TWI519612B - Pigment composition and color filter - Google Patents

Description

Pigment composition and color filter

The present invention relates to a pigment composition excellent in dispersibility, fluidity, storage stability, and brightness.

In general, when a pigment composition is produced, it is known that it is difficult to stably disperse the pigment at a high concentration, which causes various problems in the production steps and the product itself.

For example, a pigment composition containing a pigment composed of fine particles tends to exhibit high viscosity, which is difficult to remove or transport from a disperser of a product, and causes gelation during storage and even difficulty in use. Further, regarding the surface of the coloring matter of the pigment composition, a poor state such as a decrease in gloss and a poor leveling property may occur. Further, when various pigments are used in combination, color separation due to aggregation or precipitation or the like may cause color unevenness in the color former or a significant decrease in coloring power.

Therefore, in general, a dispersant is used in order to maintain a good dispersion state. The dispersant has a structure in which a portion adsorbed to the pigment and a portion having a high affinity for a solvent as a dispersion medium, and the performance of the dispersant is determined by the balance of the two functional sites. The dispersant is used in combination with the surface state of the pigment of the dispersion, and various dispersants can be used, but with a partial alkali The pigment of the surface is generally a dispersing agent having an acidic functional group for electrostatic adsorption. At this time, the acidic functional group becomes an adsorption site of the pigment. A dispersing agent having a carboxylic acid as an acidic functional group is described in, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4.

However, on the other hand, a dispersing agent having an acidic functional group is mostly ineffective for a pigment having an acidic surface. Therefore, for a pigment having an acidic surface, a basic dispersant is used, and the structure of the alkaline dispersant is controlled to have a configuration such as a block type configuration or a comb type configuration. However, in the case of a block type, a complicated polymerization method such as living radical polymerization or the like must be used for its production (refer to Patent Document 5). Further, in the case of a comb type, a functional group having a carboxyl group or an acryloyl group is used as a comb tooth portion, and a polyamine compound having a primary and/or secondary amine is grafted to form a residue. The method of adsorbing a functional group on the surface of the pigment by the amine of the first and/or second order (refer to Patent Documents 6 and 7), so that the amine of the first-order and/or the second-order amine has a highly reactive active hydrogen, and there is a pigment-containing It is not preferable because the chemical structure is changed in kind and the hue is changed. Further, since the alkaline dispersant contains an amine moiety having a high basicity, the resin is heated and yellowed. Thus, the brightness of the color filter is lowered.

In addition, it has been proposed to use a dispersant having a structurally controlled dispersant and a basic resin having an uncontrolled structure to maintain the dispersed state of the pigment well (refer to Patent Documents 8 and 9). . However, the basic resin described herein is sufficient for the effect of inkjet inks when the pigment particle size is large when the pigment particle size is large, such as the use of a general coating material, the use of a lithographic ink, or the use of a gravure ink. Color filter Finer pigments such as the use of ink are insufficient in fluidity and storage stability.

In the use of the color filter, a pigment composition having excellent dispersibility, fluidity, and storage stability is disclosed in the above-described Patent Document Nos. 8 and 9 (refer to Patent Document 10). However, the basic resin containing a tertiary amine group described herein has a higher amine value than a primary or secondary amine, and has a problem of lowering the brightness, and cannot achieve a high brightness which has been demanded in recent years. Color filter.

Further, a coloring composition for a color filter using a polymer derived from an ethylenically unsaturated monomer having a hindered amine skeleton of an alicyclic tertiary amine group has been proposed (refer to Patent Document 11). However, since the resin derived from the hindered amine skeleton is used alone, the dispersibility is low and the stability with time is low. Further, there is no description about the use of a dispersing agent having an aromatic carboxyl group in combination.

Prior technical literature Patent literature

Patent Document 1: JP-A-61-61623

Patent Document 2: Japanese Patent Publication No. 1-141968

Patent Document 3: JP-A-2-219866

Patent Document 4: Japanese Laid-Open Patent Publication No. Hei 11-439842

Patent Document 5: Japanese Patent Publication No. 2002-534542

Patent Document 6: Japanese Patent Publication No. 08-038875

Patent Document 7: Japanese Patent Publication No. 08-143813

Patent Document 8: Japanese Patent Publication No. 5-9405

Patent Document 9: Japanese Laid-Open Patent Publication No. Hei 10-338835

Patent Document 10: JP-A-2009-185277

Patent Document 11: JP-A-2010-54808

It is an object of the present invention to provide a pigment composition which is of course used for coatings, lithographic inks and gravure inks, and the like, even if it is finer for inkjet inks, color filter inks, and the like. The use of the pigment particle size also exhibits excellent dispersibility, fluidity, storage stability, adhesion, and brightness.

The present invention relates to a pigment composition comprising a pigment, a resin type dispersant (A) having an aromatic carboxyl group, and a vinyl resin type dispersant (B) having a piperidyl skeleton.

Furthermore, the present invention relates to the above pigment composition, wherein the resin type dispersant (A) having an aromatic carboxyl group is a polymer (C) having a hydroxyl group and an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic acid. A resin type dispersant obtained by reacting acid dianhydride (D2).

Further, the present invention relates to a pigment composition, wherein the pigment is capable of adsorbing the amine of 50 to 700 micromolar / g (μ mol / g).

Moreover, the present invention relates to the aforementioned pigment composition, wherein the polymer (C) having a hydroxyl group is a polymer (C1) having a hydroxyl group at a single terminal.

Moreover, the present invention relates to the aforementioned pigment composition, wherein the polymer (C) having a hydroxyl group is a polymer (C2) having a hydroxyl group in a side chain.

Moreover, the present invention relates to the aforementioned pigment composition, wherein the polymer (C1) having a hydroxyl group at a single terminal is a polymer (C3) having two hydroxyl groups at a single terminal.

Furthermore, the present invention relates to the above pigment composition, wherein the vinyl resin type dispersant (B) having a piperidinyl skeleton has an amine value of 50 to 350 mgKOH/g.

Moreover, the present invention relates to the aforementioned pigment composition, wherein the pigment is a zinc phthalocyanine pigment.

Moreover, the present invention relates to the aforementioned pigment composition, which further contains a photopolymerizable monomer and/or a photopolymerization initiator.

Furthermore, the present invention relates to a color filter characterized in that a filter segment formed of the pigment composition is provided on a substrate.

According to the present invention, by using a resin-type dispersant (A) having an aromatic carboxyl group and a vinyl-based resin type dispersant (B) having a piperidinyl skeleton, a dispersibility, fluidity, and A pigment composition having both stability and adhesion and brightness, and a color filter excellent in brightness using the same are stored.

First, each constituent component of the pigment composition of the present invention will be described.

Furthermore, in this case, the note is "(meth) acrylonitrile. When "(meth)acrylic acid group", "(meth)acrylic acid", "(meth)acrylic acid ester", and "(meth)acryloxyloxy group", unless otherwise specified, "Acrylhydrazine and/or methacrylic acid", "acrylic and/or methacrylic", "acrylic and/or methacrylic", "acrylate and/or methacrylate" and "propylene" Alkoxy and/or methacryloxycarbonyl.

<pigment>

The pigment composition of the present invention comprises a pigment, a resin type dispersant (A) having an aromatic carboxyl group, and a vinyl resin type dispersant (B) having a piperidinyl skeleton, the vinyl group having a piperidinyl skeleton The resin-type dispersant (B) is adsorbed on the surface of the pigment, and the surface of the resin can be made alkaline even if it has a neutral-acidic surface. On the other hand, the resin-type dispersant (A) having an aromatic carboxyl group is the remaining amine group and aromatic carboxyl group of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton adsorbed on the surface. The electrostatic interaction is carried out, and at the same time, by the affinity of the polymer portion present in the resin-type dispersant (A) having an aromatic carboxyl group and the solvent of the dispersion medium, the pigment can be stably present in the dispersion medium.

The red pigment which can be used in the present invention may, for example, be CI (color index) pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52, 53, 57, 57:1, 81, 81:1, 81:2 81:3, 81:4, 83, 88, 90, 97, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 226, 238, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, or the diketopyrrolopyrrole pigment described in Japanese Patent Laid-Open Publication No. 2011-523433, but is not particularly limited to these. . Further, a red dye such as xanthene, azo, disazo or fluorene may also be used. Specific examples thereof include a salt-forming compound of a xanthene-based acid dye such as C.I. Acid Red 52, 87, 92, 289, and 338.

The orange pigment which can be used in the present invention may, for example, be C.I. Pigment Orange 13, 13, 37, 38, 43, 51, 55, 59, 61, 64, 71, 73 or 74, but is not particularly limited thereto.

The yellow pigment which can be used in the present invention may, for example, be CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127,128,129,137,138,139,147,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221, etc., but is not particularly limited to such . Further, a quinoline system, an azo system, a disazo system, a methine group or the like can also be used. Yellow dye.

The green pigment which can be used in the present invention, for example, CI Pigment Green 7, 10, 36, 37, and 58, Japanese Laid-Open Patent Publication No. 2008-19383, JP-A-2007-320986, and JP-A-2004-70342 The zinc phthalocyanine pigment or the like described is not particularly limited to these.

The blue pigment which can be used in the present invention may, for example, be CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22 The aluminum phthalocyanine pigments described in Japanese Patent Publication No. 2004-333817 and Japanese Patent No. 4893859 are not particularly limited.

The purple pigment which can be used in the present invention may, for example, be CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50, etc., but are not particularly limited to these.

Preferred pigments which can be used in the present invention include, for example, a diketopyrrolopyrrole-based organic pigment, a naphthol-based organic pigment, an anthraquinone-based organic pigment, a phthalocyanine-based organic pigment, and a quinophthalone-based organic pigment.

The diketopyrrolopyrrole type organic pigment is a red-orange pigment having excellent light resistance and heat resistance. Specific examples of the diketopyrrolopyrrole-based organic pigment, when represented by a color index number, may, for example, be C.I. Pigment Red 254, 255, 264 or 272, or C.I. Pigment Orange 71, 73 or 81, or the like. Further, the brominated diketopyrrolopyrrole pigment described in JP-A-2011-523433 is preferably used.

The naphthol azo organic pigment is a red organic pigment having excellent light resistance and heat resistance. Specific examples of the naphthol azo organic pigments, which are represented by color index numbers, may be, for example, CI Pigment Red 30, 112, 114, 119, 150, 163, 170, 176, 183, 187, 188, 208, 253, 268, 269, etc.

The lanthanide organic pigment is a red organic pigment having excellent light resistance and heat resistance. Specific examples of the lanthanoid organic pigments, which are represented by color index numbers, may be, for example, C.I. Pigment Red 177 or the like.

The phthalocyanine-based organic pigment is a blue or green organic pigment having excellent light resistance and heat resistance. Specific examples of the blue phthalocyanine-based organic pigment, when represented by a color index number, may be, for example, CI Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16 Or a specific example of the green phthalocyanine-based organic pigment, such as 17 or the like, may be, for example, CI Pigment Green 7, 36 or 58. Further, an aluminum phthalocyanine pigment described in Japanese Patent No. 4893859 or the like can be preferably used.

<dye>

The pigment composition of the present invention can be used in combination as a coloring composition. Examples of the dye include an azo dye, an azo metal complex dye, an anthraquinone dye, an indigo dye, a thioblue dye, a phthalocyanine dye, a methine dye, and a diarylmethane. Dyes, triarylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazines Oxazine) dye, perylene dye, diketopyrrolopyrrole dye, quinacridone dye, benzoindoledione (anthanthrone) dye, isoindolinone dye, isoporphyrin dye, indanthrone dye, coumarin dye, quinacridone dye, pyanthrone Dyes, flavanthrone-based dyes, perinone-based dyes, and the like, but are not limited thereto.

The pigment which can be used in the pigment composition of the present invention is, for example, various pigments used in inks and the like. The organic pigment may, for example, be a soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a halogenated phthalocyanine pigment, an azomethine pigment, a quinacridone pigment, an isoindolinone pigment, an isoindoline pigment. , anthraquinone pigment, benzalkonium pigment, dioxazine pigment, anthraquinone pigment, diterpene based pigment, pyrimidine pigment, benzoindoledione pigment, indanthrene pigment, yellow ketone pigment, dermatone pigment , diketopyrrolopyrrole pigments, and the like.

Further, in the pigment composition of the present invention, a metal oxide such as titanium oxide, iron oxide, antimony pentoxide, zinc oxide or cerium oxide, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, or talc may be used. Inorganic pigments such as chrome yellow and carbon black.

The pigment composition of the present invention is not limited to the above-exemplified pigments, and may be used as long as it is a fine powder. In particular, when the pigment composition of the present invention is used in the development of a color filter, salt milling is used (salt It is better to process and fine-tune.

The salt milling treatment refers to a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, using a kneading machine, two roll mills, three roll mills, a ball mill, an attritor, a sand mill, and the like. After mechanical mixing by heating, water-soluble inorganic salts and water-soluble are removed by washing with water. Treatment of organic solvents. It is considered that the water-soluble inorganic salt acts as a pulverization aid, and when the salt is ground, the inorganic salt has a high hardness and the pigment is pulverized, whereby an active surface is generated to cause crystal growth. Therefore, at the time of kneading, the pulverization of the pigment and the growth of the crystal are simultaneously caused, and the primary particle diameters of the pigments obtained by the kneading conditions are different.

In order to promote crystal growth by heating, it is preferred to have a heating temperature of 40 to 150 °C. When the heating temperature is less than 40 ° C, crystal growth cannot be sufficiently caused, and the shape of the pigment particles is close to a non-fixed form, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C, the crystal growth is too excessive, and the primary particle diameter of the pigment becomes large, so that it is not suitable as a coloring material for a coloring composition for a color filter. Further, the kneading time of the salt milling treatment is preferably from 2 to 24 hours from the point of balance between the particle size distribution of the primary particle diameter of the salt-treated pigment and the cost required for the salt milling treatment.

The conditions for the treatment of the pigment by salt milling are optimized, the primary particle diameter is very fine, and the width of the distribution is narrow, and a pigment having a steep particle size distribution can be obtained.

The primary average particle diameter of the pigment used in the pigment composition of the present invention by TEM (transmission electron microscope) is preferably in the range of 2 to 100 nm. If it is smaller than 2 nm, the dispersion may become difficult, and if it is larger than 100 nm, the contrast may be lowered. A particularly preferred range is from 5 to 20 nm.

Further, sodium chloride, barium chloride, potassium chloride, sodium sulfate or the like can be used as the water-soluble inorganic salt used in the salt milling treatment, but sodium chloride (salt) is preferably used from the viewpoint of price. Water soluble inorganic salt, from treatment In terms of efficiency and production efficiency, it is preferable to use 50 to 2000% by mass, and 300 to 1000% by mass, based on the total amount of the pigment.

