TWI443155B - Coloring composition containing phthalocyanine pigment, ink-jet ink containing same, and color filter substrate - Google Patents

Description

Colored composition containing an indigo pigment, inkjet ink containing the colored composition, and color filter substrate

The present invention relates to a coloring composition excellent in dispersibility, fluidity, and storage stability, an inkjet ink containing the same, and a color filter.

Recently, since the color liquid crystal display having the largest use for the color filter substrate strongly requires "color reproducibility", the ink for manufacturing the color filter substrate requires high color purity, high color density, and high transparency. In order to satisfy these required physical properties, it is necessary to finely disperse the pigment.

The formation of the pixel portion of the color filter by the inkjet method is carried out by previously providing a black matrix on the transparent substrate and filling the ink by an inkjet method in a region defined by the black matrix. At this time, if the solid content of the ink is low and/or the pigment concentration is low, in the process of producing a color filter having a desired color density, the ink overflows beyond the black matrix, and the ink is mixed into the adjacent region. And damage the hue of the filter segment. Therefore, the ink used in the filter requires high solidification differentiation. High pigment concentration. Further, in order to ensure stable discharge property, low viscosity and viscosity stability are also required for the inkjet ink (for example, Patent Document 4). The green color of one of the three primary colors (red ‧ blue ‧ green; RGB) of the color filter substrate is generally halogenated using a copper halide phthalocyanine (for example, CI pigment green 36) in the photoresist method or the inkjet method. When the copper phthalocyanine pigment is dispersed, problems such as miniaturization of the pigment, excessive viscosity, and deterioration of the transmittance cannot be achieved.

In addition, in addition to the recent expansion of demand for thin film displays, it has also begun to require

(1) The color seen by the eye is faithfully reproduced, that is, the area ratio of the color reproduction range of the color gamut defined by the NTSC (National Television Standard Committee) specification is increased.

(2) The sharpness of the image, that is, the improvement of the color characteristics such as the improvement of contrast, especially in the conventional color filter using the copper halide phthalocyanine pigment, exists between the current chromaticity of green and the required chromaticity. A big gap is difficult to meet these needs.

In order to solve such problems, it is used to change the center metal of the indigo pigment from copper to zinc or nickel (for example, Patent Document 1, Patent Document 2, and Patent Document 3). However, the chemical properties of the zinc halide indigo pigment are different from those of the conventional green pigment, and it is known that it is a pigment which is difficult to disperse in an organic solvent as compared with the conventional copper halide indigo pigment. Therefore, it is difficult to stably disperse the zinc halide indigo pigment under the maintenance of superior color characteristics as long as the dispersant and solvent suitable for the conventional copper halide phthalocyanine or other pigments are used.

Further, since the organic solvent used in the dispersion of the zinc halide indigo pigment has a low boiling point and a high evaporation rate, it has a problem that the discharge property is deteriorated when using the main solvent as the inkjet ink, and it is difficult to remove the zinc halide. Indigo is practically used as inkjet ink.

(Patent Document 1) Japanese Patent Laid-Open Publication No. 2003-161828

(Patent Document 2) Japanese Patent Laid-Open Publication No. 2003-192947

(Patent Document 3) Japanese Patent Laid-Open Publication No. 2003-192948

(Patent Document 4) Japanese Patent Laid-Open Publication No. 2005-299090

An object of the present invention is to provide a colored composition which is a zinc indigo pigment having excellent color characteristics, which is high in solid content and high in pigment concentration, and excellent in dispersibility, fluidity and storage stability. Further, an object of the present invention is to provide an inkjet ink which can be stably discharged by using the above colored composition. Furthermore, it is an object of the present invention to provide a color filter substrate formed by an inkjet method using the above inkjet ink.

The above problem can be solved by a coloring composition containing a solvent (A), a pigment (B), and a basic dispersing agent (C), wherein the solvent (A) contains the following solvent. One or more solvents selected from the group:

The solvent (A-1) represented by the general formula (1),

CH ₃ -C(=O)-O-(CnH _2n O) _m -C(=O)-CH ₃ (1)

[wherein, C _n H _2n is a linear or branched alkyl chain, 1≦m≦3, 2≦n≦5];

The solvent (A-2) represented by the general formula (2),

R-(OC ₃ H ₆ ) _p -OC(=O)-CH ₃ (2)

[wherein, R is an alkyl group having 1 to 8 carbon atoms, and C ₃ H ₆ is a linear or branched propyl chain, 1≦p≦3];

The above pigment (B) contains the indigo pigment represented by the following general formula (3).

General formula (3):

[Chemical 2]

[In the formula, the central metal element M is Zn, and X ₁ to X ₁₆ are each independently an element selected from the group consisting of H, Cl, and Br].

In a preferred embodiment of the colored composition of the present invention, one or more solvents selected from the group consisting of the solvent (A-1) and the solvent (A-2) are contained in the total solvent in an amount of 60% by weight or more.

In another preferred embodiment of the coloring composition of the present invention, one or more solvents selected from the group consisting of the solvent (A-1) and the solvent (A-2) are contained at 760 mmHg and have a boiling point of 170 ° C or higher. Solvent.

In a more preferable aspect of the coloring composition of the present invention, the solvent selected from the group consisting of the solvent (A-1) and the solvent (A-2) is a solvent having a boiling point of less than 170 ° C at 760 mmHg. A mixture of solvents having a boiling point of 170 ° C or higher at 760 mmHg, a solvent having a boiling point of less than 170 ° C at 760 mmHg and a solvent having a boiling point of 170 ° C or more at 760 mmHg is 0:100 to 70:30.

In another preferred embodiment of the colored composition of the present invention, the solvent (A-1) is derived from ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol II. One or more solvents selected from the group consisting of acetate, dipropylene glycol diacetate, butanediol diacetate, and pentanediol diacetate; in a more preferred embodiment, solvent (A-1) a solvent selected from the group consisting of diethylene glycol diacetate, propylene glycol diacetate, and butanediol diacetate;

In another preferred embodiment of the color composition of the present invention, the solvent (A-2) is propylene glycol monomethyl ether acetate and/or dipropylene glycol monomethyl ether acetate; in a more preferred embodiment, the solvent ( A-2) is dipropylene glycol monomethyl ether acetate.

In another preferred embodiment of the coloring composition of the present invention, the alkaline dispersing agent (C) contains an alkaline dispersing agent (Ca) of an acrylic polymer chain, a hydroxycarboxylic acid polymer chain, and an alkylene oxide. One or more partial structures selected from the group consisting of a polyalkylamine chain, a polyethylenimine chain, a cationic polyurethane chain, and a cationic acrylic polymer chain; One or more cationic partial structures are selected.

In another preferred embodiment of the coloring composition of the present invention, the pigment derivative (D) represented by the following general formula (4) is contained.

General formula (4):

G ⁴ -J ⁴ q (4)

(In the general formula (4), G ⁴ is a residue of a pigment prototype compound of q valence, and J ⁴ is a basic substituent, an acidic substituent or a neutral substituent, and q is an integer of 1 to 4.)

In another preferred embodiment of the colored composition of the present invention, the solid content of the colored composition is from 3 to 60% by weight based on the total weight of the colored composition.

In another preferred embodiment of the coloring composition of the present invention, the pigment (B) of the coloring composition is contained in an amount of from 1 to 30% by weight based on the total weight of the coloring composition.

In another preferred embodiment of the colored composition of the present invention, the weight ratio of the pigment (B) to the basic dispersant (C) of the colored composition is from 100:3 to 100:150.

Further, the present invention relates to an inkjet ink containing the above colored composition.

Further, the present invention relates to an inkjet ink containing the above colored composition and further containing a binder resin (E) and/or a thermally reactive compound (F).

In other preferred aspects of the inkjet ink of the present invention, the thermally reactive compound (F) is derived from a melamine compound, benzoquinone Compound, carbodiimide compound, epoxy compound, oxetane compound, phenol compound, benzo One or more compounds selected from the group consisting of a compound, a blocked carboxylic acid compound, an acid-immobilized isocyanate compound, an acrylate monomer, and a decane coupling agent; in a preferred embodiment, at least a melamine compound and / or benzoquinone Compound.

Furthermore, the present invention relates to the above inkjet ink for a color filter substrate.

