KR101487555B1 - Coloring composition containing phthalocyanine pigment, ink-jet ink containing same, and color filter substrate - Google Patents

Abstract

The present invention relates to a coloring composition using a zinc phthalocyanine pigment excellent in color characteristics and having a high solid content and a high pigment concentration and having good dispersibility, fluidity, and stability, and an inkjet ink capable of stable ejection using the same, It is an object to provide a color filter substrate formed using inkjet ink.

(A), a pigment (B) and a basic dispersant (C), wherein the solvent (A) is CH ₃ -C (═O) -O- (C _n H _{2n O) m -C (= O} ) OC ( that is a solvent (a-1) and R- represented by _{-CH 3 3 H 6) p -OC} (= O) solvent represented by -CH ₃ (a-2) , And the pigment (B) contains a phthalocyanine pigment represented by the general formula (3).

(3)

(3)

Wherein the central metal element M is Zn and each of X ₁ to X ₁₆ is independently an element selected from H, Cl, and Br.

Description

 TECHNICAL FIELD [0001] The present invention relates to a coloring composition comprising a phthalocyanine pigment, an inkjet ink containing the same, and a color filter substrate containing a coloring composition containing a phthalocyanine pigment,

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

In recent years, "color reproducibility" has been strongly demanded for a color liquid crystal display which is the maximum use of a color filter substrate. Ink used for manufacturing a color filter substrate is required to have high color purity and high color density and high transparency. It has become necessary to finely disperse the pigment in order to satisfy the required properties.

The pixel portion of the color filter according to the ink-jet method is formed by previously providing a black matrix on a transparent substrate and filling ink into the region divided by the black matrix by the ink jet method. At this time, when the solid content of the ink is low and / or the pigment concentration is low, the ink overflows beyond the black matrix and the ink is mixed into the adjacent region in the process of producing the color filter having the desired color density, The color of the filter segment may be damaged. At this time, the ink used for the color filter is required to have a high solid content and a high pigment concentration. In addition, in order to ensure stable ejection properties, ink-jet inks are also required to have low viscosity and viscosity stability (for example, Patent Document 4). Green, which is one of the three primary colors (red, blue, green, RGB) of the color filter substrate, is generally used in the resist method or in the ink-jet method using halogenated copper phthalocyanine (for example, CI Pigment Green 36) Dispersion of the phthalocyanine pigment may fail to achieve fineness of the pigment, excessively high viscosity, poor transmittance, and the like.

In addition, with the recent increase in demand for thin film displays,

(1) faithfully reproducing the color seen by the eyes, that is, the improvement of the area ratio of the color reproduction range to the chromaticity range defined by the National Television Standards Committee (NTSC) standard

(2) Improvement of color characteristics such as sharpness of images, i.e., improvement of contrast ratio

There has been a great gap between the current chromaticity of the green and the required chromaticity in the color filter using the conventional halogenated copper phthalocyanine pigment, and it is difficult to satisfy these demands.

In order to solve these problems, it has been used (for example, Patent Document 1, Patent Document 2, Patent Document 3) that the central metal of the phthalocyanine pigment is changed from copper to zinc or nickel. However, it is known that zinc halide phthalocyanine pigments are different from conventional green pigments in their chemical properties, and thus are difficult to disperse in organic solvents as compared with conventional halogenated copper phthalocyanine pigments. For this reason, it has been difficult to disperse zinc halphthalocyanine pigments in a stable manner while maintaining good color characteristics, only by using a dispersant and a solvent suitable for conventional halogenated copper phthalocyanine or other pigments.

Further, since the organic solvent used in the dispersion of the zinc halphthalocyanine pigment so far has a low boiling point and a high evaporation rate, there is a problem in that when it is used as a main solvent for the inkjet ink, the dischargeability is deteriorated. It was difficult to put them into practical use.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2003-161828

[Patent Document 2] Japanese Unexamined Patent Publication No. 2003-192947

[Patent Document 3] Japanese Unexamined Patent Publication No. 2003-192948

[Patent Document 4] Japanese Patent Application Laid-Open No. 2005-299090

It is an object of the present invention to provide a coloring composition using a zinc phthalocyanine pigment excellent in color characteristics and having a high solid content and a high pigment concentration and good dispersibility, flowability, and storage stability. It is also an object of the present invention to provide an inkjet ink capable of stable ejection using the above colored composition. It is also an object of the present invention to provide a color filter substrate formed by an inkjet method using the inkjet ink.

The above object is achieved by a coloring composition comprising a solvent (A), a pigment (B) and a basic dispersant (C), wherein the solvent (A)

Wherein C _n H _2n is a linear or branched alkylene chain, 1? M? 3, and 2? N? 5.

(A-1) represented by the general formula

Wherein R is an alkyl group having 1 to 8 carbon atoms and C ₃ H ₆ is a linear or branched propylene chain and 1? P? ₃ .

, And a solvent (A-2) represented by the following formula (3), and the pigment (B) comprises a phthalocyanine pigment represented by the following formula

By weight of the coloring composition.

(3)

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

In a preferred embodiment of the coloring composition according to the present invention, at least one solvent selected from the group consisting of the solvent (A-1) and the solvent (A-2) accounts for not less than 60% by weight of the total solvent.

In another preferred embodiment of the coloring composition according to the present invention, at least one solvent selected from the group consisting of the solvent (A-1) and the solvent (A-2) is a solvent having a boiling point of 170 ° C or higher at 760 mmHg .

In a more preferred embodiment of the coloring composition according to the present invention, at least one 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 캜 at 760 mmHg Wherein a weight mixing ratio of a solvent having a boiling point of less than 170 DEG C at 760 mmHg and a solvent having a boiling point of 170 DEG C or more at 760 mmHg is from 0: 100 to 70: 30 to be.

In another preferred embodiment of the coloring composition according to the present invention, the solvent (A-1) is selected from the group consisting of ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, (A-1) is at least one solvent selected from the group consisting of diethylene glycol diacetate, propylene glycol diacetate, and butylene glycol di Acetate, and the like.

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

In another preferred embodiment of the coloring composition according to the present invention, the basic dispersant (C) is at least one kind of partial structure selected from the group consisting of an acrylic polymer chain, a hydroxycarboxylic acid polymer chain, and an alkylene oxide polymer chain (Ca) comprising at least one cationic partial structure selected from the group consisting of polyarylamine chains, polyethyleneimine chains, cationic polyurethane chains, and cationic acrylic polymer chains.

Another preferred embodiment of the coloring composition according to the present invention comprises a pigment derivative (D) represented by the following general formula (4).

(4)

(Wherein G ⁴ is a dye derivative compound residue of q, 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 coloring composition according to the present invention, the solid content of the coloring composition is 3 to 60% by weight based on the total weight of the coloring composition.

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

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

The present invention also relates to an ink-jet ink comprising the coloring composition.

The present invention also relates to an ink-jet ink additionally comprising the coloring composition, the binder resin (E), and / or the heat-reactive compound (F).