Further, the water-soluble organic solvent-based wetting pigment and the water-soluble inorganic salt are not particularly limited as long as they are dissolved (mixed) in water and do not substantially dissolve the inorganic salt used. However, in the salt milling treatment, the temperature rises and the solvent becomes easily evaporated, and from the viewpoint of safety, a high boiling point solvent having a boiling point of 120 ° C or higher is preferred. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, Dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

When salt grinding is performed, a resin may be added as needed. The kind of the resin to be used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin can be used. The resin to be used is a solid at room temperature, and is preferably soluble in a part of the above organic solvent. The amount of the resin to be used is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of the pigment.

The pigment used in the present invention is preferably an acidic surface. The vinyl-based resin-based dispersant (B) having a piperidinyl skeleton and the resin-based dispersant (A) having an aromatic carboxyl group are adsorbed on the acidic surface, and the pigment particles are excellent in dispersibility in the dispersion.

The indicator of the acidic surface is the use of the amine adsorption energy of the pigment. In the present invention, a pigment having an amine adsorption energy of 25 to 700 μm /g (μmol/g) may be used in terms of the amount of adsorption of the amine, preferably 50 to 700 μm/g, more preferably. It is 100~600 micromoles/gram, especially preferably 200~600 micromoles/gram. In the present invention, the amine adsorption energy is defined in accordance with the method described in the color material, 67 [9], and 547-554 (1994), using n-hexylamine as the adsorbed amine substance.

The organic pigment having a slightly acidic surface may, for example, be Pigment Green 58 (a zinc halide phthalocyanine pigment, an amine adsorption amount of 200 to 700 μmol/g), and Pigment Yellow 150 (azomethine yellow pigment, an amine adsorption amount of 100). ~250 micromoles / gram) and so on. In particular, Pigment Green 58 (a zinc halide phthalocyanine pigment) can be dispersed by using a resin-based dispersant (A) having an aromatic carboxyl group and a vinyl-based resin-based dispersant (B) having a piperidinyl skeleton. The dispersibility, dispersion stability, and brightness of the pigment are particularly excellent.

(derivatives with acidic substituents)

Further, in the pigment composition of the present invention, a pigment derivative selected from an acidic functional group, an anthracene derivative having an acidic functional group, an acridon derivative having an acidic functional group, and an acidic group can be used. One or more kinds of derivatives having an acidic functional group (hereinafter sometimes referred to simply as a derivative having an acidic functional group) in which the triazine derivative of the functional group is formed.

Derivatives relating to the acidic functional groups used in the present invention are described. The derivative having an acidic functional group used in the present invention may be selected from the group consisting of the following general formula (1), the following general formula (2), and the following general formula (3). At least one or more derivatives of the group represented by the derivative. The derivative having an acidic functional group can be classified into a derivative having no opposite ion represented by the following formula (1), and a derivative having relative ions represented by the following formulas (2) and (3) Things.

General formula (1): P-Z1

(In the formula (1), P is an organic dye residue, a heterocyclic residue which may have a substituent or an aromatic residue which may have a substituent, and Z1 is a sulfonic acid group or a carboxyl group.)

General formula (2): (P-Z2) [N+(R5, R6, R7, R8)]

(In the formula (2), P is an organic dye residue, a heterocyclic residue which may have a substituent or an aromatic residue which may have a substituent, and R5 is an alkyl group having 5 to 20 carbon atoms, R6 and R7 and R8 is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z2 is SO ₃ ^- or COO ^- .)

General formula (3): (P-Z2) x My+

(In the formula (3), P is an organic dye residue, a heterocyclic residue which may have a substituent or an aromatic residue which may have a substituent, and My+ is a metal ion, and examples thereof include lithium, sodium, potassium, and magnesium. An ion of calcium, barium, iron, cobalt, nickel, copper, zinc or aluminum, y is the valence of the ion, x is the value obtained by the formula x=y÷(the number of Z2), and Z2 is the SO ₃ ^- or COO ^- .)

When P in the general formulae (1) to (3) is an organic dye residue, the organic dye may, for example, be a diketopyrrolopyrrole dye, an azo dye such as azo, disazo or polyazo, or Phthalocyanine pigment, diaminodiguanide, pyrimidine, yellow Anthraquinone dyes such as ketone, benzoindoledione, indanthrone, dermatanone, violanthrone, quinacridone dyes, dioxazine dyes, purple ketone dyes, lanthanides A pigment, a sulphur blue pigment, an isoporphyrin dye, an isoindolinone dye, a quinophthalone dye, an indanthrene dye, and a metal complex dye.

Further, when P of the general formulae (1) to (3) is a heterocyclic residue and an aromatic ring residue, the heterocyclic ring and the aromatic ring system are For example, thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoporphyrin, isoindolinone, benzimidazolone, benzothiazole, benzotriazole, anthracene ( Indole), quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone and acridone. The heterocyclic residue and the aromatic ring residue may have an alkyl group (methyl group, ethyl group, propyl group, etc.), an amine group, an alkylamino group (dimethylamino group, diethylamino group, and Dibutylamine, etc.), nitro, hydroxy, alkoxy (methoxy, ethoxy, butoxy, etc.), halogen (chlorine, bromine and fluorine, etc.), phenyl (can be alkyl, amine) a base, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen, etc.) and a phenylamine group (which may be an alkyl group, an amine group, an alkylamine group, a nitro group, a hydroxyl group, an alkoxy group, a halogen group, etc.) Substituting a substituent such as).

P in the derivative having an acidic functional group represented by the general formulae (1) to (3) is not necessarily required to be the same as the chemical structure of the pigment used in the pigment composition. However, when considering the hue of the ink or the like which is finally produced, when it is used for a green-based pigment, such as a blue-based, green-based or yellow-based organic dye residue, when used as a yellow-based pigment, such as a yellow-based organic pigment residue The base is used in red pigments such as red, orange or yellow organic pigment residues, and is similar to the color of pigments used in blue pigments such as blue or purple organic pigment residues. Or colorless is preferred.

Z1 of the formula (1) may be in the range of 0.5 to 8.0, preferably 0.7 to 3.0, relative to the P of the formula (1).

Z2 of the formula (2) may be in the range of 0.5 to 8.0, preferably 0.7 to 3.0, relative to the P of the formula (2). At the same time, corresponding to the number of Z2, [N+(R5, R6, R7, R8)] may also have the same number.

Z2 of the formula (3) may be in the range of 0.5 to 8.0, preferably 0.7 to 3.0, relative to the P of the formula (3). At the same time, the number of Z2 and the ion number y of M and the number of x can be appropriately changed.

The amount of the derivative having an acidic functional group to be used is preferably 0.1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. Further, it is preferably 1 part by mass or more and 30 parts by mass or less. When it is less than 0.1 part by mass, there is no effect. When the amount is more than 50 parts by mass, the shift of the hue becomes remarkable, and the viscosity of the pigment composition becomes high, which may increase the viscosity over time, which is not preferable.

In the present invention, among the derivatives having an acidic functional group represented by the general formulae (1) to (3), it is preferred to use a derivative having an acidic functional group represented by the general formula (2).

<Resin type dispersant (A) having an aromatic carboxyl group>

The resin-type dispersing agent (A) having an aromatic carboxyl group of the present invention is used in combination with a vinyl-based resin-based dispersing agent (B) having a piperidinyl skeleton to be described later, and a vinyl-based one is used separately from the pigment dispersion. Resin type dispersant (B) When the pigment is dispersed, the pigment can be stably present by the dispersion medium, so that a pigment composition exhibiting dispersion stability and high brightness can be obtained.

The resin type dispersant (A) having an aromatic carboxyl group of the present invention preferably has a number average molecular weight of 800 to 30,000. Even if it is less than 800 or more than 30,000, the viscosity and viscosity stability of the pigment dispersion may be deteriorated, which is not preferable.

Further, the resin-type dispersant (A) having an aromatic carboxyl group of the present invention preferably has an acid value of 10 to 200 mgKOH/g.

The resin-type dispersant (A) having an aromatic carboxyl group of the present invention is one which has an aromatic carboxyl group in its molecule. In the production method, for example, the production method 1 of reacting an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2) with a polymer (C) having a hydroxyl group; Method 2 for producing a polymer of a monomer of a carboxyl group; and a method 3 for producing an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2) while polymerizing a monomer having a hydroxyl group; Any one. Among them, from the viewpoint of the pigment dispersibility, the production method 1 in which the number of aromatic carboxyl groups in the resin-type dispersant (A) is more easily controlled is preferably produced.

(polymer with hydroxyl group (C))

The polymer (C) having a hydroxyl group as a precursor of the aromatic carboxyl group-containing resin type dispersant (A) of the present invention can be classified into a polymer (C1) having a hydroxyl group at a single terminal and a side chain. A polymer having a hydroxyl group (C2). Further, in the polymer (C1) having a hydroxyl group at one terminal, a polymer (C3) having two hydroxyl groups at a single terminal in a single terminal having two hydroxyl groups.

[Polymer (C1) having a hydroxyl group at one end, in the end Polymer (C3) having 2 hydroxyl groups at the end]

First, a description will be given of a polymer (C1) having a hydroxyl group at a single terminal. The polymer (C1) having a hydroxyl group at a single terminal used in the present invention may, for example, be a polyester having a hydroxyl group at one terminal and/or a polyether polymer (C1-1), and having a hydroxyl group at a single terminal. Vinyl polymer (C1-2). The polymer (C3) having two hydroxyl groups at one terminal is preferably a vinyl polymer.

[Polyester and/or polyether polymer (C1-1) having a hydroxyl group at a single terminal]

The polyester and/or polyether polymer (C1-1) having a hydroxyl group at a single terminal is preferably represented by the following formula (4).

[In the formula (4), Y ¹ is a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms, and X ² is -O-, -S- or -N. (Rb)- (but Rb is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms), Z ¹ is -OH, and G ¹ is a repeating unit represented by -R11O-, G ² as in -C (= O) R12O- repeating unit represented, G ³ is to -C (= O) R13C (= O) -OR14O- repeating unit represented by, R11 is a linear carbon atoms 2 to 8 a chain or branched alkyl group or a cycloalkyl group having 3 to 8 carbon atoms, and R12 is a linear or branched alkyl group having 1 to 8 carbon atoms or a ring having 4 to 8 carbon atoms. An alkyl group, R13 is a linear or branched alkyl group having 2 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms, and a ring having 3 to 20 carbon atoms. An alkyl group or an extended aromatic group having 6 to 20 carbon atoms, R14 is -CH(R15)-CH(R16)-, and any of R15 and R16 is a hydrogen atom, and the other is a carbon number of 1~ An alkyl group of 20, an alkenyl group having 2 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an alkoxymethylene group having 1 to 20 carbon atoms in the alkyl moiety, and a carbon number of the alkenyl moiety 2~20 oxymethylene, aromatic moiety Carbon atoms, an aromatic moiety of 6 to 20 optionally may be substituted with a halogen atom of an aromatic-oxy-methylene, N- methylene - phthalimide (PEI) (phthalimide) group, R ¹⁷ is the R11, -C(=O)R12- or -C(=O)R13C(=O)-OR14-, m1 is an integer from 0 to 100, m2 is an integer from 0 to 60, and m3 is an integer from 0 to 30, but m1 + m2 + m3 is 1 or more and 100 or less, the configuration of the general formula (4) of the repeating ^{unit. 1} ~ ^{G. 3} is G, based not limited to the order, the polymer was expressed in a general formula (4), and in group X ^The repeating unit G ¹ to G ³ are contained between the base ² and the base R ¹⁷ in an arbitrary order. Further, the repeating units G ¹ to G ³ may be either of a random type or a block type. ]

In the above formula (4), Y ¹ is a linear or branched alkyl group having 1 to 18 carbon atoms, and is preferred from the viewpoints of low viscosity of the pigment dispersion and storage stability.

Further, in another embodiment, in the above formula (4), Y ¹ preferably has an ethylenically unsaturated double bond. In this case, active energy ray curability can be imparted to the resin type dispersant having an aromatic carboxyl group.

Further, in the above formula (4), m2 is an integer of from 3 to 15, and is preferable from the viewpoint of low viscosity of the pigment dispersion and storage stability.

Further, in the above formula (4), when m2=0 and m3=0, Y ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms, or preferably has an ethylenically unsaturated double bond.

The polyester and/or polyether polymer (C1-1) having a hydroxyl group at a single terminal represented by the above formula (4) can be produced by a conventional method selected from monoalcohol and monoamine monoamine. a compound of a group of a monoamine and a monothiol as a starting agent, which can be selected from the group consisting of an alkylene oxide, a lactone, a lactide, a dicarboxylic anhydride, and an epoxide. The cyclic compound is easily obtained by ring-opening polymerization.

The monool type 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, third butanol, 1-pentanol, isoamyl alcohol, 1-hexanol, cyclohexanol, 4- Methyl-2-pentanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isodecyl alcohol, 1-nonanol, dodecyl alcohol, 1 - myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyl decyl alcohol, 2-octyldodecanol, 2-hexyl decyl alcohol, twenty-two An aliphatic monool such as an alkyl alcohol or an oleyl alcohol; a monoalcohol having an aromatic ring such as benzyl alcohol, phenoxyethyl alcohol or p-cumylphenoxyethyl alcohol; 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 single Propyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, two Propylene 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 single Butyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol single Hexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, four Glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol An alkanediol monoalkyl ether such as mono-2-ethylhexyl ether or tetraethylene glycol monomethyl ether.

As the monool, a monool having an ethylenically unsaturated double bond can be used. At this time, an active energy ray hardening function can be imparted to the produced dispersant having an aromatic carboxyl group.

Examples of the ethylenically unsaturated double bond include a vinyl group or a (meth) acrylonitrile group (hereinafter, hereafter referred to as "(meth)acryl fluorenyl group" or "(meth)acrylic acid. "ester", respectively, is expressed as "acryloyl fluorenyl and / or methacryl fluorenyl" or "methacrylate and / or propylene The acid ester") is preferably a (meth) acrylonitrile group. The types of the groups having the double bond may be one type or plural types.

As the monool having an ethylenically unsaturated double bond, a compound containing one, two or three or more ethylenically unsaturated double bonds can be used. The number of the ethylenically unsaturated double bonds is one monohydric alcohol, and, for example, 2-hydroxyethyl (meth)acrylate (hereinafter, the expression "(meth)acrylate" means acrylate and / Or methacrylate. The same as the following), 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-(meth)acrylate Hydroxybutyl ester, 2-hydroxybutyl (meth)acrylate, ethyl 2-(hydroxymethyl) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexane dimethanol (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether or 4-hydroxybutyl vinyl ether. The number of ethylenically unsaturated double bonds is two monols, and examples thereof include 2-hydroxy-3-acryloxypropyl methacrylate or glycerol di(meth)acrylate. The number of ethylenically unsaturated double bonds is 3 monohydric alcohols, for example, neopentyl alcohol triacrylate, and the number of ethylenically unsaturated double bonds is 5 monools, and for example, dipentaerythritol pentaacrylate .