Furthermore, the present invention also relates to a color filter substrate on which a printing layer formed by the inkjet ink is carried on a substrate.

The colored composition of the present invention is characterized by comprising:

The solvent (A) contains one or more solvents selected from the group consisting of the following solvents:

The solvent (A-1) represented by the general formula (1),

CH ₃ -C(=O)-O-(C _n H _2n O) _m -C(=O)-CH ₃ (1)

[wherein, C _n H _2n is a linear or branched alkyl chain, 1≦m≦3, 2≦n≦5];

The solvent (A-2) represented by the general formula (2),

R-(OC ₃ H ₆ ) _p -OC(=O)-CH ₃ (2)

[wherein, R is an alkyl group having 1 to 8 carbon atoms, and C ₃ H ₆ is a linear or branched propyl chain, 1≦p≦3];

The pigment (B) contains one or more pigments selected from the group consisting of the indigo pigments represented by the following general formula (3).

General formula (3):

[Chemical 3]

[wherein, the central metal element M is Zn, and X ₁ to X ₁₆ are each independently an element selected from the group consisting of H, Cl, and Br];

Alkaline dispersant (C).

The coloring composition of the present invention contains a solvent selected from the solvent (A-1) and the solvent (A-2), and has excellent dispersibility and flow even at a high solid content of ‧ high pigment concentration Sex and preservation stability. Therefore, it is possible to modulate the ink composition for ink jet recording excellent in the coloring composition of the present invention, and to provide an improved color discharge substrate or ink when the color filter substrate is manufactured by using the thus prepared ink composition for ink jet recording. The flyoff diameter is affected by the yield, and a sufficient concentration of the printed layer.

[About solvent]

The colored composition of the present invention is characterized in that a specific solvent (A) is used, and the solvent (A) contains one or more solvents selected from the group consisting of the following solvents:

The solvent (A-1) represented by the general formula (1),

CH ₃ -C(=O)-O-(C _n H _2n O) _m -C(=O)-CH ₃ (1)

[wherein, C _n H _2n is a linear or branched alkyl chain, 1≦m≦3, 2≦n≦5];

The solvent (A-2) represented by the general formula (2),

R-(OC ₃ H ₆ ) _p -OC(=O)-CH ₃ (2)

[wherein, R is an alkyl group having 1 to 8 carbon atoms, and C ₃ H ₆ is a linear or branched propyl chain, 1≦p≦3].

As characteristics required for the solvent used for the inkjet ink, for example,

(1) The most suitable affinity for pigments and dispersants for maintaining low viscosity and viscosity stability over time;

(2) The optimum drying speed and surface tension of the ink used to maintain the discharge stability.

In particular, inkjet inks used for color filter applications and the like require high pigment fraction and high solid fraction concentration from the viewpoints of productivity or prevention of color mixing, and require a solvent system to be optimally designed.

In the copper phthalocyanine pigment and the zinc phthalocyanine pigment, since the solubility of the pigment itself is different, the solvent most suitable for dispersion is also different. The solvent which is most suitable for the dispersion of the copper phthalocyanine pigment has too good affinity with the zinc phthalocyanine pigment and is not suitable for dispersion.

The solvent (A) containing one or more solvents selected from the group consisting of the solvent (A-1) and the solvent (A-2) has the most suitable affinity with the pigment (B), so that the fineness of the pigment can be achieved. Dispersion, low viscosity and good viscosity stability over time.

When the solvent (A-1) is 1 ≦m≦3 and 2≦n≦5 in the above general formula (1), the solvent (A-2) in the above general formula (2) is a carbon number of 1~ When the alkyl group of 8 is 1 ≦p≦3, the affinity with the pigment (B) is most suitable. When m and n of the above general formula (1) and the R and p of the general formula (2) of the solvent (A-2) in the solvent (A-1) are values exceeding the above-defined range, the pigment (B) The affinity is too good or too poor, so the dispersibility of the pigment is deteriorated, and the degree of miniaturization cannot be obtained, and a problem such as high viscosity and deterioration of viscosity over time occurs.

In a preferred embodiment of the coloring composition of the present invention, one or more solvents selected from the group consisting of solvent (A-1) and solvent (A-2) account for 60% by weight or more of the total solvent. If it is less than 60% by weight, the affinity for the pigment cannot be sufficiently exhibited.

In a preferred embodiment of the coloring composition of the present invention, one or more solvents selected from the group consisting of solvent (A-1) and solvent (A-2) contain a solvent having a boiling point of 170 ° C or higher at 760 mmHg. Further, a more preferable form is one or more solvents selected from the group consisting of a solvent (A-1) and a solvent (A-2), a solvent having a boiling point of less than 170 ° C at 760 mmHg and a boiling point of 170 ° C or higher at 760 mmHg. a mixture of solvents; a solvent having a boiling point of less than 170 ° C at 760 mmHg and a solvent having a boiling point of 170 ° C or more at 760 mmHg is 0:100 to 70:30. When the solvent having a boiling point of 170 ° C or higher at 760 mmHg is not the main solvent, sufficient discharge stability may not be obtained when it is prepared in the ink for inkjet. In order to prepare the dispersion stability, the viscosity, the drying property, and the like, the solvent having a boiling point of less than 170 ° C at 760 mmHg is used in the group selected from the group consisting of the solvent (A-1) and the solvent (A-2). In the solvent, if the solvent having a boiling point of less than 170 ° C at 760 mmHg exceeds 30% by weight, sufficient discharge stability may not be maintained.

The solvent (A-1) used in the present invention may, for example, be ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate or dipropylene glycol. Diacetate, butanediol diacetate, pentanediol diacetate, etc., all of which have a boiling point of 170 ° C or higher at 760 mmHg.

The butanediol diacetate system includes 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, and the like. The pentanediol diacetate system includes 1,5-pentanediol diacetate and the like.

The solvent (A-2) used in the present invention may, for example, be a solvent such as propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate having a boiling point of less than 170 ° C at 760 mmHg, propylene glycol monopropyl group. Ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether The acetate is equivalent to a solvent having a boiling point of 170 ° C or more at 760 mmHg, and propylene glycol monomethyl ether acetate or dipropylene glycol monomethyl ether acetate can be particularly suitably used.

A more preferable form of the coloring composition of the present invention is a solvent (A-3) having a boiling point of 240 ° C or more and a surface tension of 26 to 36 mN / m at 25 ° C at 760 mmHg. By using this solvent (A-3) in combination, it is possible to suppress drying in the vicinity of the head when preparing the ink for inkjet, and to improve discharge stability (especially intermittent discharge property). As the solvent (A-3) having a boiling point of 240 ° C or more and a surface tension of 26 to 36 mN/m at 25 ° C under 760 mmHg, the definitions of the above solvent (A-1) and solvent (A-2) can also be used. The compound included in the above may be used in a range of less than 40% of the total solvent in the case of the solvent (A-1) and the solvent (A-2), and may, for example, be diethylene glycol alone. N-butyl ether acetate, tripropylene glycol n-butyl ether, and the like.

[About pigments]

The pigment constituting the colored composition of the present invention is preferably colored to a desired hue, and is excellent in heat resistance, chemical resistance, liquid crystal resistance, and/or light resistance.

The pigment (B) constituting the colored composition of the present invention contains the pigment represented by the general formula (3):

[Chemical 4]

[In the formula, the central metal element M is Zn, and X ₁ to X ₁₆ are each independently an element selected from the group consisting of H, Cl, and Br]; especially a pigment containing X is Br.

In a preferred embodiment of the pigment constituting the colored composition of the present invention, the average number of hydrogen atoms in X is 0 or more and 2 or less, and the average number of Cl elements in X is 0 or more and 5 or less, and the average Br element number in X is 8 or more and 16 or less.

When a representative pigment of the general formula (3) is represented by a color index (C.I.), a green pigment such as C.I. Pigment Green 58 may be mentioned.

In the pigment (B) contained in the colored composition of the present invention, not only the above-mentioned zinc halide indigo pigment belonging to the main pigment but also other green pigments or yellow pigments may be used in combination for the purpose of color adjustment or complementary color. The green pigment which can be used in combination is represented by a color index (CI) number, and examples thereof include CI Pigment Green 7, 10, 36, and 37. Examples of the yellow pigment include CI Pigment Yellow 1, 2, 3, 4, and 5. 6,10,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42 , 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, 148, 150, 151, 152, 153, 154 , 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193 , 194, 199, etc.

