JP5408020B2 - Coloring composition containing phthalocyanine pigment, inkjet ink containing the same, and color filter substrate - Google Patents

Description

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

Recently, "color reproducibility" for color liquid crystal displays, which is the biggest use of color filter substrates
Therefore, the ink used for manufacturing the color filter substrate is required to have high color purity and color density and high transparency. In order to satisfy these required physical properties, fine dispersion of the pigment is required.

Formation of the pixel portion of the color filter by the ink jet method is performed by providing a black matrix on a transparent substrate in advance and filling the region divided by the black matrix with ink by the ink jet method. At this time, if the solid content of the ink is low and / or the pigment concentration is low, the ink overflows beyond the black matrix in the process of forming a color filter having a desired color density, and is adjacent to the ink. Ink may enter the area and impair the hue of the filter segment. Therefore, the ink used for the color filter is required to have a high solid differentiation and a high pigment concentration. Furthermore, in order to ensure the stable discharge property, inkjet ink is 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 a copper halide phthalocyanine (for example, CI Pigment Green 36), whether it is a resist method or an inkjet method. However, dispersion of the copper halide phthalocyanine pigment may cause problems such as failure to achieve finer pigment, excessively high viscosity, and poor transmittance.

In addition, along with the recent increase in demand for thin film displays,
(1) To faithfully reproduce the color seen by the eyes, that is, to improve the area ratio of the color reproduction range to the chromaticity range defined by the NTSC (National Television Standard Committee) standard. (2) The sharpness of the image, that is, the contrast. Improvements in color characteristics such as improvement in the ratio have been demanded, but there is a large gap between the current chromaticity of green and the required chromaticity, especially in color filters using conventional copper halide phthalocyanine pigments. It was difficult to satisfy these requests.

In order to solve these problems, a phthalocyanine pigment whose central metal is changed from copper to zinc or nickel has been used (for example, Patent Document 1, Patent Document 2, and Patent Document 3). However, it is known that the halogenated zinc phthalocyanine pigment is different from the conventional green pigment in its chemical properties and is difficult to disperse in an organic solvent as compared with the conventional copper halide phthalocyanine pigment. Therefore, it is difficult to stably disperse a halogenated zinc phthalocyanine pigment while maintaining excellent color characteristics only by using a dispersant and a solvent suitable for conventional copper halide phthalocyanine or other pigments. there were.

Furthermore, the organic solvents used so far in the dispersion of zinc halide phthalocyanine pigments have a low boiling point and a high evaporation rate. It was difficult to put zinc halide phthalocyanine into practical use as an inkjet ink.
JP 2003-161828 A JP 2003-192947 A JP 2003-192948 A JP 2005-299090 A

An object of the present invention is to provide a coloring composition having good dispersibility, fluidity, and storage stability at a high solid content and a high pigment concentration using a zinc phthalocyanine pigment having excellent color characteristics. Moreover, the objective of this invention is providing the inkjet ink which can be stably discharged using the said coloring composition. Furthermore, the objective of this invention is providing the color filter substrate formed by the inkjet method using the said inkjet ink.

The said subject is a coloring composition containing a solvent (A), a pigment (B), and a basic dispersing agent (C), and the said solvent (A) is 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 alkylene chain, 1 ≦ m ≦ 3, and n = 2, 3, or 5. ]
A solvent (A-1) represented by :
General formula (2):
R— (O—C ₃ H ₆ ) _p —O—C (═O) —CH ₃ (2)
[However, R is an alkyl group having 1 to 8 carbon atoms, C ₃ H ₆ is a linear or branched propylene chain, and 1 ≦ p ≦ 3. ]
And the pigment (B) includes a phthalocyanine pigment represented by the following general formula (3). can do.
General formula (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. ]

In a preferred embodiment of the colored composition according to the present invention, the solvent (A-1) and the solvent (A-2)
1) or more solvents selected from the group consisting of occupy 60% by weight or more in all the solvents.

In another preferred embodiment of the colored composition according to the present invention, the solvent (A-1) and the solvent (A
-2) The 1 or more types of solvent chosen from the group which consists of a solvent whose boiling point in 760 mmHg is 170 degreeC or more is included.

In a more preferred embodiment of the coloring composition according to the present invention, the solvent (A-1) and the solvent (
One or more kinds of solvents selected from the group consisting of A-2) are a mixture of a solvent having a boiling point of less than 170 ° C. at 760 mmHg and a solvent having a boiling point of 760 mmHg of 170 ° C. or more, and has a boiling point of 760 mmHg. The weight mixing ratio of the solvent below 170 ° C. and the solvent having a boiling point of 170 ° C. or higher at 760 mmHg is 0: 100 to 70:30.

In another preferred embodiment of the coloring composition according to the present invention, the solvent (A-1) is ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, butylene glycol. One or more solvents selected from the group consisting of diacetate and pentanediol diacetate. In a more preferred embodiment, the solvent (A-1) is diethylene glycol diacetate, propylene glycol diacetate, and butylene glycol diacetate. One or more solvents selected from the group consisting of:

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, the solvent (A-2). ) Is dipropylene glycol monomethyl ether acetate.

In another preferred embodiment of the colored composition according to the present invention, the basic dispersant (C) is one or more partial structures selected from the group consisting of an acrylic polymer chain, a hydroxycarboxylic acid polymer chain, and an alkylene oxide polymer chain. And a basic dispersant (Ca) containing at least one kind of 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.

In another preferred embodiment of the coloring composition according to the present invention, the pigment composition (D) represented by the following general formula (4) is included.
General formula (4):
G ⁴ -J ⁴ q (4)
(In the general formula (4), G ⁴ is a q-valent chromogenic compound residue, J ⁴ is a basic substituent, an acidic substituent, or a neutral substituent, and q is 1-4. Is an integer.)

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

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

 Moreover, this invention relates to the inkjet ink containing the said coloring composition.

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

In a preferred embodiment of the inkjet ink according to the present invention, the thermally 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, a blocked carboxylic acid compound, or a blocked isocyanate. It is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound, an acrylate system monomer, and a silane coupling agent, and in a more desirable mode, it is at least a melamine compound and / or a benzoguanamine compound.

Furthermore, this invention relates to the said inkjet ink for color filter substrates.

Furthermore, the present invention also relates to a color filter substrate that carries a printed layer formed of the inkjet ink on the substrate.