In a preferred embodiment of the ink-jet ink according to the present invention, the heat-reactive compound (F) is a melamine compound, a benzoguanamine compound, a carbodiimide compound, an epoxy compound, an oxetane compound, a phenol compound, a benzoxazine compound, At least one compound selected from the group consisting of an acid compound, a blocked isocyanate compound, an acrylate-based monomer, and a silane coupling agent. In a more preferred embodiment, the compound is at least a melamine compound and / or a benzoguanamine compound.

The present invention also relates to the inkjet ink for a color filter substrate.

The present invention also relates to a color filter substrate for supporting a printing layer formed of the inkjet ink on a substrate.

The coloring composition of the present invention,

(1)

[Chemical Formula 1]

Wherein C _n H _2n is a linear or branched alkylene chain, 1? M? 3, and 2? N? 5.

(A-1) represented by the general formula

(2)

Wherein R is an alkyl group having 1 to 8 carbon atoms and C ₃ H ₆ is a linear or branched propylene chain and 1? P? ₃ .

A solvent (A) comprising at least one solvent selected from the group consisting of a solvent (A-2) represented by the following formula

(3)

(3)

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

A pigment (B) comprising at least one pigment selected from the group consisting of phthalocyanine pigments represented by the following formula

The basic dispersant (C)

And is characterized by comprising:

The coloring composition of the present invention contains at least one solvent selected from a solvent (A-1) and a solvent (A-2), so that the coloring composition of the present invention has excellent dispersibility, Stability. Therefore, it is possible to prepare an ink composition for inkjet recording from the coloring composition of the present invention, and to produce a color filter substrate using the ink composition for inkjet recording prepared in this way, ) Yield is improved, and a printing layer with a sufficient concentration can be provided.

[About solvent]

The colorant composition of the present invention is characterized by using a specific solvent (A) as a solvent component, and the solvent (A)

[Chemical Formula 1]

Wherein C _n H _2n is a linear or branched alkylene chain, 1? M? 3, and 2? N? 5.

(A-1) represented by the general formula

(2)

Wherein R is an alkyl group having 1 to 8 carbon atoms and C ₃ H ₆ is a linear or branched propylene chain and 1? P? ₃ .

And a solvent (A-2) represented by the following general formula (1).

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

(1) Optimum affinity of pigment and dispersant for maintaining low viscosity and viscosity stability over time

(2) Optimum drying speed and surface tension of ink to maintain ejection stability

.

In particular, inkjet inks used for color filter applications are required to have a high pigment content and a high solid content concentration from the viewpoints of productivity and prevention of color mixing, and require optimum design of a solvent system.

Since the solubilities of the copper phthalocyanine pigment and the zinc phthalocyanine pigment are different from each other, the solvent most suitable for dispersion also differs. Zinc phthalocyanine pigments as an optimal solvent for dispersion of copper phthalocyanine pigments have too good affinity and are not suitable for dispersion.

The solvent (A) comprising at least one solvent selected from the group consisting of the solvent (A-1) and the solvent (A-2) has the best affinity with the pigment (B) And good stability of viscosity over time can be achieved.

The solvent (A-2) is preferably an alkyl group having 1 to 8 carbon atoms in the formula (2), R < 2 & When 1? P? 3, the affinity with the pigment (B) becomes optimum. When the solvent (A-1) has the values of m and n in the above formula (1) and the solvent (A-2) in the above formula (2) exceeds the defined range, the affinity with the pigment (B) The dispersibility of the pigment is deteriorated and a sufficient degree of micronization can not be obtained or problems such as a high viscosity and a deteriorated viscosity at the time of deterioration occur.

As a more preferable form of the coloring composition of the present invention, at least one solvent selected from the solvent (A-1) and the solvent (A-2) accounts for not less than 60% by weight of the total solvent. If it is less than 60% by weight, the affinity to the pigment can not be sufficiently manifested.

As a more preferred embodiment of the coloring composition of the present invention, at least one solvent selected from the solvent (A-1) and the solvent (A-2) includes a solvent having a boiling point of 170 ° C or higher at 760 mmHg. More preferably, at least one 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 and a boiling point at 760 mmHg Is a mixture of a solvent having a boiling point of 170 DEG C or higher and a weight ratio of a solvent having a boiling point of less than 170 DEG C at 760 mmHg to a solvent having a boiling point of 170 DEG C or higher at 760 mmHg is from 0: 100 to 70: 30. If the solvent having a boiling point of 770 mmHg at 170 DEG C or higher is not the main component, sufficient ejection stability may not be obtained when the ink is prepared with an ink for ink jet. (A-1) and the solvent (A-2), even if a solvent having a boiling point of less than 170 ° C at 760 mmHg is used for the purpose of controlling the dispersion stability, viscosity, The solvent having a boiling point of less than 170 占 폚 at 760 mmHg exceeds 30% by weight, sufficient ejection stability may not be maintained in some cases.

Examples of the solvent (A-1) used in the present invention include ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, butylene glycol diacetate, Pentanediol diacetate and the like, all of which have a boiling point of 170 DEG C or higher at 760 mmHg.

Butylene glycol diacetate includes 1,4-butylene glycol diacetate, 1,3-butylene glycol diacetate and the like. Pentanediol diacetate includes 1,5-pentanediol diacetate and the like.

Examples of the solvent (A-2) used in the present invention include solvents having a boiling point of less than 170 占 폚 at 760 mmHg, such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, propylene glycol monopropyl 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 acetate, etc., having a boiling point of 770 mmHg at 170 ° C or higher But propylene glycol monomethyl ether acetate or dipropylene glycol monomethyl ether acetate can be suitably used.

As a coloring composition of the present invention, a more preferable form is to use a solvent (A-3) having a boiling point of 240 ° C or more at 760 mmHg and a surface tension of 26 to 36 mN / m at 25 ° C. By using this solvent (A-3) in combination, drying in the vicinity of the head is suppressed and ejection stability (in particular, intermittent dischargeability) is improved when the ink is prepared into an inkjet ink. As the solvent (A-3) having a boiling point of 760 mmHg at 240 占 폚 or higher and a surface tension at 25 占 폚 of 26 to 36 mN / m, the definition of the solvent (A-1) and the solvent (A-2) (A-1) and the solvent (A-2) can be used in a range of less than 40% of the total solvent, and diethylene glycol mono n-butyl ether acetate , Tripropylene glycol n-butyl ether, and the like.

[About pigment]

The pigment constituting the coloring composition of the present invention is preferably colored with a desired hue and excellent in heat resistance, chemical resistance, liquor stability, and / or light resistance.

The pigment (B) constituting the coloring composition of the present invention has the formula (3)

(3)

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

In particular, X is Br.

The preferred form of the pigment constituting the coloring composition of the present invention is that the average number of hydrogen atoms in X is 0 to 2, the average number of Cl elements in X is 0 to 5, and the average number of Br elements in X is 8 to 16.

When a representative pigment of formula (3) is represented by a color index (CI) number, C.I. Pigment Green 58 and the like.