The particle diameter of the pigment (B) is preferably sufficiently small with respect to the wavelength of visible light from the viewpoint of the absorption coefficient of visible light (appropriateness of the spectrum) and transparency. That is, the average primary particle diameter of the pigment is preferably 10 nm or more and 300 nm or less, particularly preferably 10 nm or more and 100 nm or less. Moreover, the primary particle diameter means the diameter of the smallest unit of pigment particles, and is measured by an electron microscope. The primary particle diameter of the pigment can be controlled within a suitable range using a known dispersing device such as a sand mill, a kneader, a twin roll or the like.

The preferred content of the pigment (B) of the coloring composition is from 1 to 30% by weight based on the total weight of the coloring composition.

[About Dispersion Resin]

The zinc halide indigo pigment of the main pigment of the pigment (B) of the colored composition of the present invention has a higher acidity than the conventional copper indigo pigment. Therefore, when the zinc disodium pigment is finely dispersed, the alkaline dispersant (C) can be suitably used, and the colored composition and the inkjet ink using the same can be improved in low viscosity and stability over time.

As the alkaline dispersing agent (C) used in the coloring composition of the present invention, a known basic resin type dispersing agent can be used. Specific examples of the commercially available resin type dispersant include the following.

BYK Chemie Co., Ltd. is a basic resin type dispersant, and may be, for example, Anti-Terra-U, U100, 204, 205, Disperbyk-101, 106, 108, 109, 112, 116, 130, 140, 142, 161, 162. , 163, 164, 166, 167, 168, 180, 182, 183, 184, 185, 2000, 2001, 2050, 2070, 2150, BYK-9076, 9077, and the like.

Made by Lubrizol Co., Ltd. as a basic resin type dispersant, for example, Solsperse 9000, 13240, 13650, 13940, 17000, 18000, 20000, 24000 SC, 24000 GR, 28000, 31845, 32000, 32500, 32600, 33500, 34750, 35100, 35200, 37500, 38500, 44000, 55000, etc.

Chiba Specialty Chemicals Co., Ltd. is an alkaline resin type dispersant, and may be, for example, EFKA-4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4403, 4406, 4500, 4510, 4520, 4530, 4570, 4800, 5044, 5054, 5055, 5063, 5064, 5071, 5207, 5244, and the like.

Ajinomoto Fine Techno Co., Ltd. is an alkaline resin type dispersant, and examples thereof include AJISPER-PB-711, PB811, and PB821.

When a color filter is manufactured using the inkjet ink prepared by the coloring composition of the present invention, since the color filter is required to have transparency, the spray of the present invention is formed in the total wavelength region of 400 to 700 nm in the visible light region. The transmittance of the ink of the ink dispersion is preferably 80% or more, more preferably 95% or more.

Further, the alkaline dispersing agent (C) used in the coloring composition of the present invention preferably contains an alkaline dispersing agent (Ca) of an acrylic polymer chain, a hydroxycarboxylic acid polymer chain, and an oxidized stretch. One or more partial structures selected from the group consisting of alkyl polymer chains; and composed of a polyallylamine chain, a polyethylenimine chain, a cationic polyurethane chain, and a cationic acrylic polymer chain One or more cationic partial structures selected from the group.

The acrylic polymer chain is obtained by polymerizing one or more alkyl (meth)acrylate monomers. Further, if necessary, one or more kinds of (meth)acrylic acid alkyl monomers may be obtained by blocking or random copolymerization with another vinyl monomer.

A photopolymerizable group, a thermally reactive group, an anionic group, a cyclic aliphatic group, an aromatic group or the like may be optionally introduced into the side chain.

The hydroxycarboxylic acid polymer chain is obtained by subjecting a hydroxycarboxylic acid and/or a lactone as a raw material to a dehydration reaction or a ring-opening reaction.

The oxidized alkylene polymer chain is obtained by subjecting a diol and/or a cyclic ether to a dehydration reaction or a ring opening reaction.

The polyallylamine chain is obtained by removing the addition salt of polyallylamine hydrochloride obtained by radical polymerization of allylamine hydrochloride.

The polyethylenimine chain is obtained by ring-opening polymerization of ethimine.

The cationic polyurethane chain is obtained by polyaddition reaction of a dialkylamino group-containing diol with a diisocyanate.

The cationic acrylic polymer chain is obtained by radically copolymerizing a (meth) acrylate monomer containing a dialkylamino group with another monomer.

The alkaline dispersing agent (C) used in the colored composition of the present invention preferably further contains an alkaline dispersing agent (Cb) of one or more kinds selected from the group consisting of hydroxycarboxylic acid polymer chains; One or more cationic moiety structures selected from the group consisting of a polyallylamine chain, a polyethylenimine chain, and a cationic polyurethane chain.

Further, as the alkaline dispersant (C), any of a straight type or a comb type having a side chain on a main chain skeleton can be used.

The basic dispersing agent (C) which can be particularly suitably used in the coloring composition of the present invention is a polymer chain of a hydroxycarboxylic acid having a carboxyl group at one end (polyester [c-1]) and two in the main chain. a comb-type alkaline dispersing agent (Cc) obtained by a condensation reaction of a polyallylamine chain or a polyethylenimine chain (polyamine [c-2]) of the above primary or secondary amine group, but is not particularly limited Chemical structures and manufacturing methods other than these.

For example, a condensation reaction of a polyester [c-1] having a carboxyl group at a single terminal with a polyamine [c-2] having two or more primary or secondary amine groups in the main chain is a polyester [c-1] It is mixed and heated with polyamine [c-2], and is carried out by imidization of dehydration. By the reaction conditions at this time, that is, the filling ratio of the polyamine [c-2] of the polyester [c-1], the molecular weight of the polyamine [c-2] of the polyester [c-1], and the guanamine The reaction rate and the like of the reaction are controlled, and the molecular weight, amine value and acid value of the obtained alkaline dispersant (C) are controlled.

The number average molecular weight of the alkaline dispersant (C) is preferably from 1,000 to 100,000. When the number average molecular weight of the alkaline dispersant (C) is less than 1,000, the dispersion effect or storage stability is lowered. When the amount is more than 100,000, the viscosity of the dispersion is increased or the solubility in various organic solvents is lowered, resulting in poor dispersion. The alkali dispersant (C) preferably has an amine value of 5 to 100, and an acid value of preferably 0 to 50. The amine value and the acid value have a large influence on the solubility of the dispersant and the adsorption property of the pigment, and the maximum effect can be obtained within such an appropriate range.

The polyester [c-1] having a carboxyl group at a single terminal is obtained by self-condensation of a hydroxycarboxylic acid or a lactone or co-condensation of a hydroxycarboxylic acid with a lactone.

Examples of the hydroxycarboxylic acid include ricinolic acid, ricinoleic acid, a mixture of 9 and 10-hydroxystearic acid, 12-hydroxystearic acid, castor oil fatty acid, and hydrogenated hydrazine. Sesame oil fatty acid, lactic acid, etc., as lactones, for example, ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, 4-methyl The caprolactone, 2-methylcaprolactone and the like are preferably a cocondensate of 12-hydroxystearic acid and ε-caprolactone. Further, when the polyester is condensed, a carboxylic acid having no hydroxyl group is added as a polymerization stopper, for example, hexanoic acid, lauric acid, stearic acid, methoxyacetic acid or the like.

The polyamine [b-2] used in the present invention is not particularly limited as long as it has an amine group, and specific examples thereof include polyethylenimine, polyethylene polyamine, and polyallylamine. Polyethylenimine is a polyamine obtained by ring-opening polymerization of ethylenediamine in the presence of an acid catalyst. Polyethylene polyamine is obtained by polycondensation of ethylene dichloride and ammonia in the presence of a base catalyst. Polyamine. Further, the polyallylamine is a polyamine represented by the following general formula (5).