The coloring composition of the present invention comprises:
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 alkylene chain, 1 ≦ m ≦ 3, and n = 2, 3, or 5. ]
A solvent (A-1) represented by :
General formula (2):
R— (O—C ₃ H ₆ ) _p —O—C (═O) —CH ₃ (2)
[However, R is an alkyl group having 1 to 8 carbon atoms, C ₃ H ₆ is a linear or branched propylene chain, and 1 ≦ p ≦ 3. ]
A solvent (A) containing a solvent (A-2) represented by
General formula (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. ]
A pigment (B) containing one or more pigments selected from the group consisting of phthalocyanine pigments represented by the formula (1) and a basic dispersant (C)
It is characterized by containing.

The coloring composition of the present invention contains the solvent (A-1) and the solvent (A-2), and thus has excellent dispersibility, fluidity, despite high solid content and high pigment concentration. And storage stability. Therefore, an excellent ink composition for ink jet recording can be prepared from the colored composition of the present invention. When a color filter substrate is produced using the ink composition for ink jet recording thus prepared, The yield due to flying bending is improved, and a printed layer having a sufficient density can be provided.

[Solvent]
The colored composition of the present invention is characterized by using a specific solvent (A) as a solvent component, and the solvent (A) is 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 alkylene chain, 1 ≦ m ≦ 3, and n = 2, 3, or 5. ]
A solvent (A-1) represented by :
General formula (2):
R— (O—C ₃ H ₆ ) _p —O—C (═O) —CH ₃ (2)
[However, R is an alkyl group having 1 to 8 carbon atoms, C ₃ H ₆ is a linear or branched propylene chain, and 1 ≦ p ≦ 3. ]
The solvent (A-2) represented by these is included.
As the characteristics required for the solvent used in the inkjet ink,
(1) Optimum affinity between pigment and dispersant for maintaining low viscosity and viscosity stability over time (2) Optimum drying speed and surface tension of ink for maintaining 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, color mixing prevention, and the like, and an optimal solvent-based design is required.

Copper phthalocyanine pigments and zinc phthalocyanine pigments differ in solubility in the pigments themselves, so the optimum solvent for dispersion also differs. Zinc phthalocyanine pigments are not suitable for dispersion because they have a good affinity for a solvent that is optimal for the dispersion of copper phthalocyanine pigments.

Since the solvent (A ) including the solvent (A-1) and the solvent (A- 2) has an optimum affinity with the pigment (B), the fine dispersion of the pigment, low viscosity, and good viscosity stability over time are obtained. Can be achieved.

When the solvent (A-1) is 1 ≦ m ≦ 3 and n = 2, 3, or 5 in the general formula (1), the solvent (A-2) is R in the general formula (2). Is an alkyl group having 1 to 8 carbon atoms, and when 1 ≦ p ≦ 3, the affinity with the pigment (B) is optimal. When the solvent (A-1) is m and n in the general formula (1), the solvent (A-2) is a value in which R and p in the general formula (2) exceed the defined range, Since the affinity with the pigment (B) is too good or too bad, the dispersibility of the pigment is deteriorated, and a sufficient degree of fineness cannot be obtained, and problems such as high viscosity and deterioration of viscosity with time occur.

As a more preferable form as the coloring composition of the present invention, the solvent (A-1 ) occupies 60% by weight or more in the total solvent. When the amount is less than 60% by weight, the affinity for the pigment cannot be sufficiently expressed.

As a more preferable form as the coloring composition of the present invention, a solvent (A-1) and a solvent (A-
One or more kinds of solvents selected from 2) include a solvent having a boiling point at 760 mmHg of 170 ° C. or higher. Further, as a more preferable form, one or more kinds of solvents selected from the group consisting of the solvent (A-1) and the solvent (A-2) are a solvent having a boiling point of less than 170 ° C. at 760 mmHg and a boiling point of 760 mmHg. Is a mixture of a solvent having a boiling point of less than 170 ° C at 760 mmHg and a solvent having a boiling point of not less than 170 ° C at 760 mmHg of 0: 100 to 70:30. That is. When the solvent having a boiling point of 760 mmHg and a boiling point of 170 ° C. or higher is not the main solvent, sufficient ejection stability may not be obtained when it is prepared as an inkjet ink. Even if a solvent having a boiling point of less than 170 ° C. at 760 mmHg is used to adjust dispersion stability, viscosity, or drying property, the solvent (A-1) and the solvent (A-2) are used. When the solvent having a boiling point of less than 170 ° C. at 760 mmHg exceeds 30% by weight in one or more selected solvents, sufficient ejection stability may not be maintained.

Examples of the solvent (A-1) used in the present invention, for example, ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, be mentioned pen Tan diol diacetate All of these have a boiling point at 760 mmHg of 170 ° C. or higher.

Butylene glycol diacetate includes 1,4-butylene glycol diacetate, 1
, 3-butylene glycol diacetate and the like. The 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 ° C. at 760 mmHg, such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol mono Examples include butyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate and the like having a boiling point of 170 ° C. or higher at 760 mmHg. In particular, propylene glycol monomethyl ether acetate or dipropylene glycol monomethyl ether It can be used ether acetate suitably.

As the coloring composition of the present invention, as a more preferable form, a solvent (A-3) having a boiling point at 760 mmHg of 240 ° C. or higher and a surface tension at 25 ° C. of 26 to 36 mN / m is used in combination. is there. When this solvent (A-3) is used in combination, drying in the vicinity of the head is suppressed and the ejection stability (particularly intermittent ejection properties) is improved when the ink is prepared as an inkjet ink. The solvent (A-3) having a boiling point of 240 ° C. or higher at 760 mmHg and a surface tension at 26 ° C. of 26 to 36 mN / m is included in the definitions of the solvent (A-1) and the solvent (A-2). However, when the solvent is different from the solvent (A-1) and the solvent (A-2), it can be used in a range of less than 40% in the total solvent, diethylene glycol mono n-butyl ether acetate, tripropylene Examples include glycol n-butyl ether.

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

 The pigment (B) constituting the coloring composition of the present invention has the general formula (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. ]
In particular, X is characterized by containing a pigment in which X is Br.

As a preferable form of the pigment constituting the coloring composition of the present invention, the average number of hydrogen atoms in X is 0 or more and 2 or less, the average number of Cl elements in X is 0 or more and 5 or less, and the average number of Br elements in X is 8 or more and 16 or less.