Among them, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are obtained by a mixture of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, respectively, so that the generated dispersant is controlled. The molecular weight must be determined by HPLC (high-speed liquid chromatography) or the measurement of the hydroxyl value to determine the ratio of the monool. The molecular weight of the dispersant is determined by the ratio of the number of monohydric alcohols to the raw material forming G ¹ to G ³ .

The number of ethylenically unsaturated double bonds among the aforementioned monools In the case of two or more, it is preferable to use it for the active energy ray-curable pigment composition in terms of hardenability.

The monoamine monoamine may, for example, be methylamine, ethylamine, 1-propylamine, isopropylamine, 1-butylamine, isobutylamine, butylamine, 1-pentylamine, Isoamylamine, 3-pentylamine, 1-hexylamine, cyclohexylamine, 4-methyl-2-pentylamine, 1-heptylamine, 1-octylamine, isooctylamine, 2- Ethylhexylamine, 1-decylamine, isodecylamine, 1-decylamine, 1-dodecylamine, 1-tetradecylamine, hexadecylamine, 1-octadecyl Aliphatic grade 1 single such as amine, isostearylamine, 2-octyldecylamine, 2-octyldodecylamine, 2-hexyldecylamine, behenylamine or oleylamine Amines; 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 2-ethylhexyloxypropylamine, An alkoxyalkyl 1- to amine such as 3-isobutoxypropylamine, 3-methoxypropylamine or 3-tetradecyloxypropylamine; or aromatic grade 1 such as benzylamine Monoamines.

The second-stage monoamine may, for example, be dimethylamine, diethylamine, di-1-propylamine, diisopropylamine, di-1-butylamine, diisobutylamine, di-1- Amylamine, diisoamylamine, di-1-hexylamine, dicyclohexylamine, bis-(4-methyl-2-pentyl)amine, di-1-heptylamine, di-1-octyl Amine, isooctylamine, bis-(2-ethylhexyl)amine, di-1-indenylamine, diisodecylamine, di-1-indenylamine, di-1-dodecylamine , di-1-tetradecylamine, di-hexadecylamine, di-1-octadecylamine, diisooctadecylamine, di-(2-octyldecyl)amine, two -(2-octyldodecyl)amine, di-(2- Hexyl decyl)amine, N-methylethylamine, N-methylbutylamine, N-methylisobutylamine, N-methylpropylamine, N-methylhexylamine, piperazine Or an alkyl group-substituted aliphatic class 2 monoamine such as piperazine.

Examples of the monothiol include methyl mercaptan, ethyl mercaptan, 1-propyl mercaptan, isopropyl mercaptan, 1-butyl mercaptan, isobutyl mercaptan, and third butyl mercaptan. 1-pentyl mercaptan, isoamyl mercaptan, 3-pentyl mercaptan, 1-hexyl mercaptan, cyclohexyl mercaptan, 4-methyl-2-pentyl mercaptan, 1-heptyl mercaptan, 1-octyl mercaptan, isooctyl mercaptan, 2-ethylhexyl mercaptan, 1-mercapto mercaptan, isodecyl mercaptan, 1-mercapto mercaptan, 1-dodecyl mercaptan, 1-tetradecyl mercaptan, hexadecyl mercaptan, 1-octadecyl mercaptan, isostearyl mercaptan, 2-octyl mercapto mercaptan, 2-octyl dodecyl An aliphatic monothiol such as a mercaptan, a 2-hexyl mercapto mercaptan, a behenyl mercaptan or an oil-based mercaptan; or a methyl thioglycolate, an octyl thioglycolate or a thioglycolate An alkyl thioglycolate such as an alkyl thioglycolate such as oxybutyl ester, methyl cyanopropionate, octyl decyl propyl acrylate, methoxybutyl decyl propionate or lauryl decyl propionate.

In the present invention, the compound selected from the group consisting of monoalcohol, monoamine monoamine, quaternary monoamine and monothiol is not limited to the above exemplified, as long as it has one hydroxyl group, one amine group, and two amine group. The compound of the thiol group or the thiol group may be used alone or in combination of two or more kinds.

Here, the monool, the mono-monoamine, the 2-stage monoamine or the monothiol are respectively removed by a hydroxyl group, a first-group amine group, a 2-stage amine group or a thiol group, and constitute the above formula (4). Y ¹ .

The above-exemplified compound selected from the group consisting of a monoalcohol, a mono-monoamine, a 2-stage monoamine, and a monothiol is used as a starter, and is selected from the group consisting of alkylene oxides, lactones, lactides, and dicarboxylic anhydrides. When the cyclic compound of the group formed by the combination with the epoxide is subjected to ring-opening polymerization, Z ¹ in the polymer represented by the above formula (4) can be produced as -OH. However, the combination of the dicarboxylic anhydride and the epoxide must be used simultaneously and alternately polymerized.

Here, the reaction sequence of the cyclic compound selected from the group consisting of alkylene oxide, lactone, lactide, and a combination of a dicarboxylic acid anhydride and an epoxide may be in any order, for example, in the first stage, After the starting agent polymerizes the alkylene oxide, the lactone is polymerized in the second stage, and the dicarboxylic acid anhydride and the epoxide are alternately polymerized in the third stage. In this example, the initiator in the polymerization of the lactone in the second stage is an alkylene oxide polymer having a hydroxyl group at a single terminal which is polymerized in the first stage. Further, in the third stage, the initiator of the alternating polymerization of the dicarboxylic anhydride and the epoxide is a block copolymer of an alkylene oxide polymer having a hydroxyl group at one end and a lactone polymer polymerized until the second stage. . In the production method of the present invention, the initiator of the above-described polymer represented by the formula (4) is produced, and as described above, in the polymer represented by the formula (4), Z ¹ is -OH. The polymer represented by the formula (6), which will be described later, may also be a starter.

The reaction sequence of the above cyclic compound is not limited to the first stage alkylene oxide, the second stage lactone, the third stage combination of the dicarboxylic anhydride and the epoxide, and the alkylene oxide, lactone (and / The combination of the lactide and the dicarboxylic anhydride and the epoxide is carried out 1 to several times in any order. Alternatively, for alkylene oxides, lactones (and/or lactides) and dicarboxylic anhydrides and epoxides In the combination, any ring-opening polymerization can be carried out without selecting any ring-opening polymerization, and ring-opening polymerization can also be carried out.

The alkylene oxide may, for example, be ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide or 1,3-epoxybutylene. An alkane or the like may be used alone or in combination of two or more. Further, in the case of using two or more kinds of alkylene oxides, the bonding form may be any of random and/or block. The number of polymerized moles of the alkylene oxide is preferably from 0 to 100 with respect to 1 mole of the initiator.

The polymerization of the alkylene oxide can be carried out by a known method, for example, in the presence of a base catalyst at a temperature of 100 to 200 ° C under a pressurized state. An alkylene oxide polymer having a hydroxyl group at a single terminal of a hydroxyl group-polymerized alkylene oxide of a monool is commercially available, and examples thereof include a UNIOX series manufactured by Nippon Oil & Fats Co., Ltd., and a BLEMMER series manufactured by Nippon Oil & Fats Co., Ltd. In the polymer shown in (4), in the repeating unit of G ¹ to G ³ wherein Z ¹ is -OH, only G ¹ may be used, and it may be used as it is as a raw material of the dispersing agent having an aromatic carboxyl group of the present invention. Specific examples of commercial 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 is R11 in the repeating unit G1 constituting the above formula (4).

The lactone may specifically be, for example, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone or an alkane. The radically substituted ε-caprolactone in which δ-valerolactone, ε-caprolactone or alkyl-substituted ε-caprolactone is used is preferable in terms of ring-opening polymerizability.

In the production method used in the present invention, the lactone is not limited to the above-described examples, and may be used singly or in combination of two or more. When it is used in combination of two or more kinds, the crystallinity may be lowered, and it may become liquid at room temperature, and it is preferable from the point of handling property and the compatibility with other resin.

The lactide is preferably one represented by the following formula (5) (including glycolide).

[In the formula (5), R ³¹ and R ³² each independently represent a hydrogen atom, a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms; and R ³³ and R ³⁴ each independently represent a hydrogen atom; A halogen atom and a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms. ]

Particularly suitable lactides for the raw materials of the aromatic carboxyl group-containing dispersing agent of the present invention are lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide ( 1,4-Dioxane-2,5-dione). Further, in the raw material of the dispersant having an aromatic carboxyl group of the present invention, it is preferred to use a lactone in the lactone or lactide.

The ring-opening polymerization of a lactone and/or a lactide may be carried out by a conventional method, for example, in a reactor to which a dehydration tube or a condenser is connected, and an initiator, a lactone, and/or a lactide and a polymerization catalyst are placed. It was carried out under a nitrogen stream. When a low boiling point monool is used, the reaction is carried out under pressure using an autoclave. Further, when a monomer having an ethylenically unsaturated double bond is used as the monool, a polymerization inhibitor is added, and the reaction is preferably carried out under a dry air stream.

The number of polymerized moles of lactone and/or lactide 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. .

The polymerization catalyst of the lactone and/or lactide may be used without any limitation, and examples thereof include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, and tetrabutyl bromide. Tetrabasic ammonium such as tetraammonium iodide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide or benzyltrimethylammonium iodide Salt; tetramethylguanidine chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyl chloride a quaternary phosphonium salt such as methyl hydrazine, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide or tetraphenylphosphonium iodide; a phosphorus compound such as triphenylphosphine; an organic carboxylate such as potassium acetate, sodium acetate, potassium benzoate or sodium benzoate; an alkali metal alkoxide such as a sodium alkoxide or a potassium alkoxide; a tertiary amine; an organotin compound, organic Aluminum compound or organic titanate compound An organometallic compound; or a zinc compound such as zinc chloride.

The amount of the catalyst used is from 0.1 ppm to 3,000 ppm, preferably from 1 ppm to 1000 ppm. When the amount of the catalyst exceeds 3,000 ppm, the color of the resin sometimes becomes intense. Conversely, when the amount of the catalyst used is less than 0.1 ppm, the rate of ring-opening polymerization of the lactone and/or lactide may be slow.

The polymerization temperature of the lactone and/or lactide is from 100 ° C to 220 ° C, preferably from 110 ° C to 210 ° C. If the reaction temperature is less than 100 ° C, the reaction rate may be slow. If it exceeds 220 ° C, side reactions other than the addition reaction of lactone and/or lactide, such as the lactone monomer of the lactone adduct. The polymerization is carried out, and it is easy to cause formation of a cyclic lactone dimer or a trimer.

Here, the portion other than the ester group of the lactone and/or the lactide is R12 in the repeating unit G ² constituting the above formula (4).

Examples of the dicarboxylic anhydride include succinic anhydride, maleic anhydride, decanoic anhydride, methylene succinic anhydride, glutaric anhydride, dodecenyl succinic anhydride, or chlorendic anhydride.

Examples of the epoxide include methyl epoxypropyl ether, ethyl epoxypropyl ether, butyl epoxypropyl ether, 2-ethylhexyl epoxypropyl ether, and dodecyl epoxypropyl group. Ether, phenylepoxypropyl ether, p-butyl butyl epoxide, 2,4-dibromophenyl epoxypropyl ether, 3-methyl-dibromophenyl epoxide Ether (but the substitution position of bromine is arbitrary), allylepoxypropyl ether, ethoxyphenylepoxypropyl ether, epoxypropyl (meth) acrylate, epoxy propyl phthalate Formamidine or styrene oxide.

The dicarboxylic anhydride and the epoxide are used simultaneously for the initiator, and are alternately reacted. At this time, for the hydroxyl group of the initiator, the amine group of the first stage, the amine group of the second stage or the thiol group, first, the acid anhydride group of the dicarboxylic acid anhydride reacts to generate a carboxyl group, and then the epoxy group of the epoxide reacts with the carboxyl group. Hydroxyl groups are produced. Further, as the hydroxyl group reacts with the acid anhydride group of the dicarboxylic anhydride, the same reaction as described above can be carried out in the following order. The number of polymerized moles of the dicarboxylic anhydride and the epoxide relative to the 1 molar initiator is preferably from 0 to 30 moles. Further, the reaction ratio ([D]/[E]) of the dicarboxylic anhydride to the epoxide is 0.8 ≦ [D] / [E] ≦ 1.0

([D] is the molar number of the dicarboxylic anhydride, and [E] is the molar number of the epoxide). If it is less than 0.8, the epoxide is likely to remain. When it exceeds 1.0, a polymer having a hydroxyl group at a single terminal cannot be obtained, and a polymer having a carboxyl group at a single terminal may be obtained, which is not preferable.

The alternating polymerization of the dicarboxylic anhydride and the epoxide is preferably carried out at a temperature of from 50 ° C to 180 ° C, more preferably from 60 ° C to 150 ° C. When the reaction temperature is less than 50 ° C or exceeds 180 ° C, the reaction rate may be slow.

Here, the moiety other than the dicarboxylic anhydride group of the dicarboxylic anhydride forms R13 in the repeating unit G ³ of the above formula (4), and the moiety other than the oxygen atom forming the cyclic ether of the epoxide constitutes the above formula (4). ) of the repeating units G in ³ R14.

In the case of producing the above-mentioned polymer represented by the formula (4), when a monool, a dicarboxylic anhydride or an epoxide having an ethylenically unsaturated double bond is used, it is preferred to use a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6- may be mentioned. The third butyl phenol, phenothiazine or the like is preferably used alone or in combination in the range of 0.01% to 6%, preferably 0.05% to 1.0%.

[Vinyl polymer (C1-2) having a hydroxyl group at a single terminal]

The vinyl polymer (C1-2) having a hydroxyl group at a single terminal is preferably a polymer represented by the following formula (6).

[In the formula (6), Y ² is a polymerization stop group of a vinyl polymer, X ⁴ is -O- or -S-, Z ² is -R27-OH or -R28(OH) ₂ , and R27 is a carbon number. a linear, branched or cyclic alkyl group of 1 to 18, R28 is an aliphatic, alicyclic or aromatic trivalent hydrocarbon group having 1 to 18 carbon atoms, and R21 and R22 are each independently a hydrogen atom or A methyl group, any of R23 and R24 is a hydrogen atom, and the other is an aromatic group or -C(=O)-X6-R25 (wherein X6 is -O- or -N(R26)-), R25 and R26 are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a linear or branched alkane having 1 to 18 carbon atoms having an aromatic group as a substituent. The base or the alkyl group having an ether group having 1 to 18 carbon atoms, a branched chain or an alkyl group having a cyclic structure, and n is 2 to 50. ]

The polymer represented by the above 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 formula (6), that is, {-[C(R ²¹ )(R ²³ )-C(R ²² )(R ²⁴ )]n-}, may be mutually The same structure (homopolymer) can also be composed of different (copolymer). In a preferred embodiment of the polymer represented by the formula (6), any one of R ²¹ and R ²² is a hydrogen atom, and the other is a hydrogen atom or a methyl group, and any of R ²³ and R ²⁴ The one is a hydrogen atom, and the other is -C(=O)-O-R29 (R29 is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and may have an aromatic group as a substituent. Or a linear, branched or cyclic alkyl group having an ether group having 1 to 18 carbon atoms, and -X ⁴ -Z ² is -S-CH ₂ CH ₂ -OH or S-CH ₂ When CH(OH)CH ₂ -OH.