The pigment (B) contained in the coloring composition of the present invention may contain not only the zinc halide phthalocyanine pigment as the main pigment but also other green or yellow pigments for the purpose of color control or complementation. As a green pigment that can be used in combination, when expressed by a color index (C.I.) number, for example, C.I. Pigment Green 7, 10, 36, and 37, and the yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: : 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, , 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, and the like.

The particle diameter of the pigment (B) is preferably sufficiently small with respect to the wavelength of visible light in terms of the absorption coefficient of visible light (suitability of spectrum) and transparency. That is, the pigment preferably has an average primary particle diameter of 10 nm or more and 300 nm or less, particularly 10 nm or more and 100 nm or less. The primary particle diameter refers to the diameter of the pigment particle of the smallest unit and is measured by an electron microscope. The primary particle diameter of the pigment can be controlled within a proper range by using a known dispersing device, for example, sand mill, kneader, or through roll.

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

[About dispersion resin]

The halogenated zinc phthalocyanine pigment, which is the main pigment of the pigment (B) of the coloring composition of the present invention, has a higher acidity than conventional copper phthalocyanine pigments. Therefore, the basic dispersant (C) can be suitably used for the fine dispersion of the zinc phthalocyanine pigment, and the coloring composition and the ink-jet ink using the same can be lowered in viscosity and improved in the stability over time.

As the basic dispersant (C) to be used in the coloring composition of the present invention, a known basic resinous dispersant may be used. Specific examples of commercially available resinous dispersants include the following.

Examples of the basic resinous dispersant manufactured by Big Chemie include 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.

As a basic resinous dispersant made by Lubrizol Japan Ltd., Soluzpazes 9000, 13240, 13650, 13940, 17000, 18000, 20000, 24000SC, 24000GR, 28000, 31845, 32000, 32500, 32600, 33500, 34750, 35100, 35200, 37500, 38500, 44000, 55000, and the like.

Examples of basic resinous dispersants available from Ciba Specialty Chemicals include EFKA-4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4403, 4406, , 4520, 4530, 4570, 4800, 5044, 5054, 5055, 5063, 5064, 5071, 5207, 5244 and the like.

Examples of the basic resin type dispersant manufactured by Ajinomoto Fine Techno Co., Ltd. include Ajispa PB-711, PB811, and PB821.

In the case of producing a color filter using an inkjet ink prepared from the coloring composition of the present invention, transparency is required for the color filter. Therefore, in the entire wavelength range of 400 to 700 nm of the visible light region, The transmittance of the dispersing resin is preferably 80% or more, more preferably 95% or more.

The basic dispersant (C) used in the coloring composition of the present invention preferably has at least one partial structure selected from the group consisting of an acrylic polymer chain, a hydroxycarboxylic acid polymer chain, and an alkylene oxide polymer chain (Ca) comprising at least one cationic partial structure selected from the group consisting of polyarylamine chains, polyethyleneimine chains, cationic polyurethane chains, and cationic acrylic polymer chains.

The acrylic polymer chain is obtained by polymerizing one or more alkyl (meth) acrylate monomers. Further, it may be obtained by block or random copolymerization of one or more kinds of (meth) acrylic acid alkyl monomers and other vinyl monomers, if necessary.

A photo-polymerizable group, a thermally reactive group, an anionic group, a cyclic aliphatic group, and an aromatic group may optionally be introduced into the side chain thereof.

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

The alkylene oxide polymer chain is obtained by dehydration or ring-opening reaction of diol and / or cyclic ether.

The polyallylamine chain is obtained by removing an addition salt from a polyallylamine hydrochloride obtained by radical polymerization of an allylamine hydrochloride.

The polyethyleneimine chain is obtained by ring-opening polymerization of ethyleneimine.

The cationic polyurethane chain is obtained by reacting a dialkylamino group-containing diol with a diisocyanate in a mid-portion.

The cationic acrylic polymer chain is obtained by radical copolymerization of dialkylamino group-containing (meth) acrylate monomers with other monomers.

The basic dispersant (C) to be used in the coloring composition of the present invention more preferably contains at least one partial structure selected from the group consisting of a hydroxycarboxylic acid polymerized chain and a polyarylamine chain, a polyethyleneimine chain, (Cb) comprising at least one cationic partial structure selected from the group consisting of a cationic polyurethane chain.

As the structure of the basic dispersant (C), both of a straight chain type and a comb type having a side chain in the main chain backbone can be used.

The basic dispersing agent (C) which can be suitably used in the coloring composition of the present invention is a polyester resin obtained by polymerizing a hydroxycarboxylic acid polymerized chain (polyester [c-1]) having a carboxyl group at one end and a primary or secondary (Cc) obtained by the condensation reaction of a polyallylamine chain or polyethylenimine chain (polyamine [c-2]) having two or more primary amino groups, but the other chemical structures and the production method are specifically limited no.

For example, the condensation reaction between the polyester [c-1] having a carboxyl group at one end and the polyamine [c-2] having two or more primary or secondary amino groups in the main chain is carried out by reacting the polyester [c-1] The polyamine [c-2] is mixed and heated and proceeded by amidation by dehydration. The reaction conditions at that time, namely, the ratio of the addition amount of the polyester [c-1] and the polyamine [c-2], the molecular weight of the polyester [c-1] and the polyamine [c- The molecular weight, amine value, and acid value of the topographic dispersant (C) can be controlled.

The number average molecular weight of the basic dispersant (C) is preferably 1,000 to 100,000. When the number average molecular weight of the basic dispersant (C) is less than 1,000, the dispersing effect and storage stability deteriorate. When the number average molecular weight is more than 100,000, the viscosity of the dispersion increases and the solubility in various organic solvents decreases. The amine value of the basic dispersant (C) is preferably 5 to 100, and the acid value is preferably 0 to 50. The amine value and the acid value greatly affect the solubility of the dispersant and the adsorption property to the pigment, and the greatest effect can be obtained in these suitable ranges.

The polyester [c-1] having a carboxyl group at one end is obtained by the self condensation of a hydroxycarboxylic acid or a lactone, or the co-condensation of a hydroxycarboxylic acid and a lactone.

Examples of the hydroxycarboxylic acid include ricinoleic acid, ricinoleic acid, a mixture of 9 and 10-hydroxystearic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid and lactic acid, ? -caprolactone,? -propiolactone,? -butyrolactone,? -valerolactone,? -methyl-? -valerolactone, 4-methylcaprolactone and 2-methylcaprolactone, Most preferred is a co-condensation product of 12-hydroxystearic acid and epsilon -caprolactone. In condensing these polyesters, carboxylic acids not containing a hydroxyl group such as caproic acid, lauric acid, stearic acid, methoxyacetic acid and the like may be added as a polymerization terminator.

The polyamine [b-2] used in the present invention is not particularly limited as long as it is a polymer having an amino group, and specific examples thereof include polyethyleneimine, polyethylene polyamine and polyallylamine. Polyethyleneimine is a polyamine obtained by ring-opening polymerization of ethyleneimine in the presence of an acid catalyst, and polyethylenepolyamine is a polyamine obtained by polycondensing ethylene dichloride and ammonia in the presence of an alkali catalyst. The polyallylamine is a polyamine represented by the following formula (5).