A representative pigment of the general formula (3) is represented by a color index (CI) number.
C. I. And a green pigment such as CI Pigment Green 58.

In the pigment (B) contained in the coloring composition of the present invention, not only the zinc halide phthalocyanine pigment as the main pigment but also other green pigments and yellow pigments can be used in combination for the purpose of color adjustment and complementary color. . The green pigment that can be used in combination is represented by a color index (CI) number, for example, C.I. I. Pigment Green 7, 10, 36, 37, and the like include yellow pigments such as C.I. 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, 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, 17 , It can be a 177,179,180,181,182,185,187,188,193,194,199, etc., listed.

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

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

[About dispersion resin]
The zinc halide phthalocyanine pigment which is the main pigment of the pigment (B) of the coloring composition of the present invention has a higher acidity than the conventional copper phthalocyanine pigment. Therefore, the basic dispersant (C) can be suitably used for fine dispersion of the zinc phthalocyanine pigment, and the viscosity of the colored composition and the ink jet ink using the same can be reduced and the stability over time can be improved.

As the basic dispersant (C) used in the colored composition of the present invention, a known basic resin type dispersant can be used. Specific examples of commercially available resin-type dispersants include the following.

As a basic resin type dispersant manufactured by Big Chemie, Anti-Terra-U, U10
0, 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 resin type dispersant manufactured by Nippon Lubrizol, Solspers 9000, 13
240, 13650, 13940, 17000, 18000, 20000, 24000SC, 24000GR, 28000, 31845, 32000, 32500, 32600, 33500, 34750, 35100, 35200, 37500, 38500, 44000, 55000 and the like.

As a basic resin type dispersant manufactured by Ciba Specialty Chemicals, EFKA-400
8, 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.

As a basic resin type dispersing agent made by Ajinomoto Fine Techno Co., Ajisper PB-711,
PB811, PB821, etc. are mentioned.

When producing a color filter using the ink-jet ink prepared from the colored composition of the present invention, since the color filter is required to be transparent, the present invention is applied to all wavelengths in the visible light region of 400 to 700 nm. The transmittance of the dispersion resin constituting the inkjet ink is preferably 80% or more, and more preferably 95% or more.

Furthermore, the basic dispersant (C) used in the colored composition of the present invention is preferably one or more partial structures selected from the group consisting of an acrylic polymer chain, a hydroxycarboxylic acid polymer chain, and an alkylene oxide polymer chain. And a basic dispersant (Ca) containing at least one kind of 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.

The acrylic polymer chain is obtained by polymerizing one or more alkyl (meth) acrylate monomers. Moreover, it is obtained by block copolymerization or random copolymerization with one or more types of (meth) acrylic acid alkyl monomers and other vinyl monomers as required.

A photopolymerizable group, a thermally reactive group, an anionic group, a cycloaliphatic group, an aromatic group, or the like can be arbitrarily introduced into the side chain.

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

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

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

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

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

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

The basic dispersant (C) used in the colored composition of the present invention is more preferably one or more partial structures selected from the group consisting of hydroxycarboxylic acid polymer chains, a polyallylamine chain, a polyethyleneimine chain, and A basic dispersant (Cb) containing one or more kinds of cationic partial structures selected from the group consisting of cationic polyurethane chains.

Moreover, as a structure of a basic dispersing agent (C), both a linear type and a comb type having a side chain in the main chain skeleton can be used.

The basic dispersant (C) that can be particularly preferably used in the coloring composition of the present invention is a hydroxycarboxylic acid polymer chain (polyester [c-1]) having a carboxyl group at one end and a primary or secondary main chain. Comb basic dispersant (Cc) obtained by condensation reaction with polyallylamine chain or polyethyleneimine chain (polyamine [c-2]) having two or more secondary amino groups, but other chemical structure and production method Is not particularly limited.

For example, a condensation reaction between a polyester [c-1] having a carboxyl group at one end and a 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] with the polyamine [C-2] is mixed and heated, and proceeds by amidation by dehydration. The reaction conditions at that time, that is, the charge ratio of polyester [c-1] and polyamine [c-2], molecular weight of polyester [c-1] and polyamine [c-2], reaction rate of amidation reaction, etc. The molecular weight, amine value, and acid value of the resin-type dispersant (C) can be controlled.

The number average molecular weight of the basic dispersant (C) is preferably 1,000 to 100,000. If the number average molecular weight of the basic dispersant (C) is less than 1,000, the dispersion effect and storage stability are lowered. If the number average molecular weight is more than 100,000, the viscosity of the dispersion is increased and dissolution in various organic solvents is performed. Lowers the dispersion and leads to poor dispersion. 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 acid value have a great influence on the solubility of the dispersant and the adsorptivity to the pigment, and the greatest effect can be obtained within these preferred ranges.

Polyester [c-1] having a carboxyl group at one end can be obtained by self-condensation of hydroxycarboxylic acid or lactone, or co-condensation of hydroxycarboxylic acid and lactone.

Examples of the hydroxycarboxylic acid include ricinoleic acid, ricinolenic acid, a mixture of 9 and 10-hydroxystearic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, lactic acid and the like, and lactone includes ε-caprolactone , Β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, 4-methylcaprolactone, 2-methylcaprolactone, etc., most preferably 12-hydroxystearic acid Is a cocondensate of ε-caprolactone. When these polyesters are condensed, a carboxylic acid containing no hydroxy group, for example, caproic acid, lauric acid, stearic acid, methoxyacetic acid, etc. 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 include polyethyleneimine, polyethylenepolyamine, polyallylamine and the like. 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 polycondensation of ethylene dichloride and ammonia in the presence of an alkali catalyst. 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 of 2 to 1000]
From the above viewpoint, as the above-mentioned commercially available basic dispersant (C) that can be used in the colored composition of the present invention, particularly preferred are Ajinomoto Fine Techno Co., Ltd. Ajisper PB821, Nihon Lubrizol Corp. Solspers 32000, Ciba Specialty EFKA-4300 manufactured by Chemicals Co., Disperbyk-161 manufactured by Big Chemie, Inc., and Azisper PB821 and Solspers 32000 manufactured by Nihon Lubrizol Co., Ltd. are particularly preferred, but are not limited thereto.