Y ^{2 of the} above formula (6), that is, a polymerization stop group of a vinyl polymer, can be any conventional polymerization stop group introduced when a general ethylenically unsaturated monomer is polymerized by a general method. It is well known to those skilled in the art. Specifically, for example, 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 may be mentioned. Even if Y ² has any of these chemical structures, the dispersant of the present invention is not affected by the polymerization stopper Y ² and exerts its effects.

In the polymer represented by the formula (6), Z ² is -R27-OH, which can be produced by a known method. For example, a compound having a hydroxyl group and a thiol group can be mixed with an ethylenically unsaturated monomer to be heated. Come and get.

The compound having a hydroxyl group and a thiol group in the molecule may, for example, be mercapto methanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol or 2-mercapto-3-butanol. .

In the polymer represented by the formula (6), Z ² is -R28(OH) ₂ , and it can be produced by a known method, and for example, a compound having two hydroxyl groups and one thiol group and ethylene can be produced. The unsaturated monomers are mixed and heated to obtain. In this case, in the polymer (C) having a hydroxyl group at one terminal, the polymer (C3) having two hydroxyl groups at the single terminal is the most preferable.

The compound having two hydroxyl groups and one thiol group in the molecule may, for example, be 1-decyl-1,1-methylglycol, 1-mercapto-1,1-ethanediol or 3-mercapto-1. 2-propanediol (thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1- Mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol or 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

It is preferred to carry out bulk polymerization or solution polymerization using 1 to 30 parts by mass of a compound having a hydroxyl group and a thiol group with respect to 100 parts by mass of the ethylenically unsaturated monomer. The reaction temperature is preferably from 40 to 150 ° C, more preferably from 50 to 110 ° C, and the reaction time is preferably from 3 to 30 hours, more preferably from 5 to 20 hours. When the compound having a hydroxyl group or a thiol group is less than 1 part by mass, the molecular weight is increased, and the viscosity of the dispersion is increased, which may be poor. When the amount is more than 30 parts by mass, the molecular weight becomes small, and the stereoscopic rebound effect due to the solvent-affinity vinyl polymer portion is deteriorated, which may be poor.

The thiol group is a radical generating group for polymerizing an ethylenically unsaturated monomer, and the polymerization system does not necessarily require another polymerization initiator. But it can also be used. When the polymerization initiator is used, it is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the ethylenically unsaturated monomer.

As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compound include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis (cyclohexane). Alkane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypenta Nitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(2-cyanovaleric acid), 2,2'-azobis ( 2-hydroxymethylpropionitrile or 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of the organic peroxides include, for example, benzamidine peroxide, butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, Di(2-ethoxyethyl) peroxydicarbonate, 3 butyl peroxy neodecanoate, 3 butyl peroxypivalate, peroxidation (3,5,5-trimethylhexanide) Base), dipropenyl peroxide or diethylperoxy peroxide. These polymerization initiators can be used singly or in combination of two or more.

The ethylenically unsaturated single system is not particularly limited as long as it is a copolymerizable monomer, and may be appropriately selected depending on the use.

For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid Isobutyl ester, 3 butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-methyl methacrylate Ester, hexadecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, (methyl) Linear or branched alkyl (meth)acrylates such as tridecyl acrylate, isotetradecyl (meth) acrylate, stearyl (meth) acrylate and isostearyl (meth) acrylate Cyclohexyl (meth)acrylate, 3 butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and (meth)acrylic acid Cyclic (meth)acrylic acid alkyl esters such as isodecyl ester; tetrahydrofuran methyl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate, etc. Ring (meth) acrylates; benzyl (meth) acrylate, (meth) acrylates having an aromatic ring of phenoxyethyl (meth) acrylate; 2-methyl (meth) acrylate Oxyethyl ester, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol single Ethyl (meth) acrylate, diethylene glycol mono-2-methylhexyl (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (methyl) Acrylate, triethylene glycol monoethyl ether (methyl) propylene Ester, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, polypropylene glycol monoethyl ether (meth) acrylate , polyethylene glycol monolaurate (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate and octyloxy polyethylene glycol - polypropylene glycol (meth) acrylate, etc. (poly) Alkylene glycol monoalkyl ether (meth) acrylates; phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxytetraethylene glycol (methyl) Acrylate, phenoxy hexaethylene glycol (Meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, p-cumyl phenoxyethyl (meth) acrylate, p- cumyl phenoxy glycol (A) Acrylate, p-cumylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (methyl (poly)alkylene glycol monoalkyl ether (meth) acrylates having an aromatic ring such as acrylate and nonylphenoxy poly(ethylene glycol-propylene glycol) (meth) acrylate; 3-methyl Propylene methoxypropyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene methoxy propyl methyl diethoxy decane, 3-methyl (meth) acrylates having alkoxyalkylene groups such as acryloxypropyltriethoxydecane and 3-propenyloxypropyltrimethoxydecane; and trifluoroethyl (meth)acrylate , fluoroalkyl (meth) acrylate such as octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate; (meth) propylene oxime Modified polydimethyl oxirane Lipid macromolecules; (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) propylene N-substituted (meth) acrylamides such as decylamine, diacetone (meth) acrylamide, and morpholine; and nitriles such as (meth)acrylonitrile.

Further, styrene such as styrene or α-methylstyrene may be used; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; and vinyl acetate and vinyl propionate Fatty acid vinyl esters, etc.

Further, an ethylenically unsaturated monomer having a carboxyl group may also be used in combination. The ethylenically unsaturated single system containing a carboxyl group may, for example, be (meth)acrylic acid, (meth)acrylic acid dimer, methylene succinic acid, maleic acid, fumaric acid, 2-butyl Acrylic acid, 2-(methyl) propylene methoxyethyl phthalate, 2-(methyl) propylene methoxy propyl phthalate, 2-(methyl) propylene hexahydrophthalate醯 methoxyethyl ester, 2-(meth) propylene methoxy propyl hexaphthalate, β-carboxyethyl (meth) acrylate and ω-carboxy polycaprolactone (meth) acrylate, etc. .

One or two or more kinds of the above-mentioned ethylenically unsaturated monomers may be used, and at least one selected from the group consisting of benzyl (meth)acrylate, methyl (meth)acrylate, and (meth)acrylic acid B may be used. Ethylene-unsaturated monomers in which the ester and methoxyethyl (meth)acrylate are grouped are preferred.

In the step of producing the polymer represented by the above formula (6), a solvent may be used or a solvent may be used as the case may be. As the solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol single can be used. Methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate or diethylene glycol monobutyl ether acetate, but not limited to These are the same. These polymerization solvents can be used by mixing two or more types.

The amount of the solvent to be used is preferably from 0 to 300 parts by mass, more preferably from 0 to 100 parts by mass, per 100 parts by mass of the ethylenically unsaturated monomer. The solvent to be used is removed by an operation such as distillation after completion of the reaction, or may be used as a part of a dispersant.

[Polymer (C2) having a hydroxyl group in a side chain]

The polymer (C2) having a hydroxyl group in a side chain of the present invention can be obtained by polymerizing an ethylenically unsaturated monomer having a hydroxyl group with other ethylenically unsaturated monomers as needed. The ethylenically unsaturated single system having a hydroxyl group may, for example, be a (meth)acrylate monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or 2 (or 3)-hydroxyl (meth)acrylate. Propyl ester, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate or hydroxyalkyl (meth)acrylate or ethyl α-hydroxyethyl methacrylate such as cyclohexanedimethanol mono(meth)acrylate Or an α-hydroxyalkyl acrylate alkyl ester; or a (meth) acrylamide amine monomer having a hydroxyl group such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl) N-(2-hydroxyalkyl)(meth)acrylamide such as (meth)acrylamide or N-(2-hydroxybutyl)(meth)acrylamide; or vinyl ether having a hydroxyl group a monomer such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether or a hydroxyalkyl vinyl ether such as 2-(or 3- or 4-)hydroxybutyl vinyl ether Or an allyl ether-based monomer having a hydroxyl group such as 2-hydroxyethylallyl ether, 2-(or 3-)hydroxypropylallyl ether or 2-(or 3- or 4-)hydroxybutyl A hydroxyalkyl allyl ether such as allyl ether or the like.

Further, for example, a glycerin mono(meth)acrylate or the like may be mentioned. A monomer having 2 hydroxyl groups. In addition, the ethylenically unsaturated monomer having a cyclic ether group such as an epoxy group is reacted with a carboxyl group-containing ethylenically unsaturated monomer such as (meth)acrylic acid or (meth)acrylic acid or the like. The ethylenically unsaturated monomer of a carboxyl group is a reaction of a monofunctional cyclic ether compound such as a monofunctional epoxy compound.

Further, the above-mentioned (meth)acrylic acid hydroxyalkyl ester, α-hydroxyalkylalkyl acrylate, N-(hydroxyalkyl)(meth)acrylamide, hydroxyalkyl vinyl ether, hydroxyalkyl allyl Ether or glycerol mono(meth) acrylate, an ethylenically unsaturated monomer obtained by adding an alkylene oxide and/or a lactone, can be used as an ethylenically unsaturated monomer having a hydroxyl group in the process of the present invention. body. The alkylene oxide to be added may, for example, be ethylene oxide, propylene oxide or 1,2-, 1,4-, 2,3- or 1,3-epoxybutane, or may be used. More than one combination. Further, in the case of using two or more kinds of alkylene oxides, the bonding form may be any of random and/or block. The lactone to be added may, for example, be δ-valerolactone, ε-caprolactone or an alkyl-substituted ε-caprolactone having 1 to 6 carbon atoms, or a combination of two or more kinds thereof. It can also be added to both alkylene oxide and lactone.

The copolymerization ratio of the ethylenically unsaturated monomer having a hydroxyl group to the other ethylenically unsaturated monomer is preferably determined so that at least one molecule after polymerization is placed at least 0.3 to 177 hydroxyl groups.

The other ethylenically unsaturated single system may, for example, be an ethylenically unsaturated monomer described in the step of producing the polymer represented by the above formula (6), and may be used arbitrarily.

The polymerization initiator can be used, for example, in the production of the above formula (6) An azo compound or an organic peroxide described in the step of the polymer shown. When the polymerization initiator is used, it is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the ethylenically unsaturated monomer.

The polymerization solvent can be, for example, the same solvent as that described in the step of producing the polymer represented by the above formula (6).

Reaction of a polymer having a hydroxyl group (C) with an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2)

Next, a step of reacting a polymer (C) having a hydroxyl group with an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2) will be described.

The above reaction is a polymer (C1) having a hydroxyl group at one terminal or a polymer (C2) having a hydroxyl group in a side chain, and an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2). The reaction is preferred.

By the above-mentioned polymer (C1) having a hydroxyl group at a single terminal or a hydroxyl group of a polymer (C2) having a hydroxyl group in a side chain, and an aromatic tricarboxylic anhydride (D1) and/or an aromatic tetracarboxylic dianhydride (D2) The acid anhydride group reaction of the present invention can obtain the resin type dispersant (A) having an aromatic carboxyl group of the present invention.

Examples of the aromatic tricarboxylic anhydride (D1) include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride (1,2,4-benzenetricarboxylic anhydride), etc.), and naphthalene Carboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3 , 4,4'-diphenyl ketone tricarboxylic anhydride, 3,4,4'-diphenyl ether tricarboxylic anhydride, 3,4,4'-biphenyl tricarboxylic anhydride, 2,3,2'-biphenyl Tricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride or 3,4,4'-biphenylfluorene tricarboxylic anhydride.

The aromatic tetracarboxylic dianhydride (D2) is, for example, a pyromelli-4 Pyromellitic anhydride, ethylene glycol di trimellitic anhydride, propylene glycol di trimellitic anhydride, butanediol di trimellitic anhydride, 3,3', 4,4'- Phenyl ketone tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl fluorene tetracarboxylic dianhydride, 2, 2',3,3'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4'-four Phenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3' , 4,4'-perfluoroisopropylidene phthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride , p-phenyl-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)- 4,4'- Phenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)ruthenium anhydride or 9, 9-bis[4-(3,4-dicarboxyphenoxy)phenyl]ruthenium hydride.

The aromatic tricarboxylic anhydride (D1) and the aromatic tetracarboxylic dianhydride (D2) used in the present invention are not limited to the above-exemplified compounds, and may be any structure. These may be used alone or in combination. The user of the present invention is preferably trimellitic anhydride or pyromellitic dianhydride.

When the number of moles of the hydroxyl group of the polymer (C) is <H>, and the number of moles of the carboxylic anhydride group of the aromatic tricarboxylic anhydride (D1) or the aromatic tetracarboxylic dianhydride (D2) is <N>, the reaction The ratio is preferably 0.3 ≦ < H > / < N > ≦ 3, more preferably 0.5 ≦ < H > / < N > ≦ 2 . Especially using polymer (C3) When it is a polymer (C), it is preferable that it is 1 < < H> / <N> ≦2. When the reaction is carried out by <H>/<N><1, the remaining acid anhydride may be hydrolyzed by a required amount of water, or may be subjected to alcoholysis with a monofunctional alcohol.

When the polymer (C2) is used, it is preferred to introduce 0.3 to 3 aromatic tricarboxylic anhydrides or aromatic tetracarboxylic dianhydrides in one molecule. Specifically, the number average molecular weight of the polymer (C2) is measured. When the measured value is [X], when the aromatic tricarboxylic anhydride (D1) is used, the resin [X]g can be made 0.3 mol or more. The aromatic tricarboxylic anhydride below the ear is reacted. On the other hand, when the aromatic tetracarboxylic dianhydride (D2) is used, the aromatic tetracarboxylic dianhydride of 0.15 mol or more and 1.5 mol or less can be reacted with respect to the resin [X]g. Since the aromatic tetracarboxylic dianhydride has two acid anhydride groups, in order to bridge the polymer (C2) molecule, when the aromatic tetracarboxylic dianhydride (D2) is used, it may be used in half.

A catalyst may also be used for the reaction of the polymer (C) having a hydroxyl group with the aromatic tricarboxylic anhydride (D1) and/or the aromatic tetracarboxylic dianhydride (D2). As the catalyst system, a tertiary amine compound can be used, and examples thereof include triethylamine, triethylamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-di. Azabicyclo-[5.4.0]-7-undecene or 1,5-diazabicyclo-[4.3.0]-5-decene.

The reaction of the polymer (C) having a hydroxyl group with the aromatic tricarboxylic anhydride (D1) and/or the aromatic tetracarboxylic dianhydride (D2) can be carried out without a solvent, or an appropriate dehydrated organic can be used. Solvent. The solvent used in the reaction is removed by an operation such as distillation after the completion of the reaction, or may be used as a part of the dispersant. Solvent used, none It is particularly limited to use the same solvent as that described in the step of producing the polymer represented by the above formula (6).