(5)

[In the formula (5), n7 represents an integer of 2 to 1000]

From the above viewpoints, particularly suitable as the above-mentioned commercially available basic dispersant (C) that can be used in the coloring composition of the present invention is Aji Spa PB821 manufactured by Ajinomoto Pine Techno Co., Ltd., Solvar Spaz 32000 manufactured by Lubrizol Japan, EFKA-4300, Disperbyk-161 manufactured by Big Chemie, Especially suitable are Aji Spa PB821, Solurupazu 32000 manufactured by Lubrizol Japan, but the present invention is not limited thereto.

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

[About pigment derivative (D)]

In the present invention, a pigment derivative may be used if necessary. As the pigment derivative usable in the present invention, for example, those represented by the following formula (4) can be used.

(4)

[Chemical Formula 4]

(Wherein G ⁴ is a dye derivative compound residue of q, J ⁴ is a basic substituent, an acidic substituent or a neutral substituent, and q is an integer of 1 to 4.)

Examples of the basic substituent include substituents represented by the following formulas (6), (7), (8), and (9)

(6)

(In the formula (6), X ^{61 represents} -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -, -CH ₂ -, or a direct bond.

n6: Represents an integer from 1 to 10. R ^a6 and R ^b6 are each independently a substituted or unsubstituted alkyl group, an optionally substituted alkenyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted substituent comprising R ^a6 and R ^b6 and containing a further nitrogen, oxygen or sulfur atom Or a heterocyclic ring which may be substituted. The alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.)

(7)

(7)

R ^a7 and R ^b7 each independently represent an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a substituent which is ^combined with R ^a7 and R ^b7 and contains an additional nitrogen, oxygen or sulfur atom Or a heterocyclic ring which may be substituted. The alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.)

(8)

(8)

X ^{81 represents} -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -, -CH ₂ -, or a direct bond.

R ^{a8 represents} an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. The alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.

R ^b8 , R ^c8 , R ^d8 and R ^e8 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. The alkyl group and the alkenyl group preferably have 1 to 5 carbon atoms.)

(9)

(9)

X ^{91 represents} -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -, -CH ₂ -, or a direct bond.

Y ⁹ : -NR ^a9 -Z ⁹ -NR ^b9 - or a direct bond.

R ^a9 and R ^b9 each independently represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. The alkyl group and alkenyl group preferably have 1 to 5 carbon atoms.

Z ⁹ represents an alkylene group which may be substituted, an alkenylene group which may be substituted, or a phenylene group which may be substituted. The alkyl group and the alkenyl group preferably have 1 to 8 carbon atoms.

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

Q ⁹ : a hydroxyl group, an alkoxyl group, a substituent represented by the above formula (7), or a substituent represented by the above formula (8).

Formula 9a:

[Formula 9a]

(9a)

n9: Represents an integer from 1 to 10.

R ^c9 and R ^d9 each independently represent an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted or a substituent which is combined with R ^c9 and R ^d9 and which further contains nitrogen, oxygen or sulfur atom Or a heterocyclic ring which may be substituted. The alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.)

9b:

[Formula 9b]

(9b)

R ^{e9 represents} an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. The alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.

R ^f9 , R ^g9 , R ^h9 and R ⁱ⁹ each independently represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. The alkyl group and the alkenyl group preferably have 1 to 5 carbon atoms.)

Examples of the acidic or neutral substituent include substituents represented by the following general formula (10), (11), or (12).

10

(10)

M ^{10 represents a} hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom.

I ¹⁰ represents the mantissa of M ^10. )

Formula 11

(11)

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

Formula 12

(12)

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

and k ₁₂ represents an integer of 1 to 4.)

The dye-forming compound (G ⁴ ) refers to a compound having a generally known dye skeleton and a compound having a skeleton similar to that of the pigment skeleton, with little absorption in the visible light region.

Examples of the dye derivative compound residue include diketopyrrolopyrrole dye residue, azo dye residue (for example, azo, disazo, polyazo etc.), phthalocyanine dye residue, anthraquinone dye residue Anthanthrone, indanthrone, pyranthrone, biorantrone, etc.), quinacridone dye residue, dioxazine dye residue, perinone dye residue, perylene dye An isoindolinone dye residue, a quinophthalone dye residue, a threne dye residue, a metal complex system dye residue, an anthraquinone residue, or a triazine residue, and the like can be used as a dye residue, a thioindigo dye residue, an isoindoline dye residue, .

As the anthraquinone derivative, anthraquinone having a basic, acidic or neutral substituent may be used. Examples of the triazine derivative include an alkyl group (e.g., methyl group, ethyl group), an amino group, an alkylamino group (e.g., dimethylamino group, diethylamino group, dibutylamino group and the like), a nitro group, Group (e.g., methoxy group, ethoxy group, butoxy group, etc.), or halogen (e.g., chlorine, etc.); A phenyl group which may be substituted with a methyl group, a methoxy group, an amino group, a dimethylamino group, or a hydroxyl group; Or a phenylamino group which may be substituted with a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group, a dimethylamino group, a diethylamino group, a nitro group or a hydroxyl group, The above-mentioned basic, acidic or neutral substituent-introduced derivatives may be used.

The coloring composition of the present invention can be used at a low viscosity with a high solid content and a high pigment concentration and can be used in gravure ink, offset ink, ink jet, or automotive paint, but it is possible to obtain a printed matter with high tinting / high transmittance, It can be suitably used particularly for a color filter substrate. The color filter substrate can be used for an inkjet inkjet ink, a photoresist ink, or a printing ink for a transfer method, but can be suitably used for an inkjet ink, taking advantage of the properties of the solvent (A).

The zinc phthalocyanine halide used as the main pigment in the coloring composition of the present invention has a higher acidity than the conventional copper phthalocyanine and has good affinity for the polar solvent used in the post-production process of the color filter, In many cases.

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

[About binder resin (E)] [

The inkjet ink prepared from the coloring composition of the present invention preferably contains a binder resin (E). The binder resin (E) is preferably a thermoplastic resin.

Examples of the thermoplastic resin that can be used for the binder resin (E) include petroleum resin, maleic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, alkyd resin, acrylic resin, A resin, a vinyl resin, or a butyral resin.

(F) at a temperature of 100 占 폚 or more, preferably 150 占 폚 or more, and a functional group capable of reacting with the functional group capable of reacting with the thermally reactive compound (F) May be used as far as they can satisfy the conditions capable of storing the inkjet ink at room temperature for a long period of time without increasing the viscosity and capable of stable discharge at room temperature for a long period of time.

Examples of the self-crosslinkable functional group include a combination of a hydroxyl group and a carboxyl group, an alkoxyl group, an alkoxysilyl group, a blocked isocyanate group, a combination of a blocked carboxyl group and an epoxy group, and a photopolymerizable group.