General formula (5):

H-[CH ₂ -CH(CH ₂ -NH ₂ )] _n7 -H (5)

[In general formula (5), n7 represents an integer from 2 to 1000. ]

In view of the above, the commercially available alkaline dispersant (C) which can be used as the coloring composition of the present invention is, for example, AjISPER-PB821 manufactured by Ajinomoto Fine Techno Co., Ltd., and Solsperse 32000 manufactured by Lubrizol Corporation of Japan. EFKA-4300 manufactured by Chiba Specialty Chemicals Co., Ltd., and Disperbyk-161 manufactured by BYK Chemie Co., Ltd., and more preferably, for example, AJISPER-PB821 and Solsperse 32000 manufactured by Lubrizol Co., Ltd., but are not limited thereto.

The preferred weight ratio of the pigment (B) to the basic dispersant (C) contained in the colored composition of the present invention is from 100:3 to 100:150.

[About pigment derivatives (D)]

In the present invention, a pigment derivative can be used as needed. As the pigment derivative which can be used in the present invention, for example, those shown in the following general formula (4) can be used.

General formula (4):

G ⁴ -J ⁴ q (4)

(In the formula (4), G ⁴ is a residue of a dye prototype compound having a q valence, and J ⁴ is a basic substituent, an acidic substituent or a neutral substituent, and q is an integer of 1 to 4.)

The basic substituent may, for example, be a substituent represented by the general formula (6), the general formula (7), the general formula (8) or the general formula (9).

General formula (6):

[Chemical 5]

(In general formula (6), X ⁶¹ represents: -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -, -CH ₂ - or direct bonding. n6 represents an integer of 1 to 10. R ^a6 , R ^B6 represents an independently substituted alkyl group, a substituted alkenyl group, a substituted phenyl group, or a combination of R ^a6 and R ^b6 and further containing a nitrogen, oxygen or sulfur atom. The heterocyclic group has preferably a carbon number of from 1 to 10 in the alkyl group and the alkenyl group.

General formula (7):

[Chemical 6]

(In the general formula (7), R ^a7 and R ^b7 represent an independently substituted alkyl group, a substituent-substituted alkenyl group, a substituted phenyl group, or R ^a7 and R ^{b7 are} integrated and further a heterocyclic ring which may be substituted with a nitrogen, oxygen or sulfur atom. The alkyl group and the alkenyl group preferably have a carbon number of from 1 to 10.

General formula (8):

[Chemistry 7]

(In general formula (8), X ⁸¹ represents: -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -, -CH ₂ - or direct bonding.

R ^a8 represents an alkyl group which may be substituted, an alkenyl group which may be substituted, and a phenyl group which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably from 1 to 10.

R ^b8 , R ^c8 , R ^d8 and R ^e8 represent a hydrogen atom which may be independently substituted, an alkyl group which may be substituted, an alkenyl group which may be substituted, and a phenyl group which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably from 1 to 5. )

General formula (9):

[化8]

(In general formula (9), X ⁹¹ represents: -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -, -CH ₂ - or direct bonding.

Y ⁹ represents: -NR ^a9 -Z ⁹ -NR ^b9 - or direct bonding.

R ^a9 and R ^b9 represent a hydrogen atom which may be independently substituted, an alkyl group which may be substituted, an alkenyl group which may be substituted, and a phenyl group which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably from 1 to 5.

Z ⁹ represents a substituted alkyl group, an alkenyl group which may be substituted, and a phenyl group which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably from 1 to 8.

P ⁹ represents a substituent represented by the following general formula (9a) or a substituent represented by the following general formula (9b).

Q ⁹ represents a hydroxyl group, an alkoxy group, a substituent represented by the above general formula (7) or a substituent represented by the above general formula (8). )

General formula (9a):

[Chemistry 9]

(General formula (9a),

N9 means: an integer from 1 to 10.

Rc ⁹ and R ^d9 represent an independently substituted alkyl group, a substituent-substituted alkenyl group, a substituted phenyl group, or R ^c9 and R ^{d9 are} integrated and further contain a nitrogen, oxygen or sulfur atom. A heterocyclic ring which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably from 1 to 10. )

General formula (9b):

[化10]

(General formula (9b),

R ^e9 represents an alkyl group which may be substituted, an alkenyl group which may be substituted, and a phenyl group which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably from 1 to 10.

R ^f9 , R ^g9 , R ^h9 and R ⁱ⁹ represent a hydrogen atom which may be independently substituted, an alkyl group which may be substituted, an alkenyl group which may be substituted, and a phenyl group which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably from 1 to 5. )

The acidic or neutral substituent may, for example, be a substituent represented by the following general formula (10), general formula (11) or general formula (12).

General formula (10):

[11]

-SO ₃ M ¹⁰ /l ¹⁰ (10)

(in general formula (10),

M ¹⁰ represents a hydrogen atom, a calcium atom, a ruthenium atom, a ruthenium atom, a manganese atom or an aluminum atom.

l ¹⁰ means: the price of M ¹⁰ . )

General formula (11):

[化12]

(General formula (11)

R ^a11 , R ^b11 , R ^c11 and R ^d11 represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (except when all of them are hydrogen atoms).

General formula (12):

[Chemistry 13]

(in general formula (12),

A ¹² represents a hydrogen atom, a halogen atom, -NO ₂ , -NH ₂ or SO ₃ H.

k ₁₂ represents: an integer from 1 to 4. )

The pigment prototype compound (G ⁴ ) refers to a compound having a pigment skeleton generally known, and a compound having a similar pigment skeleton which hardly absorbs in the visible light region.

Examples of the residue of the dye prototype compound include a diketopyrrolopyrrole pigment residue, an azo dye residue (for example, azo, disazo, polyazo, etc.), an indigo pigment residue, and an anthracene. Pigment residues (eg, diamino dioxime, pyrimidine, yellow ketone, anthanthrone, indanthrene, pyranthrone, purine ketone (violanthrone, etc.), quinoline Pyridone-based pigment residue, two Pigment residue, perinone pigment residue, ruthenium pigment residue, thiophene pigment residue, isoporphyrin pigment residue, isoindolinone dye residue, quinoline Quinophthalone is a pigment residue, a Shilin pigment residue, a metal complex pigment residue, a lanthanide residue or three Residues, etc.

Further, as the anthracene derivative, an anthracene having the above basic, acidic or neutral substituent can be used. Again, as three Derivatives, for example, can be used for 1,3,5-three which may have the following substituents a derivative of the above basic, acidic or neutral substituent is introduced: an alkyl group (e.g., methyl, ethyl, etc.), an amine group, an alkylamino group (e.g., dimethylamino, diethylamino, Dibutylamino, etc.), nitro, hydroxy, alkoxy (eg methoxy, ethoxy, butoxy, etc.) or halogen (eg chlorine, etc.); may be methyl, methoxy, amine a phenyl group substituted with a dimethylamino group or a hydroxyl group; or may be methyl, ethyl, methoxy, ethoxy, amine, dimethylamino, diethylamino, nitro or A phenylamine group or the like substituted with a hydroxyl group or the like.

The coloring composition of the invention can be used as a high solid content, a high pigment concentration and a low viscosity, and can be used for a gravure ink, a lithographic ink, an inkjet or an automobile paint, etc., because a high coloring power/high transmittance printing material can be obtained, Since it is a coating material, it is especially suitable for use in a color filter substrate. When used as a color filter substrate, it can be used for inkjet inkjet inkjet, photolithographic resistive ink, transfer printing ink, etc., and is particularly suitable for use when using the solvent (A). Ink ink.

The use of the zinc halide indigo as the main pigment in the colored composition of the present invention is higher in acidity than the conventional copper indigo, and is compatible with the polar solvent used in the post-manufacturing step of the color filter. The properties are good, so there are many problems caused by solvent resistance or heat resistance.

Therefore, when the inkjet ink is prepared from the coloring composition of the present invention, it is preferred to blend the binder resin (E) and/or the thermally reactive compound (F).

[About binder resin (E)]

It is preferable to mix the binder resin (E) from the inkjet ink prepared by the coloring composition of the present invention. The binder resin (E) is preferably a thermoplastic resin.

Examples of the thermoplastic resin which can be used as the binder resin (E) include petroleum resins, maleic acid resins, nitrocellulose, cellulose acetate butyrate, cyclized rubber, and chlorination. Rubber, alkyd resin, acrylic resin, polyester resin, amine resin, vinyl resin or butyral resin.

a functional group selected from a functional group that undergoes self-crosslinking, a functional group that reacts with a thermally reactive compound, and a crosslinking reaction that promotes the reaction of the thermally reactive compound (F) at 100 ° C or higher, preferably 150 ° C or higher, and The resin having one or more functional groups of the functional group cross-linked by the reaction with the thermally reactive compound (F) can be stored in the inkjet ink at a normal temperature without causing long-term viscosity increase, and can be long at normal temperature. The conditions for stable time discharge can be used.