The reaction temperature of the polymer (C) having a hydroxyl group, the aromatic tricarboxylic anhydride (D1) or the aromatic tetracarboxylic dianhydride (D2) is preferably from 50 ° C to 180 ° C, more preferably from 60 ° C to 160 ° C. Under the scope of the. When the reaction temperature is less than 50 ° C, the reaction rate becomes slow. When the reaction temperature exceeds 180 ° C, the reaction-opened acid anhydride forms a cyclic anhydride again, and the reaction may be difficult to complete.

<Vinyl Resin Type Dispersant (B) having a piperidinyl skeleton>

The vinyl-based resin type dispersing agent (B) having a piperidinyl skeleton of the present invention can have a monomer having a piperidinyl skeleton represented by the formula (7) and other ethylenically unsaturated monomers as required. Aggregated.

(In the formula (7), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an anthracenyl group, an oxygen radical or OR ⁴ , R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and an aromatic group having a carbon number 6 to 20 carbon atoms, an aralkyl group having 7 to 12 acyl, R ² and R ³ independently represent methyl, ethyl, Base or phenyl. "*" means bonding.)

In the above formula (7), the alkyl group having 1 to 18 carbon atoms of R ¹ and R ⁴ may, for example, be a linear, branched or cyclic alkyl group, and specific examples thereof include methyl group and ethyl group. Base, n-propyl, isopropyl, n-butyl, butyl, n-hexyl, cyclohexyl, n-octyl, hexadecyl and the like.

Further, in the above formula (7), the aromatic group having 6 to 20 carbon atoms of R ¹ and R ⁴ may, for example, be a phenyl group, a 1-naphthyl group or a 2-naphthyl group.

Further, in the above formula (7), the aralkyl group having 7 to 12 carbon atoms of R ¹ and R ⁴ may, for example, be an alkyl group having a carbon number of 6 to 20 bonded to an alkyl group having 1 to 8 carbon atoms. Specific examples thereof include a benzyl group, a phenethyl group, an α-methylbenzyl group, and a 2-phenylpropan-2-yl group.

Further, examples of the fluorenyl group of R ¹ and R ⁴ in the above formula (7) include an alkanoyl group and an aryl group having 2 to 8 carbon atoms, and specific examples thereof include an ethyl fluorenyl group and a benzamidine group. .

In the present invention, R ^{1 is} preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an oxygen radical, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

The piperidinyl skeleton represented by the formula (7) is not particularly limited, and is preferably a partial structure derived from an ethylenically unsaturated monomer.

The ethylenically unsaturated monomer having a piperidinyl group is preferably contained in an amount of from 1% by mass to 100% by mass based on the solid content of the ethylenically unsaturated monomer, from the viewpoint of the viscosity and the viscosity stability of the pigment dispersion. 25% by mass to 100% by mass is more preferable, and 40% by mass to 100% by mass is particularly preferable.

Since the piperidinyl skeleton has an antioxidant function, even if it is contained in a small amount, the oxidation of the color filter material can be prevented, and as a result, the decrease in brightness can be prevented.

Further, the vinyl-based resin type dispersant (B) having a piperidinyl skeleton of the present invention preferably has an amine value of 50 to 350 mgKOH/g. When the amine price is less than 50 mgKOH/g, the viscosity and viscosity stability of the pigment dispersion sometimes deteriorate. When it exceeds 350 mgKOH/g, the brightness sometimes decreases.

Further, the number average molecular weight of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton of the present invention is preferably from 500 to 30,000, more preferably from 2,000 to 30,000. When it is less than 500 or exceeds 30,000, the viscosity and viscosity stability of the pigment dispersion sometimes deteriorate.

Specific examples of the ethylenically unsaturated monomer having a piperidinyl group are, for example, a compound represented by the formula (8-1), a compound represented by the following formula (8-2), and the like.

(In the formula (8-1) and the formula (8-2), R ⁵ and R ⁷ each represent a hydrogen atom or a methyl group, and R ⁶ represents a methylene group or a C 2 to 5 alkyl group, X The above is represented by the formula (7), and Y represents -CONH-*, -SO ₂ -*, -SO ₂ NH-* (wherein the "*" bond hand and X bond are attached) , n represents an integer of 0 to 9.) R ^{6 is} preferably an ethyl group, a propyl group, and particularly preferably an ethyl group. n is an integer of 0 to 8, and particularly preferably an integer of 0 to 6.

Specific examples of the monomer represented by the formula (8-1) above may be used. Examples thereof include compounds represented by the general formulae (9-1) to (9-7) and the like.

(In the formulae (9-1) to (9-7), the R ^{5 group} has the same meaning as the R ⁵ of the formula (8-1).)

Further, specific examples of the monomer represented by the formula (8-2) include, for example, the compounds represented by the following formulas (10-1) to (10-4).

(In the formulae (10-1) to (10-4), the R ^{7 group} has the same meaning as R ⁷ of the formula (8-2).)

Among these, a compound of 2,2,6,6-tetramethylpiperidyl methacrylate (in the above formula 9-1, wherein R ⁵ is a methyl group), 1, 2, 2 is preferable. 6,6-pentamethylpiperidinyl methacrylate (in the above formula 9-2, a compound wherein R ⁵ is a methyl group), particularly preferably 1,2,2,6,6-pentamethyl Piperidinyl methacrylate (formula 9-2 above).

The other ethylenically unsaturated monomer system is not particularly limited as long as it is a monomer copolymerizable with the ethylenically unsaturated monomer having a piperidinyl skeleton, and may be appropriately selected depending on the use.

For example, the ethylenically unsaturated monomer described in the step of producing the polymer represented by the formula (6) and the polymer (C2) having a hydroxyl group in the side chain can be used arbitrarily. Further, an ethylenically unsaturated monomer having an amine group may also be used in combination, and examples thereof include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylamine (meth)acrylate. (meth) acrylate having a 3-stage amine group, such as ethyl ethyl ester, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl a (meth) acrylamide having a tertiary amino group such as a (meth) acrylamide and an N,N-diethylaminopropyl (meth) acrylamide; and a dimethylamino benzene Ethylene, diethylaminostyrene, and the like.

Further, a (meth) acrylate having an alkoxyalkylene group described above in the step of producing the polymer represented by the formula (6) and the polymer having a hydroxyl group in the side chain may be used in combination. Further, the (meth) acrylate having an alkoxyalkyl group has 0.01 with respect to the ethylenically unsaturated monomer solid component from the viewpoint of adhesion to the substrate, viscosity of the pigment dispersion, and viscosity stability. The mass % to 10% by mass is preferable, and the content of 0.05% by mass to 5% by mass is particularly preferable.

As the polymerization initiator, for example, the above-mentioned general formula can be used. (6) An azo compound or an organic peroxide described in the step of the polymer shown. When the polymerization initiator is used, it is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the ethylenically unsaturated monomer.

The step of producing the vinyl-based resin-type dispersant (B) having a piperidinyl skeleton as described above can be carried out in the same manner as in the step of producing the polymer represented by the above formula (6), or as the case may be. Use a solvent. As the solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexane, toluene, xylene, acetone, methyl ethyl ketone, methoxypropyl acetate, cyclohexanone, propylene glycol monomethyl ether can be used. Acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate or diethylene glycol monobutyl ether The acid ester or the like is not particularly limited to these, and may be arbitrarily selected depending on the use, cost, and the like. The polymerization solvent can be used by mixing two or more types.

The amount of the solvent to be used is preferably from 0 to 300 parts by mass, more preferably from 0 to 100 parts by mass, per 100 parts by mass of the ethylenically unsaturated monomer. The solvent to be used is removed by an operation such as distillation after completion of the reaction, or may be used as a part of a dispersant.

Further, a resin type dispersant (A) having an aromatic carboxyl group and a vinyl resin type dispersant (B) having a piperidinyl skeleton are preferably used for pigment dispersion.

When the pigment dispersion is carried out, the vinyl-based resin type dispersant (B) having a piperidinyl skeleton becomes more easily adsorbed on the surface of the pigment, and the interaction with the pigment becomes stronger, thereby improving the dispersibility.

<Pigment Composition>

(mixing ratio)

In the pigment composition of the present invention, the blending ratio of the pigment, the resin-type dispersing agent (A) having an aromatic carboxyl group, and the vinyl-based resin-based dispersing agent (B) having a piperidinyl skeleton is 100 parts by mass based on the pigment. The resin type dispersant (A) having an aromatic carboxyl group is 5 to 100 parts by mass, and the vinyl resin type dispersant (B) having a piperidinyl skeleton is preferably 1 to 20 parts by mass, more preferably relative to the pigment. The resin-type dispersant (A) having an aromatic carboxyl group is 10 to 50 parts by mass, and the vinyl-based resin type dispersant (B) having a piperidinyl skeleton is preferably 2 to 10 parts by mass, more preferably 100 parts by mass.

(pigment dispersion)

The pigment composition of the present invention is a mixed pigment, a resin type dispersant (A) having an aromatic carboxyl group, a vinyl resin type dispersant (B) having a piperidinyl skeleton, and a dye derivative having an acidic substituent as needed. In addition to the various solvents, binder resins, additives, etc., depending on the situation, the pigment can be prepared by dispersion such as a horizontal sand mill, a vertical sand mixer, a ring bead mill, an attritor or the like. The composition is dispersed into a pigment dispersion of varnish.

Further, before being dispersed by a horizontal sand mill, a vertical sand mill, a ring bead mill, an attritor or the like, it can be dispersed before using a kneader or a three-roller meat mixer. It is dispersed by solids such as two roll mills. Further, a so-called disperser or a mixer such as a high-speed mixer, a homomixer, a ball mill, a roll mill, a ballast mill, or an ultrasonic disperser can be used for the production of the dispersion of the present invention.

(dispersion solvent)

The various solvents which can be used in the pigment composition of the present invention can be exemplified. Such as organic solvents, water, and the like. The solvent used in the synthesis of the resin-type dispersant (A) having an aromatic carboxyl group and the vinyl-based resin dispersant (B) having a piperidinyl skeleton can be used as it is. Further, after the completion of the reaction in the organic solvent used in the synthesis, the same organic solvent or a different solvent may be used after the removal by distillation or the like. Further, depending on the purpose, two or more organic solvents may be used in combination.

The organic solvent may, for example, be hexane, isophorone, toluene, o-xylene, m-xylene, m-diethylbenzene, n-butylbenzene, o-diethylbenzene or p-diethylbenzene. , 2 butyl benzene, 3 butyl benzene, ethyl acetate, n-amyl acetate, n-butyl acetate, isoamyl acetate, n-butyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester , n-propyl acetate, cyclohexanol acetate, ethyl 3-ethoxypropionate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, N, N- Dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, γ-butyrolactone, acetonitrile, 1,2,3-trichloropropane, o-chlorotoluene, p-chloro Toluene, o-dichlorobenzene, m-dichlorobenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, 3 ,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, n-butanol, isobutanol, benzyl alcohol, cyclohexanol, 3-methyl Oxybutanol, methylcyclohexanol, 3-methoxy-3-methyl-1-butanol, diacetone alcohol, 1,3-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, Glycol diethyl ether, ethylene glycol dibutyl ether, 1,4-dioxane, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene Alcohol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl Ether, two Ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol single Ethyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether Acid ester, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, 1,3-butylene glycol diacetate, propylene glycol diacetate, ethylene glycol diacetate, diethylene glycol Alcohol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, butyl Diol diacetate, pentanediol diacetate, butanediol diacetate, 1,4-butanediol diacetate, pentanediol diacetate, 1,5-pentane Alcohol diacetate or triacetin, etc., but is not necessarily limited to these.

(use)

The pigment composition of the present invention can be used for non-aqueous, water-based or solvent-free coatings, gravure inks, lithographic inks, inkjet inks, color filter inks, digital paper inks, plastic colorants, etc. It is especially suitable for transfer to inkjet inks and color filter inks.

When the pigment composition of the present invention is used as a color filter ink, the pigment composition is dispersed in the pigment dispersion of the varnish, and color is added. The coloring composition (pigment dispersion) of the color filter is further added with a photopolymerizable monomer and/or a photopolymerization initiator, and can be used as a photosensitive coloring composition (photoresist material) for a color filter.

<Photopolymerizable monomer>

The photopolymerizable monomer to be used in the present invention contains a monomer or an oligomer which is formed by curing by ultraviolet rays or heat, and these may be used singly or in combination of two or more.

The photopolymerizable single system may, for example, be methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate or methacrylic acid β. -carboxyethyl ester, polyethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylol Propane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,6-hexanediol diepoxypropyl ether dimethacrylate, bisphenol A Epoxypropyl ether dimethacrylate, neopentyl glycol diepoxypropyl ether dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethyl acrylate, A Various acrylates and methacrylates, acryls, methyl groups, such as tricyclononyl acrylate, acrylate, methyl methacrylate methacrylate, epoxy methacrylate, and urethane acrylate. Acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol diethyl Alkenyl ether, pentaerythritol trivinyl ether, methacrylamide, N-hydroxymethylmethacrylamide, N-vinylformamide, acrylonitrile, etc., but are not necessarily limited thereto.

The content of the photopolymerizable monomer is relative to the pigment 100 The amount of the component is preferably from 5 to 400 parts by mass, more preferably from 10 to 300 parts by mass from the viewpoint of photocurability and development.

<Photopolymerization initiator>

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl) can be used. )-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl Propan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butene Acetophenone-based compound such as ketone or 2-benzyl-2-methylamino-1-(4-morpholinylphenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin compounds such as isopropyl ether or benzyl dimethyl ketal; diphenyl ketone, benzamidine benzoic acid, methyl benzyl benzoyl benzoate, 4-phenyl diphenyl ketone, hydroxy diphenyl Ketone, acrylated diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide or 3,3',4,4'-tetra(t-butylperoxycarbonyl)diphenyl Diphenyl ketone compound such as ketone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Or a thioxanthone compound such as 2,4-diethylthioxanthone; 2,4,6-trichloro-s-three Triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl) -s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl) )-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethane) -s-triazine, 2-(4-methoxy-naphthalen-1-indolyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl a triazine-based compound such as (sodium)-6-triazine or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzhydryl)] or O-(ethenyl)-N-(1-phenyl-2-oxy(oxo)-2 An oxime ester compound such as -(4-methoxy-naphthyl)ethenyl)hydroxylamine; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6- a phosphine compound such as trimethylbenzhydryldiphenylphosphine oxide; an anthraquinone compound such as phenanthrenequinone, camphorquinone or ethylhydrazine; a borate ester compound; an oxazole compound; An imidazole compound; or a titanocene compound or the like.

These polymerization initiators may be used alone or in combination of two or more kinds in any ratio as needed.

The content of the polymerization initiator is preferably 5 to 200 parts by mass based on 100 parts by mass of the pigment, and more preferably 10 to 150 parts by mass from the viewpoint of photocurability and development.