Examples of the functional group that promotes the crosslinking reaction of the thermally reactive compound (F) include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

Examples of the functional group which reacts with and crosslinks with the thermally reactive compound (F) include a hydroxyl group, a carboxyl group, and an epoxy group.

As the resin having a crosslinkable functional group, an acrylic resin having a hydroxyl group and a carboxyl group, which does not react at room temperature at all, and which crosslinks the resin mildly by an esterification reaction at a high temperature, is preferable. The acrylic resin having a hydroxyl group and a carboxyl group is 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 can be effectively used not only as a self-crosslinking agent but also as a crosslinking agent or a crosslinking reaction promoter in the case of using the thermally reactive compound (F).

[Regarding the thermoreactive compound (F)] [

In the inkjet ink prepared from the coloring composition of the present invention, it is preferable to blend the heat-reactive compound (F). The thermally reactive compound (F) may be used alone or in combination with the resin binder (E). The heat-reactive compound (F) that can be used in the ink-jet ink prepared by the coloring composition of the present invention is non-reactive at room temperature, but may be crosslinked at a temperature of, for example, 100 캜 or higher (preferably 150 캜 or higher) A polycondensation reaction, or a mid-addition reaction. The zinc phthalocyanine pigment having high acidity to be used in the coloring composition of the present invention becomes a reaction promoter even when the stability at the time of storage and saturation is prioritized and the reactivity at 150 to 250 ° C is selected, A higher durability can be obtained.

The molecular weight of the thermoreactive compound usable in the ink composition of the present invention is not particularly limited, but is preferably 50 to 2000, more preferably 100 to 1000.

Examples of the heat-reactive compound include a melamine compound, a benzoguanamine compound, an epoxy compound, an oxetane compound, a phenol compound, a benzoxazine, a blocked carboxylic acid compound, a blocked isocyanate compound, a carbodiimide compound, , Or a silane coupling agent can be used. Further, it is preferable that at least a melamine compound and / or a benzoguanamine compound is contained as the heat-reactive compound. The melamine compound or the benzoguanamine compound is very small in discoloration after the heat treatment and can be imparted with high resistance with a small addition amount. Therefore, it is possible to reduce the addition amount of the thermoreactive compound and to improve the high pigment concentration and stability .

In addition, the melamine compound and / or the benzoguanamine compound is remarkably influenced by the hardening of the acidity of the pigment, and even if there is no binder resin, a highly resistant cured product can be provided by self-condensation.

Examples of the melamine compound or benzoguanamine compound include those having an imino group, a methylol group, or an alkoxymethyl group. Among them, a melamine compound or a benzoguanamine compound containing an alkoxyalkyl group is particularly preferable. When a melamine compound or a benzoguanamine compound containing an alkoxyalkyl group is used, the storage stability of the paint or ink containing the colored resin composition of the present invention is remarkably improved.

Examples of the melamine compound or benzoguanamine compound containing an alkoxyalkyl group include hexamethoxymethylol melamine, hexabutoxymethylol melamine, tetramethoxymethylolbenzoguanamine, tetrabutoxymethylolbenzoguanamine and the like But the present invention is not limited thereto.

Specific examples of commercially available melamine compounds include the following. However, the present invention is not limited thereto.

MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX750, MX-708 and MX-706 manufactured by Nippon Carbide Co., MX-042, MX-035, MX-45, MX-500, MX-520, MX-43, MX-417, MX- 350, 370, 325, 327, 703, 712, 01, 285, 232, 235, 236, 238, 211, 254, 204, 202, 207, Mycote 506, 508, 212, 715 and the like.

MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX-43 and MX- 302, Cymel 300, 301, 303, 350, 285, 232, 235, 236, 238, and Mycot 506 manufactured by Japan Scientific Industries.

Specific examples of commercially available products of benzoguanamine compounds include Nikalkak BX-4000, SB-401, BX-37, SB-355, SB-303, SB-301, BL- SB-203, SB-201, Cymel 1123 manufactured by Japan Syntex Industry Co., Ltd., Mycoat 105, 106, 1128 and the like.

Of these, NiKalac BX-4000 and SB-401 manufactured by Nippon Carbide, which is an alkoxyalkyl group-containing benzoguanamine compound, and Cymel 1123 manufactured by Japan Syntex Industry Co., Ltd. are suitable.

Other examples of effective heat-reactive compounds include, but are not limited to, the following examples.

Examples of the epoxy compound include bisphenol fluorene diglycidyl ether, biscresol fluorene diglycidyl ether, bisphenoxyethanol fluorene diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylol propane polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, di Such as glycidyl terephthalate, diglycidyl o-phthalate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, or polypropylene glycol diglycidyl ether. Glycidyl ethers of polyols, polyglycidyl isocyanurates, and the like, but are not limited thereto.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [[(3-ethyloxetan-3- yl) methoxy] methyl] (3-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, 3- 1,3-bis [(3-ethyloxetan-3-yl) methoxy] benzene, 1,6-hexanedioxy silane, Methyl [3-ethyl] methoxy] methyl] biphenyl, 1-ethyl-3-oxetanylmethyl methacrylate, or benzene-1,4-dicarboxylic acid bis [1-ethyl (3-oxetanyl) methyl] ester, and the like, but are not limited thereto.

As the phenol compound, there can be used, for example, a novolac phenol compound obtained by reacting phenols and aldehydes under an acidic catalyst, and a resol-type phenol compound reacted in the presence of a basic catalyst. Examples of phenols include orthocresol, paracresol, paraphenyl phenol, paranonyl phenol, 2,3-xylenol, phenol, metacresol, 3,5-xylenol, resorcinol, catechol, Bisphenol A, bisphenol F, bisphenol B, bisphenol E, bisphenol H, bisphenol S, and the like, but are not limited thereto. As the aldehydes, formaldehyde or acetaldehyde can be mentioned, but not always limited thereto. The phenols and aldehydes may be used singly or in combination of two or more.

Specific examples of commercially available products of benzoxazine compounds include, but are not limited to, benzoxazine P-d type and benzoxazine F-a type manufactured by Shikoku Chemical Industry Co.,

Examples of the blocked carboxylic acid compound include a combination of the following carboxylic acid compound and a block agent.

Examples of the carboxylic acid compound include 1,2-phthalic acid, 1,3-phthalic acid, 1,4-phthalic acid, 1,2,4-trimellitic acid, pyromellitic acid, cyclohexanedicarboxylic acid, But are not limited to, adipic acid, butane tetracarboxylic acid, maleic acid, fumaric acid, itaconic acid, C1-CIC acid, CIC acid, C3-CIC acid and Bis-CIC acid.

Examples of the blocking agent include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, and 2-ethylhexyl vinyl ether However, the present invention is not limited thereto. Also, one kind of the compound is used singly or two or more kinds are used in combination.

Examples of the blocked isocyanate compound include a combination of the following isocyanate compound and a block agent.

