KR20090029643A - Coloring composition containing phthalocyanine pigment, ink-jet ink containing same, and color filter substrate - Google Patents

Abstract

A coloring composition is provided to ensure excellent dispersibility, fluidity and preserving stability while showing high pigment concentration, by using zinc phthalocyanine pigment with excellent coloring property. A coloring composition comprises solvent(A), pigment(B) and basic dispersing agent(C). The solvent(A) comprises at least one kind of solvent selected from the group consisting of the solvent (A-1) represented by the chemical formula 1: CH3-C(=O)-O-(CnH2nO)m-C(=O)-CH3, and the solvent (A-2) represented by the chemical formula 2: -(O-C3H6)p-O-C(=O)-CH3. The pigment(B) comprises phthalocyanine pigment represented by the chemical formula 3. In the chemical formula 1, CnH2n is linear or branched alkylene chain; 1<=m<=3; and 2<=n<=5. In the chemical formula 2, R is C1-8 alkyl group; C3H6 is linear or branched propylene chain; and 1<=p<=3. In the chemical formula 3, M is Zn as a central metal element; and X1~X16 are an element selected from the group consisting of H, Cl, and Br.

Description

 Coloring composition containing phthalocyanine pigment, ink-jet ink containing same, and color filter substrate}

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

In recent years, "color reproducibility" is strongly required for color liquid crystal displays, which are the largest applications of color filter substrates, and inks used for the production of color filter substrates are required to have high color purity and color density and high transparency. In order to satisfy these required physical properties, fine dispersion of pigments is required.

The pixel portion of the color filter according to the inkjet method is formed by providing a black matrix on a transparent substrate in advance and filling ink with the inkjet method in a region divided by the black matrix. At this time, if the solid content of the ink is low and / or the pigment concentration is low, in the process of producing a color filter having a desired color density, the ink overflows beyond the black matrix, and the ink is mixed in the adjacent regions, Sometimes the color of the filter segment may be impaired. At this time, the ink used for a color filter requires high solidification and high pigment concentration. Moreover, low viscosity and viscosity stability are also required for inkjet ink in order to ensure stable discharge property (for example, patent document 4). Green, which is one of the three primary colors (red, blue, green; RGB) of the color filter substrate, generally uses copper halide phthalocyanine (for example, CI pigment green 36) in both the resist method and the inkjet method. Dispersion of the phthalocyanine pigment may cause problems such as miniaturization of the pigment, excessively high viscosity, or poor transmittance.

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

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

(2) improvement of color characteristics such as sharpness of image, that is, improvement of contrast ratio

Although this has been demanded, especially in the color filter which used the conventional copper halide phthalocyanine pigment, there exists a big gap between the present chromaticity and required chromaticity of green, and it was difficult to satisfy these requirements.

In order to solve these problems, what changed the central metal of a phthalocyanine pigment from copper to zinc, nickel, etc. has been used (for example, patent document 1, patent document 2, patent document 3). However, it is known that zinc halide phthalocyanine pigments are different from the conventional green pigments in their chemical properties and are difficult to disperse in organic solvents as compared with conventional copper halide phthalocyanine pigments. For this reason, it was difficult to stably disperse a zinc halide phthalocyanine pigment stably, maintaining excellent color characteristics only by using the dispersing agent and solvent suitable for conventional copper halide phthalocyanine or another pigment.

In addition, since the organic solvents used in the dispersion of zinc halide phthalocyanine pigments have low boiling point and high evaporation rate, when used as a main solvent of ink jet ink, there is a problem that lead to deterioration in ejection properties. Zinc halide phthalocyanine is used in ink jet ink It was difficult to put it to practical use.

[Patent Document 1] Japanese Patent Laid-Open No. 2003-161828

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

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

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

An object of the present invention is to provide a coloring composition having a high solids content and a high pigment concentration, excellent dispersibility, fluidity, and storage stability, 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. Moreover, the objective of this invention is providing the color filter substrate formed by the inkjet method using the said inkjet ink.

The subject is a coloring composition comprising a solvent (A), a pigment (B), and a basic dispersant (C), wherein the solvent (A) is represented by the formula 1:

[Wherein C _n H _2n is a straight or branched alkylene chain, 1 ≦ m ≦ 3, and 2 ≦ _n ≦ 5).

Solvent represented by (A-1), and Formula 2:

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

One or more types of solvents selected from the group consisting of a solvent (A-2) represented by the above, and the pigment (B) containing a phthalocyanine pigment represented by the following formula (3)

It can solve by the said coloring composition characterized by the above-mentioned.