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

[Pigment derivative (D)]
In the present invention, a pigment derivative can be used as necessary. As a pigment derivative which can be used for this invention, what is shown by following General formula (4) can be used, for example.
General formula (4):
G ⁴ -J ⁴ q (4)
(In the formula, G ⁴ is a q-valent chromogenic compound residue, J ⁴ is a basic substituent, an acidic substituent, or a neutral substituent, and q is an integer of 1 to 4. .)
As a basic substituent, the substituent shown by following General formula (6), General formula (7), General formula (8), or General formula (9) is mentioned, for example.
General formula (6):

(In the general formula (6), X ^{61 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond.
n6 represents an integer of 1 to 10. R ^a6 , R ^b6 : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ^a6 and R ^b6 Represents an optionally substituted heterocycle containing a nitrogen, oxygen, or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. )
General formula (7):

(In general formula (7),
R ^a7 and R ^b7 : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or R ^a7 and R ^b7 Represents an optionally substituted heterocycle containing a nitrogen, oxygen, or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. )
General formula (8):

(In general formula (8),
X ^{81 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond.
R ^{a8 represents an optionally} substituted alkyl group, an ^optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ^b8 , R ^c8 , R ^d8 , R ^e8 : each independently represents a hydrogen atom, an ^optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred. )
General formula (9):

(In general formula (9),
X ^{91 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond.
Y ⁹ represents —NR ^a9 —Z ⁹ —NR ^b9 — or a direct bond.
R ^a9 and R ^b9 each independently represents a hydrogen atom, an ^optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred.
Z ^{9 represents an} alkylene group that may be substituted, an alkenylene group that may be substituted, or a phenylene group that may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-8 are preferable.
P ⁹ represents a substituent represented by the following general formula (9a) or a substituent represented by the following general formula (9b).
Q ⁹ : a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (7), or the general formula (
The substituent shown by 8) is represented. )
General formula (9a):

(In the general formula (9a),
n9 represents an integer of 1 to 10.
R ^c9 and R ^d9 : each independently an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group, an ^optionally substituted phenyl group, or a combination of R ^c9 and R ^d9 Represents an optionally substituted heterocycle containing a nitrogen, oxygen, or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. )
General formula (9b):

(In the general formula (9b),
R ^{e9 represents an optionally} substituted alkyl group, an ^optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ^f9 , R ^g9 , R ^h9 , R ⁱ⁹ : each independently represents a hydrogen atom, an ^optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred. )
As an acidic or neutral substituent, the substituent shown by following General formula (10), General formula (11), or General formula (12) is mentioned, for example.
General formula (10)

(In the general formula (10),
M ^{10 represents a} hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom.
l ¹⁰ : represents the valence of M ¹⁰ )
Formula (11)

(In general formula (11),
R ^a11 , R ^b11 , R ^c11 , R ^d11 : each represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (except when all are hydrogen atoms).
Formula (12)

(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 of 1 to 4. )

Dye prototype compound (G ⁴ refers to a compound having a generally known dye skeleton and a compound having a skeleton similar to the dye skeleton, which hardly absorbs in the visible light region.
Examples of the chromogenic compound residue include a diketopyrrolopyrrole dye residue, an azo dye residue (eg, azo, disazo, polyazo, etc.), a phthalocyanine dye residue, and an anthraquinone dye residue (eg, diamino). Dianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, etc.), quinacridone dye residue, dioxazine dye residue, perinone dye residue, perylene dye residue, thioindigo dye residue , Isoindoline dye residues, isoindolinone dye residues, quinophthalone dye residues, selenium dye residues, metal complex dye residues, anthraquinone residues, or triazine residues.

Moreover, as an anthraquinone derivative, the anthraquinone which has the said basic, acidic, or neutral substituent can be used. Examples of triazine derivatives include alkyl groups (eg, methyl group, ethyl group), amino groups, alkylamino groups (eg, dimethylamino group, diethylamino group, dibutylamino group), nitro groups, hydroxyl groups, alkoxy groups. A group (for example, methoxy group, ethoxy group, butoxy group, etc.), or a halogen (for example, chlorine, etc.); a phenyl group optionally substituted with a methyl group, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group, or the like; Alternatively, it may have a substituent such as 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. Use a derivative in which the above basic, acidic, or neutral substituent is introduced into 1,3,5-triazine. It can be.

The coloring composition of the present invention can have a low viscosity at a high solid content and a high pigment concentration, and can be used for gravure ink, offset ink, ink jet, or automobile paint, etc. / Because printed materials and coated materials with high transmittance can be obtained, they can be suitably used particularly for color filter substrates. As for the color filter substrate, it can be used for inkjet ink for inkjet system, resist ink for photolithography system, printing ink for transfer system, etc., but it can be suitably used for inkjet ink, taking advantage of the characteristics of the solvent (A).

Since the halogenated zinc phthalocyanine used as the main pigment in the colored composition of the present invention has a higher acidity than conventional copper phthalocyanine and has good affinity for the polar solvent used in the post-color filter production process, Solvent resistance and heat resistance are often problematic.

Therefore, when adjusting an inkjet ink from the coloring composition of this invention, it is desirable to mix | blend binder resin (E) and / or a heat-reactive compound (F).

[Binder resin (E)]
Ink jet inks prepared from the colored composition of the present invention include a binder resin (E).
It is desirable to blend. The binder resin (E) is preferably a thermoplastic resin.

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

A functional group that self-crosslinks, a functional group that reacts with a thermally reactive compound, a functional group that promotes a crosslinking reaction of the thermally reactive compound (F), and a thermally reactive compound (F Resin having one or more functional groups selected from functional groups that crosslink by reacting with), ink jet ink can be stored for a long time without thickening at room temperature, and can be stably discharged for a long time at room temperature If it can satisfy | fill, it can be used.

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, or 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 that reacts with the thermally reactive compound (F) to crosslink include a hydroxyl group, a carboxyl group,
Or an epoxy group etc. are mentioned.

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 is gradually crosslinked by an esterification reaction at a high temperature, is preferable. The acrylic resin having a hydroxyl group and a carboxyl group can be obtained, for example, by copolymerizing a monomer having a hydroxyl group, 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 but also as a crosslinking group or a crosslinking reaction promoting group when using the thermally reactive compound (F).