Examples of the blocked isocyanate compound include diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, toluidine isocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane- Diisocyanate such as diisocyanate, bis (4-isocyanatocyclohexyl) methane, or tetramethylxsilylene diisocyanate, or an isocyanurate of these diisocyanates, a trimethylolpropane duct type, a biuret type, or an isocyanate residue (Low polymer obtained from diisocyanate and polyol), uretdione having isocyanate residue, and the like, but the present invention is not limited thereto.

Examples of the blocking agent include phenol (dissociation temperature 180 DEG C or higher), epsilon -caprolactam (dissociation temperature 160-180 DEG C), oxime (dissociation temperature 130-160 DEG C), or active methylene (100-120 DEG C) But the present invention is not limited thereto. Also, one kind of the compound is used singly or two or more kinds are used in combination.

Specific examples of commercially available products of the carbodiimide compound include Carbodilite V-01, V-03, V-05 and the like manufactured by Nisshinbo, but the present invention is not limited thereto.

Examples of the acrylate monomer include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (Meth) acrylate, glycerin di (meth) acrylate, triethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (methyl Acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl (Meth) acrylate, dipentaerythritol hexa (metha) acrylate, caprolactone modified dipentaerythritol hexa (metha) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylol melamine Acrylic acid esters such as (meth) acrylic acid esters, epoxy (meth) acrylates and urethane acrylates, methacrylic acid esters such as (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like, but are not limited thereto.

When an acrylate monomer is used, a polymerization initiator may be used for the purpose of further improving the curability. As the polymerization initiator, a heat polymerization initiator may be used for the purpose of improving the curability at the time of heating. Examples of the thermal polymerization initiator include an organic peroxide-based initiator and an azo-based initiator.

Examples of the silane coupling agent include vinylsilanes such as vinyltris (? -Methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, and? -Methacryloxypropyltrimethoxysilane (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - (3,4-epoxycyclohexyl) methyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ) Epoxy silanes such as ethyltriethoxysilane,? - (3,4-epoxycyclohexyl) methyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane or? -Glycidoxypropyltriethoxysilane, Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, or N-phenyl- Mino is amino silanes, such as the propyl triethoxysilane, γ- mercaptopropyltrimethoxysilane, γ- or mer in the mercapto propyltriethoxysilane and the like thio silanes such as silane.

Of these heat-reactive compounds, a melamine compound or a benzoguanamine compound is preferably contained in the ink composition of the present invention in an amount of 1% by weight to 40% by weight. The epoxy compound, the phenolic compound, the blocked isocyanate compound, or the acrylate monomers and the like are preferably contained in the ink composition of the present invention in an amount of 1 to 40% by weight. The silane coupling agent is preferably contained in the ink composition of the present invention in an amount of 0.1% by weight to 40% by weight. If the content is insufficient, heat resistance or chemical resistance may be deteriorated. If the content is more than 40%, the viscosity may increase or the storage stability may be lowered.

[About properties]

In the coloring composition of the present invention, the solid content is preferably 3 to 60 wt%, more preferably 4 to 40 wt% with respect to the total weight of the composition. When the solid content is less than 3% by weight, the concentration and resistance of the ink coating prepared with the coloring composition are insufficient. When the content is more than 60% by weight, the viscosity of the coloring composition is increased and the stability with time is lowered.

The viscosity of the coloring composition of the present invention is preferably 2 mPa · s or more and 100 mPa · s or less at 25 ° C., more preferably 3 mPa · s or more and 50 mPa · s or less, furthermore 3 mPa · s or more and 40 mPa · s or less Is more preferable. If the viscosity of the coloring composition is too large, the viscosity of the inkjet ink prepared with the coloring composition becomes too large, and stable ejection is impossible when the ink is continuously ejected. The viscosity of the inkjet ink prepared from the coloring composition of the present invention is preferably 3 mPa · s or more and 40 mPa · s or less.

The average dispersed particle diameter of the coloring 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 size of the coloring composition is too large, the inkjet ink prepared from the coloring composition is liable to clog the head, and stable discharge is impossible. Also, if the average dispersed particle size is too small, re-aggregation tends to occur and the stability over time is deteriorated.

The surface tension of the ink-jet ink prepared from the colored 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 can not be stably discharged from the head. On the other hand, if the surface tension is too low, it becomes impossible for the ink to form droplets after ejection from the head.

The coloring composition of the present invention and the ink-jet ink prepared with the coloring composition can be produced by mixing the dispersion resin, the pigment, the heat-reactive compound, and the organic solvent and, if necessary, the binder resin and / And then dispersing the mixture until the desired average particle size / particle size distribution is obtained. The raw materials for the coloring composition and the ink-jet ink may be mixed and dispersed at one time, and may be separately mixed and dispersed in consideration of the properties and economy of each raw material. When the viscosity of the ink-jet ink is too high and dilution is required, it is also possible to add a diluting liquid medium to the ink stock solution and uniformly stir to prepare an ink-jet ink.

As the dispersing device, a sand mill, a bead mill, an agitator mill, a dyno mill, or a cob ball mill is suitable. When each disperser has a viscosity region suitable for pigment dispersion, the viscosity can be adjusted by changing the ratio of the various resin components to the pigment. The coloring composition and the inkjet ink are preferably dispersed in a disperser and then filtered by a filter or centrifugal method for the purpose of removing coarse particles or foreign matter.

When the coloring composition of the present invention is produced, a surfactant type dispersant, an anthraquinone derivative, and / or a triazine derivative may be further used. Examples of the surfactant type pigment dispersant include naphthalenesulfonic acid formalin condensate salts, aromatic sulfonic acid formalin condensates, polyoxyethylene alkylphosphoric acid esters, polyoxyethylene nonylphenyl ethers, and stearylamine acetates.

The inkjet ink prepared from the coloring composition of the present invention may contain various additives in the range of the viscosity, the average particle size, and 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, it is necessary to consider the compatibility with other ink constituent components. The surfactant may be anionic, cationic, amphoteric or nonionic, and may be selected appropriately.

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 above viscosity, average particle diameter, or surface tension .

The inkjet ink prepared with the coloring composition of the present invention has a high pigment concentration and a low viscosity so that it has excellent ejection stability and the pigment content is larger than that of a normal inkjet ink so that the amount of ejection can be reduced, , It is possible to improve the productivity and dignity of a printed matter for which a high printing density is desired. In particular, the ink composition for ink jet recording of the present invention is suitable for the production of a color filter substrate requiring high productivity and durability.

In addition, since the pigment is dispersed at a high concentration, the ink-jet ink prepared with the coloring composition of the present invention can be used even when the ink composition penetrates in the depth direction or is plastic, glass or metal that spreads in the lateral direction, can do. In addition, since the amount of ejection can be suppressed, it is possible to avoid that the ink is outflowed (outflowed) in excess of the ink capacity of the receptive layer, or the dot shape does not become a true circle, It can also be used for applications that have been.