Formula 3:

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

In the preferable aspect of the coloring composition which concerns on this invention, the 1 or more types of solvent chosen from the group which consists of a solvent (A-1) and a solvent (A-2) occupy 60 weight% or more in all the solvents.

In another preferable aspect of the coloring composition which concerns on this invention, the 1 or more types of solvent chosen from the group which consists of a solvent (A-1) and a solvent (A-2) have a solvent whose boiling point in 760 mmHg is 170 degreeC or more. Include.

In a more preferable aspect of the coloring composition which concerns on this invention, the at least 1 sort (s) of solvent chosen from the group which consists of a solvent (A-1) and a solvent (A-2) is a solvent whose boiling point in 760 mmHg is less than 170 degreeC; As a mixture of the solvent whose boiling point in 760 mmHg is 170 degreeC or more, the weight mix ratio of the solvent whose boiling point in 760 mmHg is less than 170 degreeC and the solvent whose boiling point in 760 mmHg is 170 degreeC or more is 0: 100-70: 30. to be.

In another preferred aspect 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 At least one solvent selected from the group consisting of glycol diacetate and pentanediol diacetate, and in a more preferred embodiment, solvent (A-1) is diethylene glycol diacetate, propylene glycol diacetate, and butylene glycol di At least one solvent selected from the group consisting of acetates.

In another preferable aspect of the coloring composition which concerns on this invention, a solvent (A-2) is propylene glycol monomethyl ether acetate and / or dipropylene glycol monomethyl ether acetate, In a further more preferable aspect, a solvent (A-2) ) Is dipropylene glycol monomethyl ether acetate.

In another preferred aspect of the coloring composition according to the present invention, the basic dispersant (C) is one or more types of substructures 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) comprising at least one cationic substructure selected from the group consisting of polyallylamine chains, polyethyleneimine chains, cationic polyurethane chains, and cationic acrylic polymer chains.

In another preferable aspect of the coloring composition which concerns on this invention, the pigment derivative (D) represented by following formula (4) is included.

Formula 4:

(In the formula 4, G ⁴ is a q-valent dye circular compound residue, J ⁴ is a basic substituent, acid substituents, a neutral substituent, q is an integer of 1 to 4.)

In another preferable aspect of the coloring composition which concerns on this invention, solid content of a coloring composition is 3 to 60 weight% with respect to the coloring composition total weight.

In another preferable aspect of the coloring composition which concerns on this invention, content of the pigment (B) of a coloring composition is 1-30 weight% with respect to the coloring composition total weight.

In another preferable aspect of the coloring composition which concerns on this invention, the weight ratio of the pigment (B) and basic dispersing agent (C) of a coloring composition is 100: 3-100: 150.

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

Furthermore, this invention relates to the inkjet ink which further contains the said coloring composition, 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 carboxyl It is 1 type, or 2 or more types of compound chosen from the group which consists of an acid compound, a blocked isocyanate compound, an acrylate monomer, and a silane coupling agent, In a more preferable aspect, it is at least a melamine compound and / or a benzoguanamine compound.

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

Moreover, this invention relates also to the color filter board | substrate which supports the printed layer formed with the said inkjet ink on the board | substrate.

The coloring composition of the present invention,

Formula 1:

[Formula 1]

[Wherein C _n H _2n is a straight or branched alkylene chain, 1 ≦ m ≦ 3, and 2 ≦ _n ≦ 5).

Solvent represented by (A-1), and Formula 2:

[Formula 2]

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

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

Formula 3:

[Formula 3]

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

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

Basic Dispersant (C)

It is characterized by including the.

The coloring composition of this invention contains 1 or more types of solvents chosen from a solvent (A-1) and a solvent (A-2), and is excellent dispersibility, fluidity, and preservation, despite being a high solid content and a high pigment concentration. Have stability. Therefore, an excellent inkjet recording ink composition can be prepared from the coloring composition of the present invention, and in the case of producing a color filter substrate using the inkjet recording ink composition prepared in this way, it is possible to discharge or discharge the ink. The yield by bending) can be improved to provide a printing layer of more sufficient concentration.

[About solvent]

The coloring composition of this invention uses the specific solvent (A) as a solvent component, The said solvent (A) is a chemical formula 1:

[Formula 1]

[Wherein C _n H _2n is a straight or branched alkylene chain, 1 ≦ m ≦ 3, and 2 ≦ _n ≦ 5).

Solvent represented by (A-1), and Formula 2:

[Formula 2]

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

One or more types of solvents chosen from the group which consists of a solvent (A-2) represented by these are included.