Examples of the functional group capable of self-crosslinking include a combination of a hydroxyl group and a carboxyl group, an alkoxy group, an alkoxyalkyl group, a blocked isocyanate group, or a combination of a carboxyl group and an epoxy group, and light. A polymerizable group or the like.

The functional group which promotes the crosslinking reaction of the thermally reactive compound (F) may, for example, be a carboxyl group, a sulfonic acid group or a phosphoric acid group.

The functional group which is crosslinked by the reaction with the thermally reactive compound (F) may, for example, be a hydroxyl group, a carboxyl group or an epoxy group.

The resin having a functional group capable of crosslinking reaction is preferably an acrylic resin which has no reaction at room temperature and which is slowly crosslinked by an esterification reaction at a high temperature and which has a hydroxyl group and a carboxyl group. The acrylic resin having a hydroxyl group and a carboxyl group can be obtained, for example, by copolymerizing a monomer having a hydroxyl group with a monomer having a carboxyl group and a monomer having no hydroxyl group and a carboxyl group. The hydroxyl group and the carboxyl group are not only self-crosslinked, but also can be effectively utilized as a crosslinking group or a crosslinking reaction promoting group when the thermally reactive compound (F) is used.

[About Thermally Reactive Compound (F)]

Among the inkjet inks prepared by the coloring composition of the present invention, it is preferred to formulate the thermally reactive compound (F). The thermally reactive compound (F) may be used alone or in combination with the binder resin (E). The thermally reactive compound (F) which can be used in the inkjet ink prepared by the coloring composition of the present invention is non-reactive at normal temperature, for example, at a temperature of 100 ° C or higher (preferably 150 ° C or higher). A compound of a crosslinking reaction, a polymerization reaction, a polycondensation reaction or a polyaddition reaction. Even when the stability at the time of storage and discharge is prioritized, and the reactivity is retarded at 150 to 250 ° C, the acidic zinc halide indigo pigment used in the colored composition of the present invention is promoted. A higher durability can be obtained.

The molecular weight of the above thermally reactive compound which can be used in the ink composition of the present invention is not particularly limited, but is preferably from 50 to 2,000, more preferably from 100 to 1,000.

As the above thermally reactive compound, for example, a melamine compound or a benzoquinone can be used. Compound, epoxy compound, oxycyclobutane compound, phenol compound, benzo A capping carboxylic acid compound, a capping isocyanate compound, a carbodiimide compound, an acrylate monomer or a decane coupling agent. Further, as the above thermally reactive compound, it is preferred to contain at least a melamine compound and/or a benzoquinone. Compound. Melamine compound or benzoquinone Since the color change of the compound after heat treatment is extremely small, high resistance can be imparted with a small addition amount, so that the addition amount of the heat-reactive compound can be reduced, and the high pigment concentration or the stability with time of the ink can be improved.

In addition, melamine compounds and / or benzoquinone The effect of the curing of the acidity of the compound-based pigment is remarkable, and further, even if the resin is not used, it is possible to provide a highly resistant cured product by self-condensation.

As a melamine compound or benzoquinone The compound may, for example, be an imido group, a methylol group or an alkoxymethyl group. Among them, the melamine compound or benzoquinone containing an alkoxymethyl group Compound. For the use of alkoxymethyl-containing melamine compounds or benzoquinones In the case of a compound, the storage stability of the coating or ink containing the colored composition of the present invention can be remarkably improved.

As a melamine compound containing alkoxyalkyl group or benzoquinone The compound may, for example, be hexamethoxymethylol melamine, hexabutoxymethylol melamine or tetramethoxyhydroxymethylphenylhydrazine. Tetrabutoxyhydroxymethylphenylhydrazine Etc., but not necessarily limited to this.

Specific examples of the commercial product of the melamine compound include the following. However, it is not necessarily limited to this.

Nikalac MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX750, MX-708, MX-706, manufactured by CARBIDE, Japan , MX-042, MX-035, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410, MX-302, Cymel300, 301, 303, 350, manufactured by CYTECS Industry, Japan. 370, 325, 327, 703, 712, 01, 285, 232, 235, 236, 238, 211, 254, 204, 202, 207, Mycoat 506, 508, 212, 715, and the like.

Among them, Nikalac MW-30M, MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX- made by Japan CARBIDE Co., Ltd., which are alkoxyalkyl group-containing melamine compounds. 43. MX-302, Cymel 300, 301, 303, 350, 285, 232, 235, 236, 238, Mycoat 506 manufactured by CYTECS Industry Co., Ltd., Japan.

Benzoquinone Specific examples of the commercially available compound include, for example, Nikalac BX-4000, SB-401, BX-37, SB-355, SB-303, SB301, BL-60, SB-255, and SB-203 manufactured by CARBIDE Corporation of Japan. SB-201, Cymel 1123, Mycoat 105, 106, 1128, etc., manufactured by CYTECS Industry, Japan.

Among them, the most suitable one is a benzoquinone containing an alkoxyalkyl group. Nikalac BX-4000, SB-401 manufactured by Japan CARBIDE Co., Ltd., and Cyme 11123 manufactured by CYTECS Industry Co., Ltd., Japan.

In addition, the heat-reactive compound which is effective is mentioned below, but it is not necessarily limited to this.

Examples of the epoxy compound include bisphenol quinone diepoxypropyl ether, biscresol thin diepoxypropyl ether, bisphenoxyethanol hydrazine diepoxypropyl ether, and neopentyl glycol epoxide. Propyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol polyepoxypropyl ether, trimethylolpropane polyepoxypropyl ether, pentaerythritol polyepoxypropyl ether, diglycerol polycyclic Oxypropyl propyl ether, sorbitol polyepoxypropyl ether, diepoxypropyl terephthalate, diepoxypropyl phthalate, ethylene glycol diepoxypropyl ether, diethylene glycol a glycidyl ether or a polyepoxypropyl trimer isocyanate of a polyol such as diepoxypropyl ether, polyethylene glycol diepoxypropyl ether or polypropylene glycol diepoxypropyl ether, but not It must be limited to this.

Examples of the oxycyclobutane compound include 3-ethyl-3-hydroxymethyloxycyclobutane and 1,4-bis{[(3-ethyloxycyclobutane-3-yl)methoxy]. Methyl}benzene, bis[1-ethyl(3-oxocyclobutane)]methyl ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxycyclobutane, 3- Ethyl-3-(phenoxymethyl)oxycyclobutane, 3-ethyl-3-(cyclohexyloxy)methyloxycyclobutane, oxycyclobutane sesquioxane, oxygen ring Butanyl phthalate, phenol novolac oxycyclobutane, 1,3-bis[(3-ethyloxycyclobutane-3-yl)methoxy]benzene, 1,4-double {[(3) -ethyloxycyclobutane-3-yl)methoxy]methyl}biphenyl, 1-ethyl-3-oxocyclobutanemethyl methacrylate or benzene-1,4-dicarboxylic acid Bis[1-ethyl(3-oxocyclobutane)methyl]ester or the like, but is not necessarily limited thereto.

As the phenol compound, for example, any of a novolac type phenol compound in which a phenol and an aldehyde are reacted under an acidic catalyst, and a cresol type phenol compound which is reacted under an alkaline catalyst can be used. Examples of the phenols include o-cresol, p-cresol, p-phenol, p-nonylphenol, 2,3-xylenol, phenol, methyl cresol, 3,5-xylenol, resorcinol. And catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol E, bisphenol H or bisphenol S, etc., but are not necessarily limited thereto. Examples of the aldehydes include formaldehyde or acetaldehyde, but are not necessarily limited thereto. The phenols and the aldehydes may be used alone or in combination of two or more.

Benzo Specific examples of the commercial product of the compound include benzene produced by Shikoku Chemicals Co., Ltd. Pd type, benzo Fa type, etc., but not necessarily limited to this.

The sealing carboxylic acid compound may, for example, be a combination of the following carboxylic acid compound and a block agent.

