in the same manner except that the dispersant A1 was changed to A3 in Example 4.

[Comparative Example 1]
A pigment dispersion was obtained in the same manner as in Example 1 except that the organic dye derivative (D3) was changed to 0 part and the organic dye derivative (D4) was changed to 1 part.
[Comparative Example 2]
A pigment dispersion was obtained in the same manner as in Example 1, except that 1 part of the organic dye derivative (D3) and 0 part of the organic dye derivative (D4) were changed.
[Comparative Example 3]
A pigment dispersion was obtained in the same manner as in Example 1, except that the organic dye derivative (D3) was changed to 0.8 part and the organic dye derivative (D4) was changed to 0.2 part.
[Comparative Example 4]
A pigment dispersion was obtained in the same manner as in Comparative Example 1 except that Pigment Green 36 was changed to Pigment RED254 (Irga Fore Red B-CF: manufactured by Ciba Specialty Chemicals).
[Comparative Example 5]
A pigment dispersion was obtained in the same manner as in Comparative Example 2, except that Pigment Green 36 was changed to Pigment RED254 (Irga Fore Red B-CF: manufactured by Ciba Specialty Chemicals).

The present invention makes it possible to disperse highly fine pigments, which has been difficult with the prior art, and to achieve a very high contrast. Therefore, it can be expected to be applied to high-definition televisions and monitors.

Claims (4)

Following at least a pigment, dispersing agent, a pigment composition comprising a solvent and an organic dye induction body (D), an organic dye derived material organic dye derived material (D) is represented by the following general formula (1) and (D1) includes organic dye derived derivatives represented by the general formula (2) and (D2), D1: the weight ratio of D2 is 5: 95 to 40: pigment dispersions for color filters, which is a 60.
General formula (1):

General formula (2):

The symbols in the formula have the following meanings.
Q; azo colorant residue X; direct binding
R ₁ ;

(Y ₂ ; —NH— or —O—)
(R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group, or R ₂ and R ₃ may form a heterocycle containing at least a nitrogen atom.)
m: integer of 1-6 n: integer of 1-4 Pigment and an organic dye induction body ratio of (D) is 100: 0.1 to 100: 11 for a color filter pigment dispersion of claim 1 wherein the a.   The dispersant (A) having an aromatic carboxyl group is a reaction between the aromatic tricarboxylic acid anhydride (B1) and / or the aromatic tetracarboxylic acid anhydride (B2) and the polymer (C) having a hydroxyl group. The pigment dispersion for a color filter according to claim 1 or 2, wherein A pigment ink for a color filter comprising the pigment dispersion for a color filter according to any one of claims 1 to 3.