As a characteristic required for the solvent used for inkjet ink,

(1) Optimum affinity of pigment and dispersant to maintain low viscosity and time-viscosity stability

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

Can be mentioned.

In particular, inkjet inks used for color filter applications and the like require high pigment concentrations and high solids concentrations from the viewpoints of productivity, prevention of mixed color, and the like, and an optimum design of a solvent system is required.

Since copper phthalocyanine pigment and zinc phthalocyanine pigment differ in the solubility of the pigment itself, the solvent which is optimal for dispersion also differs. As a solvent which is most suitable for dispersion of a copper phthalocyanine pigment, a zinc phthalocyanine pigment has too much affinity and is not suitable for dispersion.

Since the solvent (A) containing at least one solvent selected from the group consisting of a solvent (A-1) and a solvent (A-2) has an optimum affinity with the pigment (B), fine dispersion and low point of the pigment Fig. And good time-point stability can be achieved.

When the solvent (A-1) is 1≤m≤3 and 2≤n≤5 in the formula (1), the solvent (A-2) is R in the formula (2) is an alkyl group having 1 to 8 carbon atoms, When 1≤p≤3, the affinity with the pigment (B) is optimum, respectively. Solvent (A-1) is m and n of the formula (1), solvent (A-2) is a value of R and p in the formula (2) exceeds the above defined range, the affinity with the pigment (B) is excessive Since it is good or too bad, the dispersibility of a pigment worsens and sufficient degree of refinement | miniaturization is not obtained, and problems, such as high viscosity and time-lapse deterioration, arise.

As a more preferable aspect as the coloring composition of this invention, the 1 or more types of solvent chosen from a solvent (A-1) and a solvent (A-2) occupy 60 weight% or more of all the solvent. If less than 60% by weight, the affinity for the pigment cannot be sufficiently expressed.

As a more preferable aspect as the coloring composition of this invention, the 1 or more types of solvent chosen from a solvent (A-1) and a solvent (A-2) contain the solvent whose boiling point in 760 mmHg is 170 degreeC or more. Moreover, as a more preferable aspect, the 1 or more types of solvent chosen from the group which consists of a solvent (A-1) and a solvent (A-2) have the boiling point in 760 mmHg and the solvent whose boiling point in 760 mmHg is less than 170 degreeC. It is a mixture of this solvent of 170 degreeC or more, and the weight mix ratio of the solvent whose boiling point in 760 mmHg is less than 170 degreeC, and the solvent whose boiling point in 760 mmHg is 170 degreeC or more is 0: 100-70: 30. If the solvent having a boiling point of 760 mmHg of 170 ° C. or more is not the main solvent, sufficient ejection stability may not be obtained in the case of preparing with inkjet ink. In order to adjust dispersion stability, viscosity, or drying property, even if a solvent having a boiling point of less than 170 ° C at 760 mmHg may be used, it is selected from the group consisting of solvent (A-1) and solvent (A-2). If the solvent having a boiling point at 760 mmHg of less than 170 ° C exceeds 30% by weight among one or more kinds of solvents, sufficient discharge stability may not be maintained.

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 etc. are mentioned, These all have a boiling point of 170 degreeC or more in 760 mmHg.

The 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.

As a solvent (A-2) used for this invention, the solvent whose boiling point in 760 mmHg, such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, is less than 170 degreeC, propylene glycol monopropyl ether acetate, The boiling point in 760 mmHg, such as propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate, is 170 degreeC or more. Although a solvent is mentioned, Especially propylene glycol monomethyl ether acetate or dipropylene glycol monomethyl ether acetate can be used suitably.

As a coloring composition of this invention, As a more preferable aspect, it uses together the solvent (A-3) whose boiling point in 760 mmHg is 240 degreeC or more and the surface tension in 25 degreeC is 26-36 mN / m. By using this solvent (A-3) together, when it prepares with inkjet ink, drying in the head vicinity is suppressed and discharge stability (especially intermittent dischargeability) is improved. As a solvent (A-3) whose boiling point in 760 mmHg is 240 degreeC or more and the surface tension in 25 degreeC is 26-36 mN / m, it defines to the definition of the said solvent (A-1) and a solvent (A-2). Although it is also possible to use the compound included, when it is different from the said solvent (A-1) and a solvent (A-2), it can be used in less than 40% of the total solvent, and diethylene glycol mono n-butyl ether acetate And tripropylene glycol n-butyl ether.

[About Pigment]

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

Pigment (B) constituting the coloring composition of the present invention is represented by the formula 3:

[Formula 3]

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

In particular, the pigment represented by X is characterized by including a pigment which is Br.