Examples of the carboxylic acid compound include 1,2-decanoic acid, 1,3-decanoic acid, 1,4-nonanoic acid, 1,2,4-trimellitic acid, pyromellitic acid, and cyclohexane dicarboxylic acid. Acid, succinic acid, adipic acid, butane tetracarboxylic acid, maleic acid, fumaric acid, itaconic acid, C1-CIC acid, CIC acid, C3-CIC acid or BiS-CIC acid, etc. It is not necessarily limited to this.

Examples of the block agent include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and tert-butyl vinyl ether. 2-ethylhexyl vinyl ether or the like, but is not necessarily limited thereto. Further, one type may be used alone or two or more types may be used in combination.

The sealing isocyanate group compound may, for example, be a combination of the following isocyanate groups and block agents.

The blocked isocyanate compound may, for example, be hexamethylene diisocyanate, isophorone diisocyanate, o-toluidine isocyanate, diphenylmethane-4,4'-diisocyanate or diphenylmethane-2. Diisocyanate such as 4'-diisocyanate, bis(4-isocyanatecyclohexyl)methane or tetramethylphenyldimethylisocyanate, trimer isocyanate of these diisocyanates, trimethylolpropane addition, double A urerea type or a prepolymer having an isocyanate residue (an oligomer obtained from a diisocyanate and a polyhydric alcohol), a uretdione having an isocyanate residue, or the like, but is not necessarily limited thereto.

Examples of the block agent include phenol (dissociation temperature of 180 ° C or higher), ε-caprolactone (dissociation temperature of 160 to 180 ° C), hydrazine (dissociation temperature of 130 to 160 ° C), or active methylene (100 to 120 ° C). ), etc., but not necessarily limited to this. Further, one type may be used alone or two or more types may be used in combination.

Specific examples of the commercial product of the carbodiimide compound include, for example, CARBODILITE V-01, V-03, and V-05 manufactured by Nisshinbo Co., Ltd., but are not necessarily limited thereto.

Examples of the acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Base) cyclohexyl acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol di(methyl) Acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, trimethylolpropane Tris(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diepoxypropylether di(meth)acrylate, bisphenol A Diepoxypropyl ether di(meth)acrylate, neopentyl glycol diepoxypropyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol six ( Methyl) acrylate, tricyclodecyl (meth) acrylate, ester acrylate, (meth) acrylate of methylolated melamine, epoxy (meth) acrylate or amine methyl acid Various acrylates or methacrylates such as ester acrylates; (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (A) Base) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide or acrylonitrile; however, it is not necessarily limited thereto.

When an acrylate monomer is used, a polymerization initiator can be used for the purpose of further improving the hardenability. As the polymerization initiator, a thermal polymerization initiator can also be used for the purpose of improving the hardenability upon heating. The thermal polymerization initiator may, for example, be an organic peroxide-based initiator or an azo-based initiator.

The decane coupling agent may, for example, be a vinyl decane such as vinyl gin (β-methoxyethoxy) decane, vinyl ethoxy decane or vinyl trimethoxy decane; γ-methyl propylene oxime; (meth)acrylic decanes such as oxypropyltrimethoxydecane; β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxy ring) Hexyl)methyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, β-(3,4-epoxycyclohexyl)methyltriethoxydecane Or an epoxy group such as γ-glycidoxypropyltrimethoxydecane or γ-glycidoxypropyltriethoxydecane; N-β(aminoethyl)γ-amino group Propyltrimethoxydecane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldiethoxydecane , γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane or N-phenyl-γ-aminopropyl Amino decanes such as triethoxy decane; γ-mercaptopropyltrimethoxydecane or γ-mercaptopropyltriethoxydecane Such as thioxane and the like.

Among these thermally reactive compounds, melamine compounds or benzoquinones The compound is preferably contained in an amount of from 1% by weight to 40% by weight based on the ink composition of the present invention. Further, the epoxy compound, the phenol compound, the encapsulated isocyanate compound or the acrylic monomer are preferably contained in an amount of from 1% by weight to 40% by weight based on the ink composition of the present invention. Further, the decane coupling agent is preferably contained in an amount of from 0.1% by weight to 40% by weight based on the ink composition of the present invention. If the content is insufficient, there is a case where the heat resistance or the chemical resistance is inferior. Further, when the content is more than 40%, the viscosity may increase or the storage stability may be lowered.

[about physical properties, etc.]

In the coloring composition of the present invention, the solid content is preferably from 3 to 60% by weight, more preferably from 4 to 40% by weight, based on the total weight of the composition. When the solid content is less than 3% by weight, the concentration or the resistance of the ink film prepared by the coloring composition is insufficient. When the content exceeds 60% by weight, the viscosity of the colored composition increases and the stability with time decreases.

The viscosity of the colored composition of the present invention is preferably 2 mPa ‧ or more and 100 mPa ‧ or less at 25 ° C, more preferably 3 mPa ‧ or more and 50 mPa ‧ or less, and particularly preferably 3 mPa ‧ or more and 40 mPa ‧ s below. When the viscosity of the colored composition is too large, the viscosity of the inkjet ink prepared by the coloring composition is also increased, and when the ink is continuously discharged, the discharge cannot be stably performed. Further, the viscosity of the inkjet ink prepared by the coloring composition of the present invention is preferably 3 mPa ‧ or more and 40 mPa ‧ s or less.

The average dispersed particle diameter of the colored composition of the present invention is preferably 5 nm or more and 200 nm or less, more preferably 10 nm or more and 100 nm or less. When the average dispersed particle diameter of the colored composition is too large, when the inkjet ink prepared by the colored composition is discharged, clogging of the head is liable to occur, and stable discharge cannot be performed. Further, when the average dispersed particle diameter is too small, re-aggregation is likely to occur, and the stability over time deteriorates.

The surface tension of the inkjet ink prepared by the coloring composition of the present invention is preferably 20 mN/m or more and 40 mN/m or less, more preferably 24 mN/m or more and 35 mN/m or less. If the surface tension is too high, the ink cannot be stably discharged. Conversely, if the surface tension is too low, the ink cannot form droplets after being discharged from the head.

The colored composition of the present invention and the inkjet ink prepared by the colored composition can be produced by using the dispersion resin, the pigment, the thermally reactive compound, the organic solvent, and optionally the above-mentioned binder resin. / or the pigment derivative is put into a general disperser and dispersed to a desired average particle diameter ‧ particle size distribution. The coloring composition and the raw material of the inkjet ink may be mixed and dispersed at one time, and may be separately mixed and dispersed in consideration of the characteristics or economy of each raw material. In the case where the viscosity of the inkjet ink is too high and dilution is required, the liquid medium for dilution may be added to the ink stock solution and uniformly stirred to prepare the inkjet ink.

As a dispersing machine, it is suitable for a sand mill, a bead mill, a grinder, a Dyno-mill or a small ball mill. In various dispersing machines, when the pigment is dispersed in an appropriate viscosity region, the ratio of various resin components to the pigment can be changed to adjust the viscosity. The coloring composition and the inkjet ink are preferably dispersed by a filter or a centrifugal method for the purpose of removing coarse particles or foreign matter after being dispersed by a disperser.

In the manufacture of the colored composition of the present invention, a surfactant-type dispersant or an anthracene derivative and/or three may be further used. derivative. The surfactant-type pigment dispersant may, for example, be a naphthalenesulfonic acid formaldehyde condensate salt, an aromatic sulfonic acid formaldehyde condensate, a polyoxyethylene alkyl phosphate, a polyoxyethylene nonylphenyl ether or a stearylamine acetic acid. Ester and the like.

In the inkjet ink prepared by the coloring composition of the present invention, various additives may be contained in the range of the viscosity, the average particle diameter or the surface tension. For example, in order to control the wettability of the ink to the substrate, a surfactant may be contained. When selecting a surfactant, compatibility with other ink constituents must be considered. If the surfactant is anionic, cationic, amphoteric or nonionic, it may be selected as appropriate.

Further, in the inkjet ink of the present invention, an organic solvent such as an alcohol solvent, a glycol solvent, an ester solvent, and/or a ketone solvent may be added in the range of the viscosity, the average particle diameter or the surface tension.