[About thermally reactive compound (F)]
The inkjet ink prepared from the coloring composition of the present invention includes a thermally reactive compound (F).
It is desirable to blend. The thermally reactive compound (F) can 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 from the colored composition of the present invention is non-reactive at room temperature, but for example, a temperature of 100 ° C. or higher (preferably 150 ° C. or higher). And a compound showing a crosslinking reaction, a polymerization reaction, a polycondensation reaction, or a polyaddition reaction. The zinc halide phthalocyanine pigment with high acidity used in the colored composition of the present invention accelerates the reaction even when the one having low reactivity at 150 to 250 ° C. is selected giving priority to stability during storage and ejection. It becomes an agent, and higher durability can be obtained.

The molecular weight of the thermally reactive compound that can be used 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 thermally reactive compound include melamine compounds, benzoguanamine compounds, epoxy compounds, oxetane compounds, phenol compounds, benzoxazines, blocked carboxylic acid compounds, blocked isocyanate compounds, carbodiimide compounds, acrylate monomers, or silane couplings. An agent can be used. Furthermore, it is preferable to contain at least a melamine compound and / or a benzoguanamine compound as the thermoreactive compound. Melamine compounds or benzoguanamine compounds have extremely small discoloration after heat treatment and can impart high resistance with a small addition amount, so it is possible to reduce the addition amount of heat-reactive compounds, increasing the pigment concentration of the ink, This leads to improvement of stability over time.

The melamine compound and / or benzoguanamine compound has a remarkable effect of curing the acidity of the pigment, and can provide a highly resistant cured product by self-condensation even without a binder resin.

Examples of the melamine compound or benzoguanamine compound include those having an imino group, a methylol group, or an alkoxymethyl group. Among these, a melamine compound or a benzoguanamine compound containing an alkoxyalkyl group is particularly preferable. When a melamine compound or 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, tetramethoxymethylol benzoguanamine, and tetrabutoxymethylol benzoguanamine, but are not necessarily limited thereto. Absent.

Specific examples of commercially available melamine compounds include the following. However, it is not necessarily limited to these.

Nicarac MW-30M, MW-30, MW-22, MS-21, manufactured by Nippon Carbide Corporation
MS-11, MW-24X, MS-001, MX-002, MX-730, MX750, MX-708, MX-706, MX-042, MX-035, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410, MX-302, Nippon Cytex Industry's Cymel 300, 301, 303, 350, 370, 325, 327, 703, 712, 01, 285, 232, 235, 236 238, 211, 254, 204, 202, 207, My Coat 506, 508, 212, 715 and the like.

Among them, preferred are alkamine-containing melamine compounds, Nicalac MW-30M, MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX-, manufactured by Nippon Carbide Corporation. 43, MX-302, Cymel 300, 301, 303, 350, 285, 232, 235, 236, 238, and Mycoat 506 manufactured by Nippon Cytex Industries.

Specific examples of commercially available benzoguanamine compounds include, for example, Nicarak BX-4000, SB-401, BX-37, SB-355, SB-303, SB301, BL-60, SB-255, SB- manufactured by Nippon Carbide Corporation. 203, SB-201, Nippon Cytex Industry's Cymel 1123, My Coat 105, 106, 1128, and the like.

Among them, preferred are alkoxyalkyl group-containing benzoguanamine compounds.
They are Nicalack BX-4000 and SB-401 manufactured by Nippon Carbide, and Cymel 1123 manufactured by Nippon Cytex Industry.

Other effective heat-reactive compounds are listed below, but are not necessarily limited thereto.

As an epoxy compound, for example, bisphenol fluorenediglycidyl ether,
Biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, di Glycidyl ethers of polyols such as glycerol polyglycidyl ether, sorbitol polyglycidyl ether, diglycidyl terephthalate, diglycidyl o-phthalate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, or polypropylene glycol diglycidyl ether, or Poly It can be exemplified glycidyl isocyanurate, not necessarily limited thereto.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane,
1,4-bis [[(3-ethyloxetane-3-yl) methoxy] methyl] benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) ) Oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxy) methyloxetane, oxetanylsilsesquioxane, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3- Ethyloxetane-3-yl) methoxy] benzene, 1,4-bis [[(3-ethyloxetane-3-yl) methoxy] methyl] biphenyl, 1-ethyl-3-oxetanylmethyl methacrylate, or benzene-1,4 -Dicarboxylate bis [1-ethyl (3-oxetanyl) methyl] ester Although and the like, not necessarily limited thereto.

As the phenol compound, for example, both a novolac type phenol compound obtained by reacting phenols and aldehydes under an acidic catalyst and a resol type phenol compound obtained by reacting under a basic catalyst can be used. Examples of phenols include orthocresol, paracresol, paraphenylphenol, paranonylphenol, 2,3-xylenol, phenol, metacresol, 3,5-xylenol, resorcinol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol. Examples thereof include B, bisphenol E, bisphenol H, and bisphenol S, but are not necessarily limited thereto. Examples of aldehydes include formaldehyde and acetaldehyde, but are not necessarily limited thereto. Phenols and aldehydes may be used singly or in combination of two or more.

Specific examples of commercially available benzoxazine compounds include, but are not necessarily limited to, benzoxazine Pd type and benzoxazine Fa type manufactured by Shikoku Kasei Kogyo Co., Ltd.

Examples of the blocked carboxylic acid compound include the following combinations of carboxylic acid compounds and blocking agents.

Examples of carboxylic acid compounds include 1,2-phthalic acid, 1,3-phthalic acid, and 1,4-phthalic acid.
Phthalic acid, 1,2,4-trimellitic acid, pyromellitic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid, C1-CIC acid, CIC acid, C3 -CIC acid, Bis-CIC acid, etc. can be mentioned, However, it is not necessarily limited to these.

Examples of the blocking agent include ethyl vinyl ether, n-propyl vinyl ether,
Although isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, etc. can be mentioned, it is not necessarily limited to this. Moreover, it is used individually by 1 type or in combination of 2 or more types.

Examples of the blocked isocyanate compound include the following combinations of isocyanate compounds and blocking agents.

Examples of the blocked isocyanate compound include, for example, hexamethylene diisocyanate, isophorone diisocyanate, toluidine isocyanate, diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, and bis (4-isocyanatocyclohexyl) methane. Diisocyanates such as tetramethylxylylene diisocyanate, isocyanurates of these diisocyanates, trimethylolpropane adduct type, biuret type, or prepolymers having isocyanate residues (low polymers obtained from diisocyanates and polyols) and isocyanate residues Although uretdione etc. which have these can be mentioned, it is not necessarily limited to this.