As a preferable aspect of the pigment which comprises the coloring composition of this invention, the average hydrogen atom number in X is 0 or more and 2 or less, the average Cl element number in X is 0 or more and 5 or less, and the average Br element number in X is 8 or more and 16 or less.

Representative pigments of Formula 3 are represented by color index (C.I.) numbers. Green pigments, such as pigment green 58, are mentioned.

In the pigment (B) contained in the coloring composition of this invention, not only the said zinc halide phthalocyanine pigment which is a main pigment but another green pigment and yellow pigment can be used together for the purpose of color control and complementary color. As a green pigment which can be used together, it is represented by a color index (C.I.) number, for example, C.I. Pigment Green 7, 10, 36, 37, etc. are mentioned as 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, 36, 36 : 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147 , 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 , 181, 182, 185, 187, 188, 193, 194, 199, and the like.

It is preferable that the particle diameter of the pigment (B) is sufficiently small with respect to the wavelength of visible light from a viewpoint of the absorption coefficient (property of a spectrum) and transparency of visible light. That is, it is preferable that a pigment has an average primary particle diameter of 10 nm or more and 300 nm or less, especially 10 nm or more and 100 nm or less. In addition, a primary particle diameter means the diameter of the pigment particle of the minimum unit, and is measured by an electron microscope. The primary particle size of the pigment can be controlled within an appropriate range by using a known dispersing device, for example, sand mill, kneader, two roll, or the like.

Preferable content of the pigment (B) of a coloring composition is 1-30 weight% with respect to the coloring composition total weight.

[Dispersion balance]

The zinc halide phthalocyanine pigment which is the main pigment of the pigment (B) of the coloring composition of this invention has a high acidity compared with the conventional copper phthalocyanine pigment. Therefore, a basic dispersing agent (C) can be used suitably for microdispersion of a zinc phthalocyanine pigment, and the low viscosity of the coloring composition and the inkjet ink using the same can improve the stability with time.

As a basic dispersing agent (C) used for the coloring composition of this invention, a well-known basic resin type dispersing agent can be used. As a commercial resin type dispersing agent, the following are mentioned specifically ,.

As basic resin type dispersing agent made by BIC Chem Corporation, 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 resin type dispersing agent by the Japan Lubrizol company, Solus faz 9000, 13240, 13650, 13940, 17000, 18000, 20000, 24000SC, 24000GR, 28000, 31845, 32000, 32500, 32600, 33500, 34750, 35100, 35200, 37500, 38500, 44000, 55000, etc. are mentioned.

As a basic resin type dispersing agent made by Ciba Specialty Chemicals, EFKA-4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4403, 4406, 4500, 4510 , 4520, 4530, 4570, 4800, 5044, 5054, 5055, 5063, 5064, 5071, 5207, 5244 and the like.

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

When manufacturing a color filter using the inkjet ink prepared with the coloring composition of this invention, since transparency is required for a color filter, the inkjet ink of this invention is comprised in the all wavelength range of 400-700 nm of visible region. It is preferable that the transmittance | permeability of the disperse resin mentioned to be 80% or more, and it is more preferable that it is 95% or more.

The basic dispersant (C) used in the coloring composition of the present invention is preferably 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. And a basic dispersant (Ca) comprising at least one cationic substructure selected from the group consisting of polyallylamine chains, polyethyleneimine chains, cationic polyurethane chains, and cationic acrylic polymer chains.

An acrylic polymer chain is obtained by superposing | polymerizing one or more types of (meth) acrylic-acid alkylmonomers. Moreover, it is obtained by block or random copolymerization of one or more types of (meth) acrylic-acid alkylmonomer, and another vinylic monomer as needed.

It is also possible to arbitrarily introduce a photopolymerizable group, a thermal reactive group, an anionic group, a cyclic aliphatic group, an aromatic group and the like into the side chain.

Hydroxycarboxylic acid polymer chain | strand is obtained by dehydration reaction or ring-opening reaction using hydroxycarboxylic acid and / or 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 the addition salt from the polyallylamine hydrochloride obtained by radical polymerization of allylamine hydrochloride.

Polyethyleneimine chain is obtained by ring-opening-polymerizing ethyleneimine.

A dialkylamino group containing diol and diisocyanate are obtained by cationic polyurethane chain reaction.

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 for the coloring composition of this invention, More preferably, at least 1 type of substructure chosen from the group which consists of a hydroxycarboxylic acid polymer chain, a polyallylamine chain, a polyethyleneimine chain, and A basic dispersant (Cb) comprising at least one cationic substructure selected from the group consisting of cationic polyurethane chains.