[About Color Filter Substrate]

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

The color filter substrate has filter segments of a desired color, and the filter segments are formed by discharging inkjet ink for color filter in each color in an area divided by a black matrix of a substrate on which a black matrix is formed, by an inkjet method.

The red inkjet ink and the blue inkjet ink, other than the green inkjet ink using the coloring composition of the present invention, are prepared into a coloring composition obtained using the following pigments.

In the red inkjet ink, for example, C.I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: , 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264 , 272, and the like can be used.

In the red inkjet ink, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: : 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, , 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 and / or yellow pigments such as CI Pigment Orange 36, 43, 51, 55, 59 and 61 can be used in combination.

The blue inkjet ink includes, for example, C.I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and 64 can be used. Blue inkjet inks include C.I. Violet pigments such as Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 and 50 can be used in combination.

As the substrate, a resin plate such as a glass plate, polycarbonate, polymethyl methacrylate, or polyethylene terephthalate can be used. The black matrix is formed on a substrate by, for example, a photolithography method in which a radical polymerization type black resist is applied, exposure, development and patterning, a printing method in which black ink is printed, or a vapor deposition method in which a metal is vapor- can do.

[Example]

Hereinafter, the present invention will be described in detail by way of examples, but they should not be construed as limiting the scope of the present invention. In the following Examples and Comparative Examples, parts and% are parts by weight and% by weight. The pigments, pigment derivatives, solvents and resin solutions used in Examples and Comparative Examples are shown below. Tables 1 to 7 show the dispersion prescription and the final ink composition in Examples and Comparative Examples.

[A] Solvent

Solvent (A-1) having 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) 14 BGDA: 1,4-butylene glycol diacetate

7) 13BGDA: 1,3-butylene glycol diacetate

8) 15 PtGDA: 1,5-pentanediol diacetate

Solvent (A-2) having a boiling point of less than 170 占 폚 at 760 mmHg

9) PGMAc: Propylene glycol monomethyl ether acetate

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

10) DPMA: dipropylene glycol methyl ether acetate

Solvents other than the solvent (A-1) and the solvent (A-2) having a boiling point of 770 mmHg at 170 ° C or higher

11) CBAc: diethylene glycol monoethyl ether acetate

12) BuCBAc: Diethylene glycol monobutyl ether acetate

13) TPM: tripropylene glycol methyl ether

14) TPNB: Tripropylene glycol butyl ether

15) 16HDDA: 1,6-hexanediol diacetate

Solvent having a boiling point of less than 170 占 폚 at 760 mmHg other than the solvent (A-1) and the solvent (A-2)

16) Anion: Cyclohexanone

17) Butyl acetate

[B] Pigment

Pigment (B)

1) PG58: C.I. Pigment Green 58 (Zinc phthalocyanine halide pigment) · Pigment other than halogenated zinc phthalocyanine

2) PG36: C.I. Pigment Green 36 (halogenated copper phthalocyanine pigment)

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

4) PY138: C.I. Pigment Yellow 138 (quinophthalone-based pigment)

[C] Dispersant

Basic dispersant (C)

(C-1) is obtained by condensation reaction of a hydroxycarboxylic acid polymerized chain having a carboxyl group at one end thereof with a polyallylamine chain or polyethyleneimine chain having two or more primary or secondary amino groups in the main chain, Dispersant (Cc)

1) PB821: Ajispa PB-821 (solid content 100%) manufactured by Ajinomoto Fine Techno Co.,

2) SP32000: Solsperse-32000 (100% solids) manufactured by Avicia Co.,

(C-2) a basic dispersant except for (Cc)

3) EFKA4300: EFKA-4300 (solid content 81% PGMAc) manufactured by Ciba Specialty Chemicals,

4) BYK161: Disperbyk-161 manufactured by Big Chemie (solid content 30% PGMAc / butyl acetate)

· Acid dispersant

5) PA111: Aji Spa PA-111 (solid content 100%) manufactured by Ajinomoto Fine Techno Co.,

6) BYK111: Disperbyk-111 manufactured by Big Chemie (solid content> 90%)

7) SP24000: Solsperse-24000 (100% solids) manufactured by Avicia Co.,

8) J678: John CRYL-678 (100% solids) manufactured by BASF Japan

In the case of using Aji Spa PB-821, EFKA-4300, Solsperse-32000, Ajispa PA-111, Disperbyk-111, Solsperse-24000 and Zonkryl-678, it is dissolved in the main solvent of the coloring composition and a solution of 30% Respectively.

[D] Pigment derivatives

Pigment derivatives (D)

Pigment Derivative [BD-1]

(13)

≪ / RTI >

[E] Binder Resin

· Binder resin (E)

1) J804: acrylic resin ZONCRYL-804 (acid value 15, OH group 45, weight average molecular weight 12,500, solid content 100%) manufactured by BASF Japan

Was dissolved in the main solvent of the coloring composition and used as a solution having a solid content of 30%.

[F] Heat-reactive compound

The heat-reactive compound (F)

1) MX-43: melamine compound containing an alkoxyalkyl group manufactured by Nippon Carbide Co., Ltd. Nigalak MX-43

2) MX-417: melamine compound containing imino group methylol group manufactured by Nippon Carbide Co., Ltd. Nigalak MX-417

3) SB-401: Benzoguanamine compound containing an alkoxyalkyl group manufactured by Nippon Carbide

Nikalkak SB-401

4) BL-60: benzoguanamine compound containing imino group-methylol group manufactured by Nippon Carbide

NIKOLAK BL-60

5) M-400: acrylic monomer ARONIX M-400 manufactured by Toagosei Co.

6) BL-4265: Isocyanate compound desmodule BL-4265 manufactured by Sumika Bayer Urethane

7) EPPN-201: epoxy compound EPPN-201 manufactured by Nippon Kayaku Co.

≪ Example 1 >

100 parts of PG85 as the pigment (B), 133 parts of PB-821 (30% solids solution) as the basic dispersant (C) and 307 parts of EGDA as the solvent (A-1) were mixed and mixed in a mixer, To obtain a colored composition. 20 parts of a melamine compound (MX-43) as a thermoreactive compound (F) and 250 parts of 15 PtGDA as a solvent (A-1) were added and mixed in a homodisper. The dust and the matter were filtered to obtain an ink-jet ink having a pigment concentration of 20%.

<< Examples 2 to 42 and Comparative Examples 1 to 26 >>

Dispersion and liquid preparation were carried out in the same manner as in Example 1 to obtain the compositions of Examples 2 to 34 and Comparative Examples 1 to 26 in the composition table of Tables 1 to 9 to obtain a coloring composition and an inkjet ink.

Further, in the same manner as in Example 1, dispersion and liquid conditioning were carried out so as to obtain the compositions of Examples 35 to 42 in the composition table of Table 19 to obtain a coloring 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 actually used. The material used for dissolving in the main solvent represents the solid content (parts by weight), and the main solvent (parts by weight) used for dissolving is added to the main solvent.