The inkjet ink prepared by the coloring composition of the present invention has a high pigment concentration and a low viscosity, so that the discharge stability is excellent, and since the pigment content is more than that of a general inkjet ink, the discharge amount can be reduced, so that The color filter substrate is used for the productivity and quality improvement of the printed matter of the desired high printing density. The ink composition for inkjet recording of the present invention is particularly suitable for producing a color filter substrate which requires high productivity and quality.

Further, in the inkjet ink prepared by the coloring composition of the present invention, since the pigment is dispersed at a high concentration, even the paper which penetrates the ink composition in the depth direction or the plastic, glass or metal which spreads in the lateral direction can be wetted. Increase the print density. Further, since the amount of discharge can be suppressed, it is possible to avoid the case where the ink is out of the mixed color due to the ink receiving capacity exceeding the receiving layer, or the dot shape cannot be a perfect circle. Therefore, it can be used for limitation in conventional inkjet printing. the use of.

[About color filter substrate]

The inkjet ink prepared by the coloring composition of the present invention can be used together with a red inkjet ink and a blue inkjet ink to produce a color filter substrate by an inkjet method. The color filter substrate can be used, for example, for a liquid crystal display panel used for a thin television or the like.

The color filter substrate is provided with a filter section of a desired hue, and the filter section is used for color filters by an inkjet method in a region distinguished by a black matrix on a substrate on which a black matrix is formed. Each color of the inkjet ink is discharged and formed.

The red inkjet ink and the blue inkjet ink other than the green inkjet ink using the colored composition of the present invention are prepared from the coloring composition obtained by using the following pigment.

For red inkjet ink, for example, CI Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81:2, 81:3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, Red pigments of 240, 246, 254, 255, 264, 272, etc.

In the red inkjet ink, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34 can be used in combination. , 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, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174 Yellow pigments of 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, etc., and/or, for example, CI Pigment Orange 36, 43, 51, 55, 59, 61, etc. Orange pigment.

Blue pigments such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, etc. can be used in the blue inkjet ink. A purple pigment of C. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. may be used in combination in the blue inkjet ink.

As the substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate can be used. The black matrix can be formed, for example, on a substrate by a method of applying a radical polymerization type black photoresist, performing photolithography for exposure and development, and printing a black ink; or A vapor deposition method in which metal is vapor-deposited and then etched.

(Example)

Hereinafter, the present invention will be specifically described by way of examples, but these are not intended to limit the scope of the invention. In the following examples and comparative examples, the parts and % are parts by weight and % by weight. The pigments, pigment derivatives, solvents, and resin solutions used in the examples and comparative examples are shown below. Further, the dispersion formulations and the final ink compositions in the examples and comparative examples are shown in Tables 1 to 7.

[A] solvent ‧ Solvent (A-1) with a boiling point of 170 ° C or higher at 760 mmHg

1) EGDA: ethylene glycol diacetate

2) DEGDA: diethylene glycol diacetate

3) TEGDA: triethylene glycol diacetate

4) PGDA: propylene glycol diacetate

5) DPGDA: dipropylene glycol diacetate

6) 14BGDA: 1,4-butanediol diacetate

7) 13BGDA: 1,3-butanediol diacetate

8) 15PtGDA: 1,5-pentanediol diacetate

‧The solvent with boiling point below 760mmHg is less than 170 °C (A-2)

9) PGMAc: propylene glycol monomethyl ether acetate

‧ Solvent with a boiling point of 170 ° C or higher at 760 mmHg (A-2)

10) DPMA: dipropylene glycol methyl ether acetate

‧ solvent having a boiling point of 170 ° C or higher at 760 mmHg other than solvent (A-1) and solvent (A-2)

11) CBAc: diethylene glycol monoethyl ether acetate

12) BuCBAc: diethylene glycol monobutyl acetate

13) TPM: tripropylene glycol methyl ether

14) TPNB: tripropylene glycol butyl ether

15) 16HDDA: 1,6-hexanediol diacetate

‧ Solvent (A-1), solvent (A-2) other than 760mmHg boiling point is less than 170 ° C solvent

16) Anone: cyclohexanone

17) Butyl acetate

[B] pigment ‧Pigment (B)

1) PG58: C. I. Pigment Green 58 (zinc halide indigo pigment)

‧Phosphorus other than zinc halide

2) PG36: C. I. Pigment Green 36 (copper halide indigo pigment)

3) PY150: C. I. Pigment Yellow 150 (azo pigment)

4) PY138: C. I. Pigment Yellow 138 (quinacridone pigment)

[C] dispersant ‧Alkaline dispersing agent (C) (C-1) a condensation reaction of a hydroxycarboxylic acid polymer chain having a carboxyl group at a single terminal with a polyallylamine chain or a polyethylenimine chain having two or more primary or secondary amine groups in the main chain Comb type alkaline dispersant (Cc)

1) PB821: AJISPER-PB-821 made by Ajinomoto Fine Techno Co., Ltd. (solid content 100%)

2) SP32000: Solsperse-32000 (solid content 100%) manufactured by Avecia Co., Ltd. (C-2) Alkaline dispersant other than (Cc)

3) EFKA4300: EFKA-4300 manufactured by Chiba Specialty Chemicals Co., Ltd. (solid fraction 81% PGMAc)

4) BYK161: Disperbyk-161 manufactured by BYK Chemie Co., Ltd. (solid content: 30% PGMAc / butyl acetate)

‧ acidic dispersant

5) PA111: AjISPER-PA-111 made by Ajinomoto Fine Techno Co., Ltd. (solid content 100%)

6) BYK111: Disperbyk-111 manufactured by BYK Chemie Co., Ltd. (solid fraction >90%)

7) SP24000: Solsperse-24000 manufactured by Avecia (100% solid content)

8) J678: JANGRYL-678 manufactured by BASF Japan Co., Ltd. (100% solid content)

When AJISPER-PB-821, EFKA-4300, Solsperse-32000, AJISPER-PA-111, Disperbyk-111, Solsperse-24000, and JANCRYL-678 are used, they are dissolved in the main solvent of the coloring composition to form a solid fraction 30. Use as a % solution.

[D] pigment derivative ‧Pigment Derivatives (D) Pigment derivative [BD-1]

A compound represented by the general formula (13):

[Chemistry 14]

CuPc-SO ₃ H‧H ₂ NC ₁₂ H ₂₅ (13)

[E]Adhesive resin ‧Adhesive resin (E)

1) J804: Acrylic resin JONCRYL-804 manufactured by BASF Japan Co., Ltd. (acid value 15, OH group price 45, weight average molecular weight 12,500, solid content 100%)

It was dissolved in the main solvent of the coloring composition to prepare a solution having a solid content of 30%.

[F]thermally reactive compound ‧thermally reactive compound (F)

1) MX-43: NikaLacMX-43, a melamine compound containing alkoxyalkyl group manufactured by CARBIDE, Japan

2) MX-417: NikaLacMX-417, a melamine compound containing an imido-hydroxymethyl group, manufactured by CARBIDE, Japan

3) SB-401: benzoquinone containing alkoxyalkyl group manufactured by CARBIDE Corporation of Japan Compound NikaLac SB-401

4) BL-60: benzoquinone containing imine hydroxymethyl group manufactured by CARBIDE Corporation of Japan Compound Nikalac BL-60

5) M-400: Aronix M-400, an acrylic monomer made by East Asia Synthetic Co., Ltd.

6) BL-4265: Desmodur BL-4265, an isocyanate compound manufactured by Bayer Urethane Co., Ltd.

7) EPPN-201: Epoxy compound EPPN-201 manufactured by Nippon Kayaku Co., Ltd.

(Example 1)

100 parts of PG85 as pigment (B), 133 parts of PB-821 (solid content 30% solution) as alkaline dispersant (C), and 307 parts of EGDA as solvent (A-1) were charged into a mixer. The mixture was mixed and placed in a sand mill for dispersion to obtain a colored composition. Further, 20 parts of a melamine compound (MX-43) as a thermally reactive compound (F) and 250 parts of 15PtGDA as a solvent (A-1) were added and mixed by a homodisperser. The impurities or the coarse substance were subjected to filter filtration to obtain an inkjet ink having a pigment concentration of 20%.