Examples of the blocking agent include phenol (dissociation temperature of 180 ° C. or higher), ε-caprolactam (dissociation temperature of 160 to 180 ° C.), oxime (dissociation temperature of 130 to 160 ° C.), or active methylene (100 to 120 ° C.). However, the present invention is not necessarily limited to this. Moreover, it is used individually by 1 type or in combination of 2 or more types.

Specific examples of commercially available carbodiimide compounds include Carbodilite V-01, V-03, 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, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxyethyl (meth). Acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol Modified trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tora (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, or urethane acrylate Acid ester or methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, Examples include pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile, but are not necessarily limited thereto.

When an acrylate monomer is used, a polymerization initiator can be used for the purpose of further improving curability. As the polymerization initiator, a thermal polymerization initiator may be used for the purpose of improving curability during heating. Examples of the thermal polymerization initiator include organic peroxide initiators and azo initiators.

Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, or vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4 -Epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl ) Γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltri Examples include methoxysilane, aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

Of these heat-reactive compounds, the melamine compound or 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, phenol compound, blocked isocyanate compound, or acrylate monomers 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 wt% to 40 wt%. If the content is insufficient, heat resistance or chemical resistance may be inferior. Moreover, when content exceeds 40%, the increase in a viscosity or the fall of storage stability may arise.

[About physical properties]
In the colored composition of the present invention, the solid content is preferably 3 with respect to the total weight of the composition.
-60% by weight, more preferably 4-40% by weight. When the solid content is less than 3% by weight, the concentration and resistance of the ink film prepared from the colored composition are insufficient, and when it exceeds 60% by weight, the viscosity of the colored composition increases and the stability over time decreases. There is.

The viscosity of the colored composition of the present invention is preferably 2 mPa · s to 100 mPa · s at 25 ° C., more preferably 3 mPa · s to 50 mPa · s, and even more preferably 3 mPa · s to 40 mPa · s. When the viscosity of the coloring composition is too large, the viscosity of the inkjet ink prepared from the coloring composition also increases, and stable ejection cannot be achieved when the ink is ejected continuously. Moreover, as a viscosity of the inkjet ink prepared from the coloring composition of this invention, 3 mPa * s or more and 40 mPa * s or less are preferable.

The average dispersed particle size of the colored composition of the present invention is preferably 5 nm to 200 nm, and more preferably 10 nm to 100 nm. If the average dispersed particle size of the colored composition is too large, the head is likely to be clogged when an inkjet ink prepared from the colored composition is ejected, and stable ejection cannot be achieved. On the other hand, when the average dispersed particle size is too small, reaggregation is likely to occur, and the temporal stability is deteriorated.

The surface tension of the ink-jet ink prepared from the colored composition of the present invention is 20 m
N / m or more and 40 mN / m or less is preferable, and 24 mN / m or more and 35 mN / m or less is more preferable. If the surface tension is too high, the ink cannot be stably ejected from the head. Conversely, if the surface tension is too low, the ink after ejection from the head cannot form droplets.

The production of the coloring composition of the present invention and the inkjet ink prepared from the coloring composition,
The dispersion resin, the pigment, the heat-reactive compound, the organic solvent, and the binder resin and / or pigment derivative as necessary are put into a normal disperser to obtain a desired average particle size / size distribution. Can be carried out by dispersing up to. The coloring composition and the raw material of the ink-jet ink may be mixed and dispersed all at once, or may be separately mixed and dispersed in consideration of the characteristics and economics of each raw material. When the viscosity of the inkjet ink is too high and dilution is necessary, the inkjet ink can be prepared by adding a liquid medium for dilution to the ink stock solution and stirring uniformly.

As the disperser, a sand mill, a bead mill, an agitator mill, a dyno mill, a cobol mill, or the like is suitable. In each disperser, when there is a viscosity region suitable for pigment dispersion, the viscosity can be adjusted by changing the ratio of various resin components to the pigment. The colored composition and the inkjet ink are preferably filtered by a filter or a centrifugal method for the purpose of removing coarse particles and foreign matters after being dispersed by a disperser.

In producing the colored composition of the present invention, a surfactant-type dispersant, an anthraquinone derivative, and / or a triazine derivative can be further used. Examples of the surfactant type pigment dispersant include naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl phenyl ether, or stearylamine acetate. be able to.

The ink-jet ink prepared from the colored composition of the present invention can contain various additives in the range of the above viscosity, average particle diameter, or surface tension. For example, a surfactant can be included in order to control the wettability of the ink to the substrate. When selecting a surfactant, it is necessary to consider compatibility with other ink components. There are anionic, cationic, amphoteric, and nonionic surfactants, and a suitable surfactant may be selected.

  In addition, the ink jet ink of the present invention contains an organic solvent such as an alcohol solvent, a glycol solvent, an ester solvent, and / or a ketone solvent within the range of the viscosity, the average particle diameter, or the surface tension. Can be added.

  The inkjet ink prepared from the colored composition of the present invention has a high pigment concentration and a low viscosity, so it has excellent ejection stability, and the pigment content is higher than that of normal inkjet ink, so the ejection amount should be reduced. Therefore, productivity and quality of printed matter for which a high print density is desired, such as for color filter substrates, can be improved. In particular, the ink composition for ink jet recording of the present invention is suitable for the production of a color filter substrate that requires high productivity and quality.

  In addition, the inkjet ink prepared from the colored composition of the present invention has a pigment dispersed at a high concentration, so that the ink composition penetrates in the depth direction, spreads in the lateral direction, spreads out in the lateral direction, glass, Even if it is a metal, printing density can be increased. Furthermore, since the discharge amount can be suppressed, it is possible to prevent the ink from flowing out and mixing due to exceeding the ink receiving amount of the receiving layer, and it is possible to avoid that the dot shape did not become a perfect circle. It can also be used for limited applications in printing.

[Color filter substrate]
A color filter substrate can be produced by an inkjet method using a green inkjet ink prepared from the colored composition of the present invention together with a red inkjet ink and a blue inkjet ink. The color filter substrate can be used for, for example, a liquid crystal display panel used for a thin television or the like.