For example, in Table 1, 100 parts by weight of the pigment (B) PG85, 40 parts by weight of the basic dispersant (C) PB-821, 400 parts by weight of the solvent (A-1) 20 parts by weight of the thermally reactive compound MX-43 and 250 parts by weight of the solvent A-1 and 15 PtGDA, respectively.

The viscosity, fluidity, aging stability, average particle diameter and haze of the coloring 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. The inks obtained in Examples 1 to 42 and Comparative Examples 1 to 26 were ejected by an ink jet printer having a piezo head capable of changing the frequency of 4 to 10 kHz and the ejection stability was evaluated by the following method. The results are shown in Tables 21 to 30.

[Viscosity]

The viscosity (?: MPa 占 퐏) at a shear rate of 100 (1 / s) was measured by a dynamic viscoelasticity measuring apparatus and evaluated according to the following criteria.

∘: η <40

?: 40?? <50

×: 50 ≦ η

[liquidity]

The viscosity (? A: mPa? S) at a shear rate of 10 (1 / s) was measured with a dynamic viscoelasticity measuring apparatus and the ratio? A (mPa? S) / eta was obtained, and the fluidity was evaluated on the basis of the following criteria and evaluated according to the following criteria.

?: 0.9?? A /?? 1.5

×: 1.5?? A /?

[Storage stability]

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

?: Increase in viscosity compared with viscosity before heating?? 10%

X: Increase in viscosity by 10% compared with viscosity before heating

[Average particle diameter]

0.001 g of the coloring composition was diluted with 30 g of the main solvent of the colored composition to prepare a measurement sample, and the average particle size was measured using a laser Doppler particle size distribution analyzer (UPA-EX150, manufactured by Nikkiso Co., Ltd.) And evaluated according to the following criteria.

?: 10 nm? [D] < 100 nm

?: 100 nm? [D] < 200 nm

X: [D]? 200 nm

[Hayes]

Using a spin coater, the substrate coated with glass at 1500 rpm was dried with a hot plate at 100 DEG C for 3 minutes, and the haze of the coated surface was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.) Respectively.

○: [haze] <3

?: 3? [Haze] < 4.5

×: [haze] ≥4.5

[Discharge Stability A]

The inks obtained in Examples 1 to 22, Examples 25 to 42 and Comparative Examples 1 to 26 were ejected and dried at predetermined positions of the glass substrate using the inkjet printer to perform thermal curing at 230 DEG C for 20 minutes A coating film was formed, and the reliability of the coating film was evaluated by the following method.

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

○: After 15 consecutive minutes of ejection, the nozzle dropout is 5% or less.

B: After 15 consecutive minutes of ejection, the nozzle dropout is 10% or less.

×: After 15 consecutive minutes of ejection, the nozzle dropout is 50% or more.

[Discharge Stability B]

The ink obtained in Examples 1 to 22, Examples 25 to 42, and Comparative Examples 1 to 26 was discharged onto a corrugated cardboard using the above-described inkjet printer, dried, and dried at room temperature to form a coating film. .

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

A: Nozzle dropout is 5% or less when discharging is performed after the intermittent time (15 minutes) for stopping the discharge has elapsed.

A: Nozzle slippage was 10% or less when discharging was performed after an intermittent time (15 minutes) in which the discharge was stopped.

DELTA: Nozzle dropout is 20% or less when discharging is performed after the intermittent time (15 minutes) for stopping the discharge has elapsed.

X: Nozzle dropout is 50% or more when ejected after an intermittent time (15 minutes) for stopping ejection has elapsed.

[Chemical resistance]

The glass substrate on which the coated film was formed was immersed in N-methylpyrrolidone and the color change DELTA E of the coated film before and after the immersion was measured and evaluated according to the following criteria.

?:? E? 2.5

?: 2.5 <? E? 5

×: ΔE> 5

The coloring composition of the present invention can produce a package, an outdoor signboard, an automobile paint, a color filter, or the like much more efficiently than the conventional one because the coloring composition can be used as a paint or an ink, . In addition, when the coloring composition of the present invention is used as an inkjet ink, it is possible to obtain an ink having good chemical resistance, high viscosity, low viscosity, stability over time, and excellent discharge stability, It is possible to produce a color filter with high efficiency in a much more efficient manner.

While the present invention has been described with reference to the specific embodiments thereof, modifications and improvements apparent to those skilled in the art are within the scope of the present invention.

Claims (19)

1. A coloring composition comprising a solvent (A), a pigment (B), and a basic dispersant (C) Wherein the solvent (A) is selected from the group consisting of ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, butylene glycol diacetate, and pentanediol diacetate Containing at least one kind of solvent (A-1), and Wherein the pigment (B) comprises a phthalocyanine pigment represented by the following formula (3) &Lt; / RTI &gt; (3) (3)

Wherein the central metal element M is Zn and each of X ₁ to X ₁₆ is independently an element selected from the group consisting of H, Cl, and Br. The method according to claim 1, Wherein the solvent (A-1) accounts for not less than 60% by weight of the total solvent. The method according to claim 1, Wherein the solvent (A-1) is at least one solvent selected from the group consisting of diethylene glycol diacetate, propylene glycol diacetate, and butylene glycol diacetate. The method according to claim 1, Wherein the basic dispersant (C) comprises at least one partial structure selected from the group consisting of an acrylic polymer chain, a hydroxycarboxylic acid polymer chain, and an alkylene oxide polymer chain, At least one cationic partial structure selected from the group consisting of a polyallylamine chain, a polyethyleneimine chain, a cationic polyurethane chain, and a cationic acrylic polymer chain (Ca). &Lt; / RTI &gt; The method according to claim 1, Further comprising a pigment derivative (D) represented by the following formula (4). (4) [Chemical Formula 4]

(Wherein G ⁴ is a dye derivative compound residue of q, J ⁴ is a basic substituent, an acidic substituent or a neutral substituent, and q is an integer of 1 to 4.) The method according to claim 1, Wherein the solid content is 3 to 60% by weight based on the total weight of the coloring composition. The method according to claim 1, Wherein the content of the pigment (B) is 1 to 30% by weight based on the total weight of the coloring composition. The method according to claim 1, Wherein the weight ratio of the pigment (B) and the basic dispersant (C) is 100: 3 to 100: 150. 9. An inkjet ink comprising the coloring composition of any one of claims 1 to 8. An inkjet ink comprising the coloring composition of any one of claims 1 to 8, a binder resin (E), and / or a heat-reactive compound (F). 11. The method of claim 10, Wherein the thermally reactive compound (F) is at least one selected from the group consisting of a melamine compound, a benzoguanamine compound, a carbodiimide compound, an epoxy compound, an oxetane compound, a phenol compound, a benzoxazine compound, a blocked carboxylic acid compound, a blocked isocyanate compound, And a silane coupling agent. 11. The method of claim 10, Wherein the heat-reactive compound (F) comprises at least a melamine compound and / or a benzoguanamine compound. The inkjet ink according to claim 9, which is for a color filter substrate. A color filter substrate on which a print layer formed by at least the ink jet ink of claim 9 is carried. delete delete delete delete delete