(sensitizer)

Further, a sensitizer may be contained in the pigment composition of the present invention.

The sensitizer may, for example, be a 1,2-diketone derivative represented by an unsaturated ketone represented by chalcone derivatives, dibenzalacetone or the like, benzyl or camphorquinone. , benzoin derivatives, anthraquinone derivatives, naphthoquinone derivatives, anthracene derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone (thioxanthone) derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, etc. Base pigment, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, porphyrin (indoline) derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives , tetrabenzoporphyrin derivative, tetrapyrazine porphyrin derivative, phthalocyanine derivative, porphyrazine derivative, tetraquinoxalinoporphyrazine a derivative, a naphthalocyanine derivative, a subphthalocyanine derivative, a pyrylium derivative, a thiopyrylium derivative, a tetraphylline derivative, An annulen derivative, a spiropyran derivative, a spirooxazine derivative, a thiopyran derivative, a metal aromatic hydrocarbon complex, an organic ruthenium complex or a methyl ketone ( Michler's ketone) derivative, α-methoxyl ester, decylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine, 4,4' -diethylisophthalic acid diphenyl ketone, 3,3'- or 4,4'-diethylamine Diphenyl ketone and the like.

These sensitizers may be used alone or in combination of two or more kinds in any ratio as needed.

More specifically, for example, the "Pigment Handbook" (1986, Kodansha), Okawa Shinko, etc., "Compact Pigment Chemistry" (1981, CMC), and the writing of "Mr. The sensitizer described in (1986, CMC) is not limited to these. Further, it may contain other sensitizers which exhibit absorption of light from ultraviolet rays to near-infrared rays.

The content of the sensitizer is relative to the pigment composition The amount of the photopolymerization initiator is preferably from 3 to 60 parts by mass, more preferably from 5 to 50 parts by mass, from the viewpoint of photocurability and development.

(amine compound)

Further, the pigment composition of the present invention may contain an amine compound having a function of reducing and storing oxygen. Such an amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methylamino benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

(leveling agent)

Further, in the pigment composition of the present invention, it is preferred to add a leveling agent in order to improve the leveling property of the composition on the transparent substrate. The leveling agent is preferably dimethyloxane having a polyether structure or a polyester structure in the main chain. Specific examples of the dimethyl siloxane having a polyether structure in the main chain include, for example, FZ-2122 manufactured by Toray Dow Corning Co., Ltd., BYK-333 manufactured by BYK Corporation, and the like. Specific examples of the dimethyloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Corporation. Dimethyl decane having a polyether structure in the main chain and dimethyl methoxy alkane having a polyester structure in the main chain may be used in combination. The content of the leveling agent is generally from 100% by mass to the total mass of the coloring composition, and is preferably from 0.003 to 0.5% by mass.

A particularly preferred leveling agent is one which is a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. Even if it has a hydrophilic group, it has little solubility in water, and when added to a coloring composition, it has a so-called surfactant. Low surface tension reducing ability, although surface tension can be reduced If the force is low, the wettability to the glass sheet can be improved, and the chargeability can be sufficiently suppressed in the amount of the coating film defect which is not caused by foaming. As the leveling agent having such excellent characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit is an ethylene oxide unit or a propylene oxide unit, and the dimethyl polyoxyalkylene may have both a polyethylene oxide unit and a propylene oxide unit.

Moreover, the bonding form of the polyalkylene oxide unit and the dimethyl polyoxyalkylene may be a pendant type in which a polyalkylene oxide unit is bonded to a repeating unit of dimethyl polyoxyalkylene, and bonded to the second Any of the terminal block-modified type of the terminal of the methyl polyoxyalkylene and the linear block copolymer type which is alternately and repeatedly bonded to the dimethyl polyoxyalkylene. Dimethyl polyoxyalkylene having a polyalkylene oxide unit, which is sold by Toray Dow Corning, for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2207, but not limited to these.

An anionic, cationic, nonionic or amphoteric surfactant may also be added to the leveling agent. The surfactant can be used by mixing two or more types.

The anionic surfactant which is additionally added to the leveling agent may, for example, be a polyoxyethylene alkyl ether sulfate, a sodium dodecylbenzenesulfonate, an alkali salt of a styrene-acrylic acid copolymer, or an alkylnaphthalenesulfonate. Sodium, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene - Monoethanolamine, polyoxyethylene alkyl ether phosphate, etc. of an acrylic copolymer.

The cationic surfactant to be added to the leveling agent in an auxiliary manner may, for example, be an alkyl 4-based ammonium salt or an ethylene oxide adduct. The nonionic surfactant to be added to the leveling agent in an auxiliary manner is, for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate. , polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaine such as alkyl dimethylamino acetic acid betaine, alkyl imidazoline and the like amphoteric surfactant Or a fluorine-based or polyoxyxene-based surfactant.

(hardener, hardening accelerator)

Further, in the pigment composition of the present invention, in order to assist the curing of the thermosetting resin, a curing agent, a curing accelerator, or the like may be contained as needed. The curing agent may be, for example, a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, or a sulfonic acid compound, but is not limited thereto, and may be any one that can react with a thermosetting resin. Any hardener can be used. Further, among these, for example, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferable. As the hardening accelerator, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4- Methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), a 4-grade ammonium compound (for example, triethylbenzyl chloride) Ammonium, etc.), blocked isocyanate compounds (eg dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-B) a group of 4-methylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., a phosphorus compound (for example, triphenylphosphine, etc.), hydrazine Guanamine Compounds (eg, melamine, guanamine, acetammine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methylpropenyloxyethyl-S-) Triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine, isocyanuric acid adduct, 2,4 -diamino-6-methacryloxyethyl-S-triazine, isocyanuric acid adduct, etc.). These systems may be used alone or in combination of two or more. The content of the curing accelerator is based on the total mass of the thermosetting resin (100 parts by mass), preferably 0.01 to 15 parts by mass.

(Other additive ingredients)

In the pigment composition of the present invention, a storage stabilizer may be contained in order to stabilize the viscosity of the composition over time. Further, in order to improve the adhesion to the transparent substrate, a adhesion improving agent such as a decane coupling agent may be contained.

Examples of the storage stabilizer include a 4-stage ammonium chloride such as benzyltrimethyl chloride or diethylhydroxylamine, an organic acid such as lactic acid or oxalic acid, a methyl ether thereof, and a third butyl catechol. An organic phosphine such as tetraethylphosphine or tetraphenylphosphine, or a phosphite. The storage stabilizer is used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total mass of the colorant (a).

Examples of the adhesion enhancer include vinyl decane such as vinyl ginate (β-methoxyethoxy) decane, vinyl ethoxy decane, and vinyl trimethoxy decane, and γ-methyl propylene oxy group. (meth)acrylic decane such as propyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxycyclohexyl)methyl Epoxy decane, γ-glycidylpropyltrimethoxydecane, γ-glycidylpropyltriethoxydecane, etc., N-β(aminoethyl)γ- Aminopropyltrimethoxyfluorene Alkane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldiethoxydecane, γ-amino group Propyltriethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxy A decane coupling agent such as an alkyl decane such as decane, a thiodecane such as γ-mercaptopropyltrimethoxydecane or γ-mercaptopropyltriethoxydecane. The adhesion enhancer may be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the total mass of the pigment.

(adhesive resin)

When the pigment is dispersed, the resin-type dispersant (A) having an aromatic carboxyl group and/or the vinyl-based resin (B) having a piperidinyl skeleton of the present invention can also be used as the binder resin.

Further, unlike the resin-based dispersant (A) having an aromatic carboxyl group and the vinyl-based resin (B) having a piperidinyl skeleton, an example of a binder resin to be used in the pigment composition of the present invention can be obtained. For example, a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin can be mentioned.

When the pigment composition of the present invention is used as a resist ink for a color filter or the like, an alkali-soluble or solvent-soluble resin can be used among the binder resins.

The thermoplastic resin may, for example, be an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, or a polyacetic acid. Vinyl ester, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber tree Fat, cellulose, polyethylene (HDPE, LDPE), polybutadiene and polyimine resin.

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

The vinyl-based alkali-soluble resin copolymerized with the ethylenically unsaturated monomer having an acidic substituent may, for example, be a resin having an acidic substituent such as a carboxyl group or a fluorenyl group. The alkali-soluble resin may specifically be, for example, an acrylic resin having an acidic substituent, an α-olefin/maleic anhydride copolymer, a styrene/styrenesulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer or an isobutylene. / maleic anhydride copolymer and the like. Among them, at least one resin selected from the group consisting of an acrylic resin having an acidic substituent and a styrene/styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is suitably used because of its high heat resistance and transparency.

The active energy ray-curable resin having an ethylenically unsaturated double bond may, for example, be a resin obtained by introducing an ethylenically unsaturated double bond by the method (i) or (ii) shown below.

[method (i)]

The method (i) is, for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers, and having an ethylenically unsaturated double bond. The carboxyl group of the unsaturated monobasic acid is subjected to an addition reaction, and then the polyhydroxy acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

An ethylenically unsaturated single system having an epoxy group can be exemplified For example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxy (meth)acrylate Butyl ester and 3,4-epoxycyclohexyl (meth)acrylate may be used alone or in combination of two or more. From the viewpoint of the reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.

Examples of the unsaturated monobasic acid include (meth)acrylic acid, 2-butenoic acid, o-, m-, p-vinylbenzoic acid, α-halogenalkyl group of (meth)acrylic acid, alkoxy group, and halogen. A monocarboxylic acid such as a nitro group or a cyano substituent may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used singly or in combination of two. the above. The number of the carboxyl groups may be increased, and if necessary, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining acid anhydride group or the like. Further, in the case of a polybasic acid anhydride, if tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used, an ethylenically unsaturated double bond can be further increased.

A similar method of the method (i) is, for example, a part of a side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another one or more monomers, and having an epoxy group. A method in which an ethylenically unsaturated monomer is subjected to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

[method (ii)]

The method (ii) is exemplified by using an ethylenically unsaturated monomer having a hydroxyl group. A method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerizing a monomer having another carboxyl group-containing unsaturated monobasic acid or another monomer.

The ethylenically unsaturated single system having a hydroxyl group may, for example, be 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-(meth)acrylate. a hydroxyalkyl (meth)acrylate such as hydroxybutyl ester, glycerin (meth) acrylate or cyclohexane dimethanol mono(meth) acrylate, and these may be used singly or in combination of two or more. Further, in the above (meth)acrylic acid hydroxyalkyl ester, a polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide, or a poly-γ-pentane An addition of a polyester mono(meth)acrylate such as lactone, poly-ε-caprolactone, and/or poly 12-hydroxystearic acid. From the viewpoint of suppressing the foreign matter of the coating film, 2-hydroxyethyl (meth)acrylate or glycerin (meth) acrylate is preferable.

The ethylenically unsaturated single system having an isocyanate group may, for example, be 2-(meth)acryloxyethyl isocyanate or 1,1-bis[methylpropenyloxy]ethyl isocyanate, and is not limited thereto. Two or more types may be used in combination.

In order to disperse the pigment well, the weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. Further, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

Further, from the viewpoints of dispersibility, stability, development, and heat resistance of the pigment, it acts as a carboxyl group of the alkali-soluble group at the time of adsorption of the colorant and the development, and acts as an affinity group for the colorant support and the solvent. It The balance between the aliphatic group and the aromatic group, the dispersibility of the pigment, the permeability of the developing solution of the coating film, the solubility of the developing solution in the uncured portion, and the durability are important, and the acid value is 20 to 300 mgKOH. The resin of /g is preferred. When the acid value is less than 20 mgKOH/g, the solubility in the developing solution is poor, and it is difficult to form a fine pattern. Further, when it exceeds 300 mgKOH/g, the fine pattern may not remain.

The resin is excellent in film formability and various kinds of resistance, and is preferably used in an amount of 30 parts by mass or more based on 100 parts by mass of the total mass of the pigment, and a high colorant concentration can exhibit good color characteristics, and 500 parts by mass or less is used. The amount is better. More preferably, it is 100 to 400 parts by mass, and more preferably 160 to 320 parts by mass. Such a composition ratio of the pigment can further expand the chromaticity region.

<Method for Producing Pigment Composition>

In the pigment composition of the present invention, a pigment, a resin-based dispersant (A) having an aromatic carboxyl group, a vinyl-based resin (B) having a piperidinyl skeleton, a solvent, and the like are used, and three roll mills and two are used together. Various dispersing means such as a roll mill, a sand mill, a kneader, a trimix, and an attritor can be produced by finely dispersing (pigment dispersion). Further, the pigment composition of the present invention may be dispersed together with other coloring agents such as a green pigment or a yellow pigment, or may be produced by mixing the respective dispersers.

Further, when used as a photosensitive pigment composition (photoresist material) for a color filter, it can be prepared as a solvent development type or an alkali development type coloring composition. The solvent-developing type or the alkali-developing type coloring composition may dissolve the pigment dispersion, the photopolymerizable monomer, and/or the photopolymerization initiator, as needed The agent, other dispersing agents and additives are mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added after the coloring composition is prepared.

(removal of coarse particles)

The pigment composition of the present invention can remove coarse particles of 5 μm or more by means of centrifugation, sintering filtration, membrane filtration, etc., preferably removes coarse particles of 1 μm or more, and more preferably removes coarse particles of 0.5 μm or more. Particles and dust that is mixed in. Such a pigment composition is preferably substantially free of particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color Filter>

Next, a color filter relating to the present invention will be described. The color filter of the present invention includes a filter segment formed by using the colored composition for a color filter of the present invention. The color filter may be, for example, a red filter segment, a green filter segment, and a blue filter segment, and the filter segment may be coated by a spin coating method or a slit coating method. After the colored filter is colored with a composition, it is irradiated with an active energy ray such as an ultraviolet ray to partially cure the filter segment, and then formed on the substrate by development.

The coloring composition for a color filter of the present invention is used for formation of at least one filter segment, and other color filter segments other than the color filter composition can be used by using a conventionally used red coloring composition and blue coloring composition. The object is formed by a green coloring composition. In the coloring composition of each color other than the coloring composition of the color filter of the present invention, each coloring composition containing a coloring agent (any one of a pigment and a dye), the above-mentioned binder resin, and the photopolymerizable composition can be used. And formed.

The color filter of the present invention is provided with a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further be a member having a magenta filter segment, a cyan filter segment, and a yellow filter segment. At least one of the color filter of the present invention, which is a red filter segment, a green filter segment, and a yellow filter segment, is formed from the pigment composition of the present invention. In particular, green filter segments are preferably formed from the pigment composition of the present invention.

The blue filter segment can be formed using a general blue coloring composition comprising a blue pigment and a colorant support. The blue pigment may be, for example, CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64. Wait. Further, a violet pigment can be used in combination with the blue coloring composition. The purple pigments which can be used in combination are, for example, CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, Purple pigments such as 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50. Further, a salt-forming compound which exhibits a blue or violet basic dye or an acid dye can also be used. When a dye is used, a triarylmethane dye or an oxonium dye is preferred from the viewpoint of brightness.