  The color filter substrate is provided with a filter segment having a desired hue, and the filter segment discharges each color ink-jet ink for the color filter by an ink-jet method in a region divided by the black matrix of the substrate on which the black matrix is formed. It is formed by doing.

  Red inkjet ink and blue inkjet ink other than the green inkjet ink using the colored composition of the present invention are prepared from a colored composition obtained using the following pigments.

  Examples of red inkjet ink include C.I. I. 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, 240, 246, 254, 255, 264, Red pigments such as 272 can be used.

  Examples of red inkjet ink include C.I. 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, 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, 17 Yellow pigments such as 177,179,180,181,182,185,187,188,193,194,199, and / or, for example, C. I. Orange pigments such as CI Pigment Orange 36, 43, 51, 55, 59, and 61 can be used in combination.

  Examples of blue inkjet ink include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. For blue inkjet ink, C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

  As the substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate can be used. The black matrix is formed on the substrate by, for example, a photolithography method in which a radical polymerization type black resist is applied, exposed, developed, and patterned, a printing method in which black ink is printed, or a vapor deposition method in which metal is evaporated and then etched. Can be formed.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention. In the following examples and comparative examples, parts and% represent parts by weight and% by weight. The pigments, pigment derivatives, solvents and resin solutions used in Examples and Comparative Examples are shown below. Moreover, the dispersion | distribution prescription and final ink composition in an Example and a comparative example are shown to Tables 1-7.

[A] Solvent: Solvent having a boiling point of 170 ° C. or higher at 760 mmHg (A-1)
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-butylene Glycol diacetate 7) 13BGDA: 1,3-butylene glycol diacetate 8) 15PtGDA: 1,5-pentanediol diacetate Solvent having a boiling point of less than 170 ° C. at 760 mmHg (A-2)
9) PGMAc: propylene glycol monomethyl ether acetate / solvent having a boiling point of 170 ° C. or higher at 760 mmHg (A-2)
10) DPMA: Dipropylene glycol methyl ether acetate / solvent (A-1), Solvent having a boiling point of 170 ° C. or higher at 760 mmHg other than solvent (A-2) 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) 16 HDDA: 760 mmHg other than 1,6-hexanediol diacetate / solvent (A-1) and solvent (A-2) Solvent having a boiling point of less than 170 ° C. 16) Anone: Cyclohexanone 17) Butyl acetate

[B] Pigment / Pigment (B)
1) PG58: C.I. I. Pigment Green 58 (halogenated zinc phthalocyanine pigment) and pigments other than halogenated zinc phthalocyanine 2) PG36: C.I. I. Pigment Green 36 (copper halide phthalocyanine pigment)
3) PY150: C.I. I. Pigment Yellow 150 (azo pigment)
4) PY138: C.I. I. Pigment Yellow 138 (quinophthalone pigment)

[C] Dispersant / Basic Dispersant (C)
(C-1) Comb basic obtained by a condensation reaction between a hydroxycarboxylic acid polymer chain having a carboxyl group at one end and a polyallylamine chain or polyethyleneimine chain having two or more primary or secondary amino groups in the main chain Dispersant (Cc)
1) PB821: Ajinomoto Fine Techno Co., Ltd. Ajisper PB-821 (100% solid content)
2) SP32000: Solsperse-32000 (100% solid content) manufactured by Avicia
(C-2) Basic dispersant excluding (Cc) 3) EFKA4300: EFKA-4300 manufactured by Ciba Specialty Chemicals (solid content 81% PGMAc)
4) BYK161: Disperbyk-161 (solid content 30% PGMAc / butyl acetate) manufactured by Big Chemie
Acidic dispersant 5) PA111: Ajinomoto Fine Techno Co., Ltd. Addispar PA-111 (100% solid content)
6) BYK111: Disperbyk-111 (solid content> 90%) manufactured by Big Chemie 7) SP24000: Solsperse-24000 (100% solid content) manufactured by Avicia
8) J678: Joncrill-678 (100% solid content) manufactured by BASF Japan

  When using Azisper PB-821, EFKA-4300, Solsperse-32000, Azisper PA-111, Disperbyk-111, Solsperse-24000, Joncrill-678, it dissolves in the main solvent of the coloring composition and has a solid content of 30% And used as a solution.

[D] Pigment derivative / pigment derivative (D)
Pigment derivative [BD-1]
General formula (13):

A compound represented by

[E] Binder resin / Binder resin (E)
J804: Acrylic resin Joncryl-804 (acid value 15, OH group value 45, weight average molecular weight 12,500, solid content 100%) manufactured by BASF Japan
It was dissolved in the main solvent of the coloring composition and used as a solution having a solid content of 30%.

[F] Thermally reactive compound / thermally reactive compound (F)
1) MX-43: Nippon Carbide Corp. alkoxyalkyl group-containing melamine compound Nicalak MX-43
2) MX-417: Nicarac MX-417, an imino group / methylol group-containing melamine compound manufactured by Nippon Carbide Corporation
3) SB-401: Nippon Carbide Corp. alkoxyalkyl group-containing benzoguanamine compound Nicalac SB-401
4) BL-60: Nippon Carbide Co., Ltd. imino group / methylol group-containing benzoguanamine compound Nicalak BL-60
5) M-400: acrylic monomer made by Toagosei Co., Ltd. Aronix M-400
6) BL-4265: Isocyanate Compound Death Module BL-4265 manufactured by Sumika 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 (30% solids solution) as basic dispersant (C), and 307 parts of EGDA as solvent (A-1) are mixed in a mixer, and further mixed with a sand mill. The mixture was dispersed into a colored composition to obtain a colored composition. Further, 20 parts of a melamine compound (MX-43) as a heat-reactive compound (F) and 250 parts of 15PtGDA as a solvent (A-1) were added and mixed with a homodisper. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 20% was obtained.

<< Examples 2-42 and Comparative Examples 1-26 >>
In the same manner as in Example 1, dispersion and preparation were performed so that the compositions in Examples 2 to 34 and Comparative Examples 1 to 26 in the composition tables of Tables 1 to 9 were obtained, and colored compositions and inkjet inks were obtained. It was.
Moreover, it carried out similarly to Example 1, and disperse | distributed and prepared so that it might become a composition of Examples 35-42 in the composition table | surface of Table 19, and obtained the colored composition and inkjet ink.
However, Examples 1 to 24 and 26 to 42 are reference examples.