(Examples 2 to 42 and Comparative Examples 1 to 26)

As in Example 1, dispersion and liquid adjustment were carried out in accordance with the compositions of Examples 2 to 34 and Comparative Examples 1 to 26 in the composition tables of Tables 1 to 9, to obtain a colored composition and an inkjet ink.

Further, as in Example 1, dispersion and liquid adjustment were carried out in accordance with the compositions of Examples 35 to 42 in the composition table of Table 19 to obtain a colored composition and an inkjet ink.

Further, the numerical values in the composition tables of Tables 1 to 9 and Table 19 indicate the parts by weight which are substantially used. The material used for dissolving in the main solvent is a solid content (parts by weight), and the main solvent (parts by weight) used for dissolution is added to the main solvent.

That is, in the case of Example 1, the pigment (B) PG85 is 100 (parts by weight), the alkaline dispersant (C) PB-821 is 40 (parts by weight), and the solvent (A-1) is shown in Table 1. The EGDA was 400 parts by weight, the thermally reactive compound (F) MX-43 was 20 parts by weight, and the solvent (A-1) 15 PtGDA was 250 parts by weight.

The viscosity, fluidity, stability over time, average particle diameter, and haze value of the colored compositions obtained in Examples 1 to 42 and Comparative Examples 1 to 26 were evaluated by the following methods. The results are shown in Tables 10 to 18 and 20. Further, the inks obtained in Examples 1 to 42 and Comparative Examples 1 to 26 were discharged by an ink jet printer having a piezo head which was changeable at a frequency of 4 to 10 KHz, and the discharge stability was evaluated by the following method. . The results are shown in Tables 21 to 30.

[viscosity]

The viscosity (η: mPa ‧ s) of the friction speed of 100 (1/s) was measured by a dynamic viscoelasticity measuring apparatus, and evaluated based on the following criteria.

○: η<40

△: 40≦η<50

╳:50≦η

[fluidity]

The viscosity (ηa: mPa ‧ s) of the friction velocity 10 (1/s) was measured by a dynamic viscoelasticity measuring device to obtain a viscosity (η: mPa ‧ s) from the previously measured frictional velocity of 100 (1/s) The ratio ηa/η was evaluated for fluidity on the basis of the following criteria.

○: 0.9≦ηa/η<1.5

╳:1.5≦ηa/η

[save stability]

The viscosity after heating for 7 days was measured in an oven at 45 ° C, and evaluated according to the following criteria.

○: 10% increase in viscosity compared to the viscosity before heating

╳: Compared to the viscosity before heating, the viscosity increase rate is >10%

[The average particle size]

In the average particle diameter [D], 0.001 g of the coloring composition was diluted with 30 g of the main solvent of the coloring composition to adjust the measurement sample, and a laser Doppler particle size distribution measuring apparatus (Nikkiso Co., Ltd., UPA) was used. -EX150) The measurement was performed and evaluated according to the following criteria.

○: 10 nm ≦ [D] < 100 nm

△: 100 nm ≦ [D] < 200 nm

╳:[D]≧200nm

[fog value]

The substrate coated on the glass at 1500 rpm using a spin coater was dried at 100 ° C for 3 minutes using a spinner, and the haze value of the coated surface was measured by a haze value (manufactured by Nippon Denshoku Industries Co., Ltd.). According to the following criteria for evaluation.

○: [fog value] <3

△: 3 ≦ [fog value] < 4.5

╳: [Fog value] ≧ 4.5

[Spit stability A]

The inks obtained in Examples 1 to 22 and Examples 25 to 42 and Comparative Examples 1 to 26 were discharged at predetermined positions of the glass substrate, dried, and thermally cured at 230 ° C for 20 minutes to form a coating film. The film reliability was evaluated by the following method.

The printing state was visually observed, and the discharge stability was evaluated according to the following criteria.

○: After 15 minutes of continuous discharge, the nozzle detachment was 5% or less.

△: After 15 minutes of continuous discharge, the nozzle detachment was 10% or less.

╳: After 15 minutes of continuous discharge, the nozzle detachment is 50% or more.

[Spit stability B]

Further, the inks obtained in Examples 1 to 22 and Examples 25 to 42 and Comparative Examples 1 to 26 were discharged onto the corrugated paper by the above-described ink jet printer, dried, and dried at room temperature to form a coating film, and the printing density was evaluated by the following method. .

The printing state was visually observed, and the discharge stability was evaluated according to the following criteria.

◎: After the intermittent discharge time (15 minutes) after the discharge was interrupted, the nozzle was separated by 5% or less.

○: After the intermittent discharge time (15 minutes) after the discharge was interrupted, the nozzle was separated by 10% or less.

△: After the intermittent discharge time (15 minutes) after the discharge was interrupted, the nozzle was separated by 20% or less.

╳: After the intermittent discharge time (15 minutes) after the discharge is interrupted, the nozzle is separated by 50% or more.

[Chemical resistance]

The glass substrate on which the coating film was formed was immersed in N-methylpyrrolidone, and the color change ΔE of the coating film before and after immersion was measured and evaluated based on the following criteria.

○: △E≦2.5

△: 2.5 < △ E ≦ 5

╳: △E>5

(industrial availability)

When the coloring composition of the present invention is used as a paint or ink, even if the pigment concentration is high, the viscosity can be made low, so that the package, the outdoor kanban, the automobile paint or the color can be efficiently produced compared with the conventional one. Filters, etc. Moreover, when the coloring composition of the present invention is used as an inkjet ink, the chemical resistance is good, and even if the pigment concentration is high, the viscosity is low and the viscosity stability is excellent, and the discharge stability is good. Ink, a high performance color filter can be produced more efficiently than conventional methods.

The invention has been described above in terms of specific aspects, and it is apparent to those skilled in the art that various modifications and improvements are included in the scope of the invention.

Claims (13)

A colored composition comprising a solvent (A), a pigment (B), and a basic dispersant (C), wherein the solvent (A) contains a butanediol diacetate solvent, and the pigment (B) contains the following general Indigo pigment represented by formula (3); general formula (3): [In the formula, the central metal element M is Zn, and X ₁ to X ₁₆ are each independently an element selected from the group consisting of H, Cl, and Br]. The coloring composition of claim 1, wherein the butanediol diacetate solvent accounts for 60% by weight or more of the total solvent. The colored composition of the first aspect of the invention, wherein the alkaline dispersant (C) comprises an alkaline dispersant (Ca) having the following structure: from an acrylic polymer chain, a hydroxycarboxylic acid polymer chain, and an alkylene oxide. One or more partial structures selected from the group consisting of a base polymer chain; One or more cationic partial structures selected from the group consisting of a polyallylamine chain, a polyethylenimine chain, a cationic polyurethane chain, and a cationic acrylic polymer chain. The colored composition of the first aspect of the invention, further comprising the pigment derivative (D) represented by the following general formula (4); general formula (4): G ⁴ -J ⁴ q (4) (generally In the formula (4), G ⁴ is a q-valent dye prototype compound residue, and J ⁴ is a basic substituent, an acidic substituent or a neutral substituent, and q is an integer of 1 to 4. The coloring composition of claim 1, wherein the solid content is from 3 to 60% by weight based on the total weight of the coloring composition. The coloring composition of the first aspect of the invention, wherein the content of the pigment (B) is from 1 to 30% by weight based on the total weight of the coloring composition. The colored composition of claim 1, wherein the weight ratio of the pigment (B) to the alkaline dispersant (C) is from 100:3 to 100:150. An inkjet ink comprising the colored composition of any one of claims 1 to 7. An inkjet ink comprising the colored composition of any one of claims 1 to 7 and a binder resin (E) and/or a thermally reactive compound (F). An inkjet ink according to claim 9, wherein the thermally reactive compound (F) is a melamine compound or a benzoquinone Compound, carbodiimide compound, epoxy compound, oxetane compound, phenol compound, benzo One or two or more selected from the group consisting of a compound, a blocked carboxylic acid compound, an acid-immobilized isocyanate compound, an acrylate-based monomer, and a decane coupling agent. The inkjet ink of claim 9, wherein the thermally reactive compound (F) contains at least a melamine compound and/or a benzoquinone Compound. The inkjet ink of claim 8 is a color filter substrate. A color filter substrate is provided on a substrate carrying at least a printing layer formed by the inkjet ink of claim 8 of the patent application.