(Manufacturing method of color filter)

The color filter of the present invention can be produced by a printing method or a photolithography method.

The formation of the color filter formed by the printing method can be repeated as long as the printing and drying of the pigment composition as the printing ink are repeated, and the method of manufacturing the color filter is low-cost and Excellent productivity. Furthermore, due to the development of printing technology, it is possible to perform printing with a fine pattern of higher dimensional accuracy and smoothness. For printing, on a printed plate, or on a blanket, it is preferred that the ink is not dried and cured. Moreover, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the ink viscosity with a dispersing agent or an extender pigment.

When a color filter is formed by photolithography, a coating method such as spray coating, spin coating, slit coating, or roll coating is applied to a transparent substrate to prepare a solvent for the above-described solvent development type. Or the pigment composition of the alkali-developing colored resist material, so that the dry film thickness is 0.2 to 5 μm . According to the film to be dried, ultraviolet exposure is performed by a mask having a predetermined pattern which is provided in contact or non-contact with the film. Then, it is immersed in a solvent or an alkali developing solution, or sprayed, and the developing solution is sprayed to remove the uncured portion to form a desired pattern, and then the same operation is repeated for other colors to manufacture a color filter. . Further, in order to promote polymerization of the colored photoresist material, heating may be performed as needed. According to the photolithography method, a color filter having higher precision than the above printing method can be manufactured.

In the case of development, an aqueous solution such as sodium carbonate or sodium hydroxide can be used as the alkali developing solution, and an organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developing solution.

Further, in order to increase the ultraviolet exposure sensitivity, after drying and drying the colored photoresist, a dry water-soluble or alkali-soluble resin is applied, for example, coated with a dry polyvinyl alcohol or a water-soluble acrylic resin to prevent the formation of oxygen. After the film which is hindered by polymerization, ultraviolet exposure can also be performed.

The color filter of the present invention is in addition to the above method, It can be produced by an electrodeposition method, a transfer method, an inkjet method, or the like, but any method can be used for the pigment composition of the present invention. Further, the electrodeposition method utilizes a transparent conductive film formed on a substrate, and electrophoretically deposits the filter segments of the respective colors on the transparent conductive film by electrophoresis of the colloidal particles, thereby producing a color filter. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of the peelable transfer substrate sheet, and the filter segment is transferred onto a desired substrate.

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

The color filter is bonded to the counter substrate by using a sealant, and the liquid crystal is injected from the injection port provided in the sealing portion, and then the injection port is sealed, and if necessary, the polarizing film or the retardation film is bonded to the substrate. On the outside, a liquid crystal display panel is manufactured.

Such a liquid crystal display panel can be used for a twisted nematic (TN), super twisted nematic (STN), lateral electric field effect (IPS), vertical alignment (VA), optically compensated bend (OCB). A liquid crystal display mode in which color filters are colored.

Example

Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not particularly limited to the embodiments. Further, in the examples, "parts" means "parts by mass". Further, Mn and Mw refer to a number average molecular weight and a weight average molecular weight, respectively.

(Average molecular weight of resin type dispersant (A) having an aromatic carboxyl group)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the acrylic resin using the resin as the pigment support were TSKgel column (manufactured by Tosoh Co., Ltd.) and GPC equipped with an RI detector (Tosoh Corporation) , HLC-8120GPC), using THF as a developing solvent, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the converted polystyrene.

(acid value of resin type dispersant (A) having an aromatic carboxyl group)

The acid value of the acrylic resin used as the resin of the pigment support is a value obtained by converting the measured acid value (mgKOH/g) to the solid content according to the potential difference titration method of JIS K0070.

(Average molecular weight of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the vinyl resin type dispersant (B) are HLC-8320GPC (manufactured by Tosoh Corporation), and SUPER-AW3000 is used as a column, and 30 mM is used. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the converted polystyrene as a solution of ethylamine and 10 mM LiBr in N,N-dimethylformamide solution.

(Vinyl resin type dispersant having a piperidinyl skeleton) (B) amine price)

The amine value of the vinyl resin type dispersant is such that the total amine value (mgKOH/g) measured is converted to the value of the solid content according to the method of ASTM D2074.

<Manufacturing example>

(Production Example 1 (A-1) of the resin type dispersant (A) having an aromatic carboxyl group)

In a reaction tank equipped with a gas introduction tube, a condenser tube, a stirring blade and a thermometer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin oxide (IV) as a catalyst were placed. After replacing with nitrogen, it was heated and stirred at 120 ° C for 4 hours. After confirming the solid content, it was confirmed that 98% of the reaction was carried out, and then 36.6 parts of pyromellitic dianhydride was added thereto, and the mixture was reacted at 120 ° C for 2 hours. From the measurement of 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 dispersing agent. Thus, a resin-type dispersant (A-1) having an aromatic carboxyl group having an acid value of 49 mgKOH/g and a number average molecular weight (Mn) of 2,500 per solid component was obtained. Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-1).

(Production Example 2 (A-2) of the resin type dispersant (A) having an aromatic carboxyl group)

In a reaction tank equipped with a gas introduction tube, a condenser tube, a stirring blade, and a thermometer, 60 parts of methoxypropyl acetate was placed, and the temperature was raised to 110 ° C. After the reaction vessel was replaced with nitrogen, it was dropped into the tank, and it took 2 40 parts of methyl methacrylate, 28 parts of benzyl methacrylate, 20 parts of n-butyl acrylate, 12 parts of 2-hydroxyethyl methacrylate, and methoxy are uniformly mixed in advance. A mixture of 40 parts of propyl acetate and 6 parts of dimethyl-2,2'-azobisisobutyrate was then stirred for 3 hours at the same temperature, and the reaction was completed. Thereby, an intermediate having a number average molecular weight (Mn) of 3,800 and an average number of hydroxyl groups in one molecule of 3.5 was obtained. In the intermediate, 5.1 parts of trimellitic anhydride and 0.1 part of dimethylbenzylamine were added to 100 parts of the solid component, and the mixture was reacted at 100 ° C for 6 hours. Thus, the resin-type dispersant having an aromatic carboxyl group per one molecule of trimellitic anhydride was one, the acid value per solid component was 30 mgKOH/g, and the number average molecular weight (Mn) was 4,000. -2). Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-2).

(Production Example 3 (A-3) of the resin type dispersant (A) having an aromatic carboxyl group)

In a reaction tank equipped with a gas introduction tube, a condenser tube, a stirring blade and a thermometer, 15 parts of methyl methacrylate, 5 parts of methacrylic acid, 20 parts of butyl methacrylate, and 2-methoxy acrylate were placed. 60 parts of ester and 45 parts of methoxypropyl acetate were substituted with nitrogen. The reaction vessel was heated to 80 ° C, 6 parts of 3-mercapto-1,2-propanediol was added, and then 2 parts of 2,2'-azobisisobutyronitrile was added in 20 portions every 30 minutes to dissolve in methoxypropyl B. 60 parts of the acid ester was directly reacted at 80 ° C for 12 hours, and after measuring the solid content, it was confirmed that 95% of the reaction was carried out, and then 9.7 parts of pyromellitic dianhydride was added, and 1,8-diazabicyclo ring as a catalyst was added. -[5.4.0]0.2-undecene 0.2 parts, and reacted at 120 ° C for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride was half-esterified, and the reaction was completed, and the acid value per solid component was 71 mgKOH/g, and the number average molecular weight (Mn) was obtained. A resin-type dispersant (A-3) having an aromatic carboxyl group of 5,000. Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-3).

(Production Example 4 (A-4) of the resin type dispersant (A) having an aromatic carboxyl group)

In a reaction tank equipped with a gas introduction tube, a condenser tube, a stirring blade and a thermometer, 80 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 44 parts of methoxypropyl acetate were placed, and replaced with nitrogen. . After heating to 80 ° C in a reaction vessel and adding 2.2 parts of 3-mercapto-1,2-propanediol, 0.3 parts of 2,2'-azobisisobutyronitrile was added in 20 portions every 30 minutes to dissolve in methoxypropyl group. 24 parts of the acetate was directly reacted at 80 ° C for 12 hours, and 95% of the reaction was confirmed by measuring the solid content. Then, 7.4 parts of trimellitic anhydride and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C for 2 hours, and reacted at 80 ° C. hour. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a resin type dispersant (A-4) having an aromatic carboxyl group having an acid value of 40 mgKOH/g and a number average molecular weight (Mn) of 5,200 per solid component was obtained. Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-4).

(Production Example 5 (A-5) of the resin type dispersant (A) having an aromatic carboxyl group)

15 parts of methyl methacrylate, 5 parts of methacrylic acid, 20 parts of butyl methacrylate, and 2-methoxy acrylate were placed in a reaction vessel equipped with a gas introduction tube, a condenser tube, a stirring blade and a thermometer. Ethyl acetate 60 parts, methoxy 44 parts of propyl acetate, substituted with nitrogen. The reaction vessel was heated to 80 ° C, and after adding 2.0 parts of 3-mercapto-1,2-propanediol, 20 parts of 2,2'-azobisisobutyronitrile was added in 20 portions every 30 minutes to dissolve in methoxypropyl B. The acid ester of 58 parts was directly reacted at 80 ° C for 12 hours, and by measuring the solid content, 95% of the reaction was confirmed. Then, 3.4 parts of pyromellitic dianhydride and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C for 2 hours, and reacted at 80 ° C. 5 hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a resin type dispersant (A-5) having an aromatic carboxyl group having an acid value of 46 mgKOH/g and a number average molecular weight (Mn) of 143,000 per solid component was obtained. Then, propylene glycol monomethyl ether acetate was added to the synthesized resin solution so that the nonvolatile content was 40% by weight to prepare a solution of the resin type dispersant (A-5).

(Production Example 6 (B-1) of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton)

In a reaction vessel equipped with a gas introduction tube, a condenser tube, a stirring blade, and a thermometer, 133 parts of methoxypropyl acetate was placed, and the temperature was raised to 110 ° C while nitrogen substitution was performed. Into the tank, 120 parts of tetramethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FANCRYL FA-712HM), 70 parts of methyl acrylate, and 10 parts of 2-hydroxyethyl methacrylate were placed. 6 parts of methoxypropyl acetate and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), after stirring until uniform, it took 2 hours to the reaction tank, and then The reaction was continued at the same temperature for 3 hours. Thus, a vinyl-based resin type dispersant (B-1) having a piperidinyl skeleton having an amine value of 145 mgKOH/g and a number average molecular weight (Mn) of 3,500 per solid component was obtained.

(Production Examples 7 to 14 (B-2 to B-9) of the vinyl-based resin type dispersant (B) having a piperidinyl skeleton)

The synthesis was carried out in the same manner as in Production Example 6 except that the materials and the amounts shown in Table 1 were used, and a vinyl resin-based dispersant (B-2) to (B-9) having a piperidinyl skeleton was obtained. The solution. The respective amine valence and number average molecular weight are as described in Table 1.

In the table, 2,2,6,6-tetramethylpiperidinyl methacrylate is a FANCRYL FA-712HM manufactured by Hitachi Chemical Co., Ltd., 1, 2, 2, 6, 6, 6-five. As the methylpiperidinyl methacrylate, FANCRYL FA-711MM manufactured by Hitachi Chemical Co., Ltd. was used.

(Comparative Production Example 1 (C-1) of a vinyl-based resin type dispersant having no piperidinyl skeleton)

In a reaction vessel equipped with a gas introduction tube, a condenser tube, a stirring blade, and a thermometer, 133 parts of methoxypropyl acetate was placed, and the temperature was raised to 110 ° C while nitrogen substitution was performed. Into the tank, 200 parts of N,N-dimethylaminoethyl methacrylate, 61 parts of methoxypropyl acetate and 2,2'-azobis (2,4-dimethyl) 6 parts of valeronitrile, and after stirring until uniform, it took 2 hours to the reaction tank, and then the reaction was continued at the same temperature for 3 hours. Thus, a vinyl resin-type dispersant (C-1) having no amine group 345 mg KOH/g and a number average molecular weight (Mn) of 3000 and having no piperidinyl skeleton was obtained.

(Comparative Production Example 2 (C-2) of a vinyl-based resin type dispersant having no piperidinyl skeleton)

The mixture was synthesized in the same manner as in Comparative Production Example 1 except that the materials and the amounts of the materials described in Table 2 were used, and a solution of a vinyl resin-based dispersant (C-2) having no piperidinyl skeleton was obtained. The amine value and the number average molecular weight are as described in Table 2.

(Adjustment of Acrylic Resin Solution 1)

370 parts of propylene glycol monomethyl ether acetate was placed in the reaction vessel, and while heating to 80 ° C while injecting nitrogen gas into the container, 12.3 parts of methacrylic acid and benzyl methacrylate 49.2 were added dropwise at the same temperature for 1 hour. Share, A mixture of 24.2 parts of cumene phenol ethylene oxide-modified acrylate ("ARONIX M-110" manufactured by Toagosei Co., Ltd.) and 14.3 parts of 2-hydroxyethyl methacrylate was subjected to a polymerization reaction. After the completion of the dropwise addition, the reaction was further carried out at 80 ° C for 3 hours, and then 1.0 part of azobisisobutyronitrile was added and dissolved in 50 parts of propylene glycol monomethyl ether acetate, and the reaction was continued at 80 ° C for 1 hour to obtain a solution of an acrylic resin. . The acrylic resin has a weight average molecular weight of about 30,000. After cooling to room temperature, about 2 g of the resin solution was sampled, and dried by heating at 180 ° C for 20 minutes to measure a nonvolatile matter, and propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution to make the nonvolatile matter 40% by mass, a solution of the acrylic resin 1 was prepared.

<Confirmation of amine adsorption energy of pigment>

In a glass container which can be sealed, 1 g of CI Pigment Green 58 (hereinafter referred to as PG58) used in the examples was picked up, and a methoxypropyl acetate solution of 0.02 mol/liter of n-hexylamine (adsorbed material) was added. ML. The plug was inserted into the container and it took 1 hour in the ultrasonic cleaner to adsorb it on the surface of the pigment. It is applied to a centrifugal separator to precipitate a pigment to obtain an upper clear liquid. 15 ml of the upper clear liquid was used, and the residual n-hexylamine was back-titrated by a potentiometric titration apparatus using a solution of 0.02 mol/liter of dichloroperchloric acid. When the quantitative blank group was measured, it was confirmed to be a pigment having an amine adsorption energy of 550 μmol/g.

Similarly, CI Pigment Yellow 150 pigment (hereinafter referred to as PY150) and CI Pigment Yellow 138 (hereinafter referred to as PY138) and CI Pigment Blue 15:6 (hereinafter referred to as PB15:6) used in the examples of the present invention are also PY150 is confirmed in the same way. The results are shown in Table 3.