  In addition, the numerical value in the composition table | surface of Tables 1-9 and Table 19 shows the weight part used substantially. The material dissolved and used in the main solvent indicates the solid content (parts by weight), and the main solvent (parts by weight) used for the dissolution is shown in addition to the main solvent.

  That is, taking Example 1 as an example, in Table 1, pigment (B) PG85 is 100 (parts by weight), basic dispersant (C) PB-821 is 40 (parts by weight), solvent (A- 1) EGDA is 400 (parts by weight), thermally reactive compound (F) MX-43 is 20 (parts by weight), and solvent (A-1) 15PtGDA is 250 (parts by weight).

  The viscosity and fluidity, temporal stability, average particle diameter, and haze of the colored compositions obtained in Examples 1-42 and Comparative Examples 1-26 were evaluated by the following methods. The results are shown in Tables 10-18 and 20. Further, 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 21-30.

[viscosity]
Using a dynamic viscoelasticity measuring device, the viscosity (η: mPa · s) at a shear rate of 100 (1 / s) was measured and evaluated according to the following criteria.
○: η <40
Δ: 40 ≦ η <50
×: 50 ≦ η

[Liquidity]
Using a dynamic viscoelasticity measuring device, the viscosity (ηa: mPa · s) at a shear rate of 10 (1 / s) was measured, and the viscosity (η: mPa · s) at a shear rate of 100 (1 / s) measured previously. The ratio ηa / η was determined, the fluidity was evaluated according to the following criteria, and the following criteria were evaluated.
○: 0.9 ≦ ηa / η <1.5
×: 1.5 ≦ ηa / η

[Storage stability]
After heating for 7 days in a 45 ° C. oven, the viscosity was measured and evaluated according to the following criteria.
○: Thickening rate ≦ 10% compared to the viscosity before heating
×: Thickening rate> 10% compared to the viscosity before heating

[Average particle size]
The average particle size [D] is obtained by diluting 0.001 g of the colored composition with 30 g of the main solvent of the colored composition to prepare a measurement sample, and measuring a laser Doppler particle size distribution measuring apparatus (UPA-EX150, manufactured by Nikkiso Co., Ltd.). ) And evaluated according to the following criteria.
○: 10 nm ≦ [D] <100 nm
Δ: 100 nm ≦ [D] <200 nm
×: [D] ≧ 200 nm

[Haze]
Using a spin coater, the substrate coated on glass at 1500 rpm was dried on a hot plate at 100 ° C. for 3 minutes, and the haze of the coated surface was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.). Evaluated by criteria.
○: [Haze] <3
Δ: 3 ≦ [Haze] <4.5
×: [Haze] ≧ 4.5

[Discharge stability A]
The ink obtained in Examples 1-22, Examples 25-42 and Comparative Examples 1-26 was ejected and dried at a predetermined position of the glass substrate using the inkjet printer, and heat was applied at 230 ° C. for 20 minutes. Curing was performed to form a coating film, and coating film reliability was evaluated by the following method.
The printing state was visually observed, and the ejection stability was evaluated according to the following criteria.
○: Nozzle dropout is 5% or less after continuous discharge for 15 minutes.
(Triangle | delta): A nozzle missing is 10% or less after discharge for 15 minutes continuously.
X: Nozzle omission is 50% or more after continuous discharge for 15 minutes.

[Discharge stability B]
Moreover, the ink obtained in Examples 1-22, Examples 25-42 and Comparative Examples 1-26 was discharged onto the cardboard using the inkjet printer and dried, followed by room temperature drying to form a coating film. The print density was evaluated by the following method.
The printing state was visually observed, and the ejection stability was evaluated according to the following criteria.
(Double-circle): When intermittent time (15 minutes) which interrupts discharge passes, when it discharges, nozzle omission is 5% or less.
○: Nozzle omission is 10% or less when discharging is performed after an intermittent time (15 minutes) during which discharging is interrupted.
(Triangle | delta): When intermittent time (15 minutes) which interrupts discharge passes, when it discharges, nozzle omission is 20% or less.
X: Nozzle omission is 50% or more when discharging is performed after an intermittent time (15 minutes) during which discharging is interrupted.

[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 the immersion was measured and evaluated according to the following criteria.
○: ΔE ≦ 2.5
Δ: 2.5 <ΔE ≦ 5
×: ΔE> 5

  The coloring composition of the present invention, when used as a paint or ink, can be made to have a low viscosity despite its high pigment concentration. Signs, automobile paints, color filters, etc. can be produced. In addition, when the colored composition of the present invention is used as an ink-jet ink, the ink has good chemical resistance, excellent low-viscosity viscosity stability over time, and good ejection stability even though the pigment concentration is high. Therefore, it is possible to produce a high-performance color filter much more efficiently than the conventional method.

  As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.

Claims (5)

A coloring composition containing a solvent (A), a pigment (B), and a basic dispersant (C),
The solvent (A) is 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 alkylene chain, 1 ≦ m ≦ 3, and n = 2, 3, or 5. ]
A solvent (A-1) represented by :
General formula (2):
R— (O—C ₃ H ₆ ) _p —O—C (═O) —CH ₃ (2)
[However, R is an alkyl group having 1 to 8 carbon atoms, C ₃ H ₆ is a linear or branched propylene chain, and 1 ≦ p ≦ 3. ]
The coloring composition characterized by including the solvent (A-2) represented by these, and the said pigment (B) containing the phthalocyanine pigment represented by following General formula (3).
General formula (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. ]   The solvent (A-1) is one or more solvents selected from the group consisting of ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, and pentanediol diacetate. The coloring composition according to claim 1, wherein The basic dispersant (C) is one or more partial structures selected from the group consisting of an acrylic polymer chain, a hydroxycarboxylic acid polymer chain, and an alkylene oxide polymer chain;
It is a basic dispersant (Ca) containing 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. The coloring composition according to claim 1 or 2 . The basic dispersant (C) is obtained by a condensation reaction between a hydroxycarboxylic acid polymer chain having a carboxyl group at one end and a polyallylamine chain or polyethyleneimine chain having two or more primary or secondary amino groups in the main chain. The coloring composition according to any one of claims 1 to 3 , wherein the coloring composition is a comb-shaped basic dispersant (Cc). A color filter substrate comprising a filter segment formed of the colored composition according to any one of claims 1 to 4 on a substrate.