<Production of Pigment Composition for Color Filters>

[Example 1]

(Adjustment of pigment dispersion (pigment composition) D-1)

12.0 parts of a pigment (PG58), 56.0 parts of an organic solvent (propylene glycol monomethyl ether acetate; abbreviated as PGMAc), 7.68 parts of a dispersant (A-1) solution synthesized in Production Example 1, and a vinyl system synthesized in Production Example 9. After the mixture of 1.92 parts of the resin (B-4) solution was uniformly stirred and mixed, zirconia particles having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("Minimodel M-250 MKII" manufactured by Aegis, Japan) for 5 hours. Thereafter, the mixture was filtered through a 5.0 μm filter to prepare a pigment dispersion D-1.

[Examples 2 to 52] and [Comparative Examples 1 to 16]

(Adjustment of pigment dispersion D-2~D-68)

The pigment dispersions D-2 to D-53 were obtained in the same manner as in Example 1 except that the materials and the mixing ratios shown in Tables 4 to 7 were used.

The abbreviations in Tables 4 to 7 are as follows.

‧PG58: Pigment Green 58, zinc halide phthalocyanine pigment, amine adsorption energy 550 μ mol / g (micromol / g)

‧PY150: Pigment Yellow 150: Azomethine yellow pigment, amine adsorption energy 215 μ mol/g

‧PY138: Pigment Yellow 138: Quinone yellow pigment, amine adsorption energy 34 μ mol/g

‧PB15: 6: Pigment Blue: 15: 6: phthalocyanine blue pigment, amine adsorption energy 26 μ mol / g

‧Dispersant A-1~A-5: Resin-type dispersant (A) solution having aromatic carboxyl groups produced in Production Examples 1 to 5

Vinyl resin B-1 to B-9: a vinyl resin type dispersant (B) solution having a piperidinyl skeleton produced in Production Examples 6 to 14

‧ Vinyl resin C-1 to C-2: a vinyl resin solution having no piperidinyl skeleton produced in Comparative Production Examples 1 and 2

‧ solvent PGMAC: propylene glycol monomethyl ether acetate

‧Derivative A: The pigment skeleton is a quinophthalone type, and the metal ion of the metal salt of the dye derivative is a derivative having an aluminum ion

<Evaluation of Pigment Composition for Color Filters (Pigment Dispersions D-1 to D-68)>

The evaluation of the brightness, contrast, viscosity, and storage stability of the pigment dispersions (D-1 to D-68) obtained in the examples and the comparative examples was carried out by the following method. The results are shown in Tables 8-11.

Regarding the evaluation results, B~AA is practical.

(brightness)

The obtained pigment dispersion was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thick, dried at 70 ° C for 20 minutes, and then heated at 230 ° C for 40 minutes to obtain a chromaticity of the obtained substrate of [PG58]. C light source, x=0.224, y=0.600

[PY150] at C light source, x=0.440, y=0.510

[PG58/PY138] at C source, x=0.268, y=0.600

[PB15: 6 o'clock] at C light source, x=0.140, y=0.150

Coating the substrate. The brightness (Y) of the obtained substrate was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

The judgment results are shown in Tables 8 to 11 as AA: particularly bright, and most suitable for practical use; A: Bright, suitable for practical use; C: Dark, not suitable for practical use.

(comparative (CR))

The obtained pigment dispersion was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thick using a spin coater, and the number of rotations was changed to have a dry film thickness of about 2 μm to prepare a coated substrate of three points. After coating, the film was dried in a hot air oven at 80 ° C for 30 minutes, and the respective film thicknesses and contrasts were measured. From the data of 3 points, the contrast (CR) of the film thickness of 2 μm was determined by a single correlation method.

The judgment results are shown in Tables 8 to 11, with A: indicating good contrast and being most suitable for practical use; B: indicating that the comparison is suitable for general use, and C: indicating poor contrast and not suitable for practical use.

(viscosity)

The viscosity of the pigment dispersion was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.), and the initial viscosity at 25 ° C was measured.

(save stability)

The obtained pigment dispersion was stored in a thermostat at 40 ° C for 1 week, and the viscosity of the pigment dispersion after the passage was measured by the same method as the viscosity measurement described above, and the temperature was kept at 40 ° C for 1 week. The rate of change in viscosity before and after is evaluated in three stages according to the following criteria.

A: The viscosity change rate (viscosity increase rate) is within ±10%, and no precipitate is generated.

B: The viscosity change rate (viscosity increase rate) is within ±10 to 15%, and no precipitate is generated.

C: A case where the viscosity change rate (viscosity increase rate) exceeds ±15%, or even if the viscosity change rate is within ±15%, a precipitate is generated.

Thus, with an amine PG58 adsorption energy of 550 μ mol / g, the resin having an aromatic carboxyl dispersant (A) and a vinyl-piperidyl skeleton of the resin dispersant (B) dispersed in the embodiment 1 to 13, a low viscosity pigment composition is obtained, but a resin type dispersant (A) having only an aromatic substituent, and a vinyl resin type dispersant (B) having only a piperidinyl skeleton are The viscosity deteriorates. Further, the vinyl resin used in combination with the resin-type dispersant (A) having an aromatic carboxyl group is a pigment dispersion dispersed with a vinyl-based resin (B) having a piperidinyl skeleton, and has no ratio of piperidine. The pigment dispersion in which the vinyl-based resin (C-1, 2) of the base skeleton is dispersed has a higher brightness.

From Tables 8 to 11, it is known that Examples 1 to 52 in which a resin type dispersant (A) having an aromatic carboxyl group and a vinyl resin (B) having a piperidinyl group are dispersed are used. (equivalent to dispersibility), initial viscosity (corresponding to fluidity), viscosity increase rate (corresponding to preservation stability), and brightness Y. On the other hand, the resin-type dispersant (A) having an aromatic carboxyl group and the vinyl-based resin (C-1 or C-2) having no piperidinyl skeleton are used, and the dispersion is low. . Further, all of the physical properties of the resin-based dispersant (A) having an aromatic carboxyl group or the vinyl-based resin (B) having a piperidinyl skeleton are not preferable.

<Adjustment of photosensitive coloring composition for color filter>

[Example 53]

(Adjustment of photosensitive coloring composition R-1 for color filter)

The mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive coloring composition R-1 for an alkali development type color filter.

Propylene glycol monomethyl ether acetate 33.2 parts

[Examples 54 to 104] and [Comparative Examples 17 to 32]

(Adjustment of photosensitive coloring composition R-2 to R-68 for color filters)

The coloring compositions R-2 to R-68 for color filters were obtained in the same manner as in Example 53 except that the pigments shown in Tables 4 to 7 were used.

<Evaluation of photosensitive coloring composition (R-1 to R-68) for color filters>

The evaluation of the brightness, contrast, viscosity, and storage stability of the photosensitive coloring compositions (R-1 to R-68) obtained in the examples and the comparative examples was carried out by the following method. The results are shown in Tables 12-15. Regarding the evaluation results, B~AA is practical.

(brightness)

The obtained photosensitive colored composition was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thick, dried at 70 ° C for 20 minutes, and then exposed to ultraviolet light at a cumulative light amount of 150 mJ using an ultrahigh pressure mercury lamp, and then heated at 230 ° C. After 40 minutes, the chromaticity of the obtained substrate was changed to [C58] at the C light source, x=0.224, y=0.600.

[At the time of PY150] at C light source, x=0.440, y=0.510

[At the time of PG58/PY138] at C light source, x=0.268, y=0.600

[PB15: 6 o'clock] at C light source, x=0.140, y=0.150

Coating the substrate. The brightness (Y) of the obtained substrate was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(comparative (CR))

The obtained photosensitive coloring composition was coated using a spin coater. Made on a glass substrate of 100 mm × 100 mm and 1.1 mm thick [At the time of PG58] The chromaticity y under the C light source is 0.595, 0.600, 0.605

[PY150] The chromaticity x under the C light source is 0.395, 0.440, 0.445

[At the time of PG58/PY138] The chromaticity y under the C light source is 0.595, 0.600, 0.605

[PB15: 6] The chromaticity y under C light source is 0.145, 0.150, 0.155

The number of rotations was changed, and three sheets were applied to obtain a coated substrate. The color filter was coated with a photosensitive coloring composition, and dried at 70 ° C for 20 minutes, and then exposed to ultraviolet light at a cumulative light amount of 150 mJ using an ultrahigh pressure mercury lamp, and then heated at 230 ° C for 40 minutes, left to stand for cooling, and then measured. Compared.

(viscosity) and (preservation stability)

The color filters described above were evaluated in the same manner as the coloring compositions (pigment dispersions D-1 to D-68).

(adhesion test)

1. Formation of colored coating film

The obtained photosensitive colored composition was applied onto a 10 cm × 10 cm glass substrate by a spin coating method, and then heated at 70 ° C for 15 minutes in a clean oven to remove the solvent to obtain a colored coating film of about 2 μm . . Then, after the substrate was cooled to room temperature, ultraviolet rays were irradiated with an ultrahigh pressure mercury lamp so that the cumulative exposure amount became 50 mJ/cm ² . Further, the exposure amount was measured using "PE10 B-V2" manufactured by OPHIR.

Further, the developing solution composed of a 0.2% by mass aqueous sodium carbonate solution was subjected to spray development, and after alkali development, it was washed with ion exchanged water. The substrate was heated at 230 ° C for 20 minutes to obtain a colored coating film substrate.

2. Protective film manufacturing method

The color filters of the respective colors obtained by the above-described pattern forming method are subjected to a cleaning treatment with a predetermined exposure amount using a UV/ozone apparatus (made by Iwasaki Electric Co., Ltd., OC-4010-S), and then borrowed. The protective film ("NN901" manufactured by JSR) was applied by a spin coating method, and then dried to form a transparent protective layer having a thickness of 2 μm . Then, it was dried by heating at 90 ° C for 10 minutes (pre-baked), and exposed to ultraviolet light at a predetermined exposure amount. Then, the developing solution composed of a 0.2% by mass aqueous sodium carbonate solution was subjected to spray development, and washed with water to complete patterning. The development time is a reasonable time to wash away the unexposed coating film, respectively. Then, it was heat-treated at 230 ° C for 30 minutes to form a protective film.

3. Evaluation method

Each of the colored coating films obtained by the above production method was adhered to a cellophane tape according to JIS-Z-1522, and the adhered portion was rubbed according to the eraser of JISS-6050. The protective film adhesion evaluation was carried out in accordance with the cross peel test of the checkerboard test method of JIS-K-5400.

The rating of the assessment is as follows. B~AA is practical.

AA: The defect area is less than 5% of the total area

A: The defect area is 5% or more of the total area, and less than 10%.

B: The defect area is more than 10% of the total area, less than 20%

C: The defect area is more than 20% of the total area

As described above, the examples in which the resin-type dispersing agent (A) having an aromatic carboxyl group and the vinyl-based resin (B) having a piperidinyl skeleton are dispersed are used for comparison (corresponding to dispersibility) and initial viscosity. (equivalent to fluidity), viscosity increase rate (corresponding to preservation stability) and brightness Y are excellent. On the other hand, the resin type dispersant (A) having an aromatic carboxyl group and the vinyl resin (C-1 or C-2) having no piperidinyl skeleton are used, and the dispersion is low in either of them. the result of. Moreover, only trees with aromatic carboxyl groups When the lipid dispersing agent (A) or the vinyl resin type dispersing agent (B) having a piperidinyl skeleton is dispersed, all of the physical properties are not good.

Further, the adhesion is in the system using a vinyl-based resin (B-8) having a piperidinyl skeleton copolymerized with an alkoxyfluorenyl group, and shows good results.

<Production of Color Filters>

First, a red photosensitive pigment composition and a blue photosensitive pigment composition for use in the production of a color filter are produced.

(Production of Red Photosensitive Pigment Composition (RR-1))

After the mixture of the following composition was stirred and homogenized, zirconia particles having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("Minimodel M-250 MKII" manufactured by Aegis, Japan) for 5 hours, and then 5.0 μm. The m filter was filtered to prepare a red colored composition (DR-1).

Then, the mixture of the following composition was uniformly stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).

(Production of blue photosensitive coloring composition (RB-1))

After the mixture of the following composition was stirred and homogenized, zirconia particles having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("Minimodel M-250 MKII" manufactured by Aegis, Japan) for 5 hours, and then 5.0 μm. The m filter was filtered to prepare a blue colored composition (DB-1).

Then, the mixture of the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).

(production of color filter)

A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied onto the substrate by a spin coater to form a colored film. In the film, an ultrahigh pressure mercury lamp was used to irradiate ultraviolet rays of 150 mJ/cm ² through a photomask. Then, the developing solution composed of a 0.2% by mass aqueous sodium carbonate solution was subjected to spray development to remove the unexposed portion, and then washed with ion-exchanged water. The substrate was heated at 220 ° C for 20 minutes to form a red filter. Fragment. Here, the red filter segment was subjected to heat treatment at 200 ° C, and the chromaticity of x = 0.640 and y = 0.330 was satisfied in the C light source (the following green and blue are also used). Further, by the same method, the green filter segment uses the green photosensitive coloring composition (R-1) of the present invention, conforming to the chromaticity of x=0.290 and y=0.600, and the blue filter segment is used. The blue photosensitive coloring composition (RB-1) conformed to the chromaticities of x=0.150 and y=0.060, and each of the filter segments was formed to obtain a color filter.

By using the green photosensitive coloring composition (R-1) of the present invention, the color filter can be made brighter, and other physical properties can be suitably used without any problem.

Claims (9)

A pigment composition comprising: a pigment, a resin type dispersant (A) having an aromatic carboxyl group, and a vinyl resin type dispersant (B) having a piperidinyl skeleton; wherein the piperidinyl group The vinyl-based resin type dispersant (B) of the skeleton has an amine value of 50 to 350 mgKOH/g. The pigment composition according to claim 1, wherein the resin-type dispersant (A) having an aromatic carboxyl group is a polymer (C) having a hydroxyl group, and an aromatic tricarboxylic anhydride (D1) and/or A resin type dispersant obtained by reacting an aromatic tetracarboxylic dianhydride (D2). The pigment composition of claim 1, wherein the pigment has an amine adsorption energy of 50 to 700 micromoles per gram (μmol/g). The pigment composition according to claim 2, wherein the polymer (C) having a hydroxyl group is a polymer (C1) having a hydroxyl group at a single terminal. The pigment composition according to claim 2, wherein the polymer (C) having a hydroxyl group is a polymer (C2) having a hydroxyl group in a side chain. The pigment composition according to claim 4, wherein the polymer (C1) having a hydroxyl group at a single terminal is a polymer (C3) having two hydroxyl groups at a single terminal. The pigment composition according to any one of claims 1 to 6, wherein the pigment is a zinc halide phthalocyanine pigment. The pigment composition according to claim 1, further comprising a photopolymerizable monomer and/or a photopolymerization initiator. A color filter comprising: a filter segment formed of the pigment composition according to any one of claims 1 to 8 on the substrate.