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

In the coloring composition of this invention, the basic dispersing agent (C) which can be used especially suitably is a hydroxycarboxylic acid polymer chain (polyester [c-1]) which has a carboxyl group in one terminal, and a primary or 2 in a main chain. Although comb-type basic dispersing agent (Cc) obtained by condensation reaction of the polyallylamine chain | strand or polyethyleneimine chain (polyamine [c-2]) which has 2 or more of the amino group, the chemical structure and manufacturing method other than that are specifically limited no.

For example, the condensation reaction of polyester [c-1] having a carboxyl group at one end and polyamine [c-2] having two or more primary or secondary amino groups in the main chain thereof may be combined with polyester [c-1]. The polyamine [c-2] is mixed and heated, followed by amidation by dehydration. Number obtained by reaction conditions at that time, that is, the addition ratio of polyester [c-1] and polyamine [c-2], the molecular weight of polyester [c-1] and polyamine [c-2], the reaction rate of amidation reaction, etc. The molecular weight, amine number, and acid value of the topographic dispersant (C) can be adjusted.

As for the number average molecular weight of basic dispersing agent (C), 1,000-100,000 are preferable. If the number average molecular weight of the basic dispersant (C) is less than 1,000, the dispersing effect and the storage stability are lowered. If the number average molecular weight is greater than 100,000, the viscosity of the dispersion is increased and solubility in various organic solvents is lowered, resulting in poor dispersion. As for the amine value of a basic dispersing agent (C), 5-100 and an acid value are 0-50. The amine value and the 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 in these suitable ranges.

Polyester [c-1] which has a carboxyl group in one terminal is obtained by self-condensation of hydroxycarboxylic acid or lactone, or cocondensation of hydroxycarboxylic acid and lactone.

Examples of the hydroxycarboxylic acid include ricinolic acid, ricinoleic acid, a mixture of 9 and 10-hydroxystearic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, lactic acid, and the like. ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, 4-methylcaprolactone, 2-methylcaprolactone, and the like. Most preferred are co-condensates of 12-hydroxystearic acid with ε-caprolactone. Moreover, when condensing these polyesters, you may add carboxylic acids which do not contain a hydroxyl group, for example, capronic acid, lauric acid, stearic acid, methoxy acetic acid, etc. as a polymerization terminator.

The polyamine [b-2] to be used in the present invention is not particularly limited as long as it is a polymer having an amino group. Specific examples thereof include polyethyleneimine, polyethylene polyamine, and polyallylamine. Polyethyleneimine is a polyamine obtained by ring-opening-polymerizing 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. In addition, polyallylamine is a polyamine represented by the following formula (5).

Formula 5:

[N7 in Formula 5 represents an integer of 2 to 1000]

In view of the above, those particularly suitable as the commercially available basic dispersing agent (C) which can be used in the coloring composition of the present invention include Ajispa PB821 manufactured by Ajinomoto Fine Techno Co., Ltd., Japan Lubrizol Company, Solus Paz 32000, and Ciba Specialty Chemicals Company. EFKA-4300, Disperbyk-161 manufactured by BIC Chem Corporation, and Azispa PB821, Soluspaz 32000, manufactured by Lubrizol Japan, are mentioned, but are not limited thereto.

The preferable weight ratio of the pigment (B) and basic dispersing agent (C) contained in the coloring composition which concerns on this invention is 100: 3-100: 150.

[Pigment derivative (D)]

In this invention, a pigment derivative can be used as needed. As a pigment derivative which can be used for this invention, the thing represented by following formula (4) can be used, for example.

Formula 4:

[Formula 4]

(, Of the formula G ⁴ is a q-valent dye circular compound residue, J ⁴ is a basic substituent, acid substituents, a neutral substituent, q is an integer of 1 to 4.)

As a basic substituent, the substituent represented by following formula (6), formula (7), or formula (9) is mentioned, for example.

Formula 6:

In formula (6), X ⁶¹ : —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond is shown.

n6: represents the integer of 1-10. R ^a6 and 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 substituent including one of R ^a6 and R ^b6 and containing additional nitrogen, oxygen, or sulfur atom The hetero ring which may be used is shown. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.)

Formula 7:

(In formula 7,

R ^a7 , 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 , R ^{b7 which} is integrally substituted with an additional nitrogen, oxygen or sulfur atom The hetero ring which may be used is shown. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.)

Formula 8:

(In Formula 8,

X ⁸¹ : —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond.

R ^a8 : an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

R ^b8 , R ^c8 , R ^d8 and R ^e8 : 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. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.)

Formula 9:

(In Formula 9,

X ⁹¹ : —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. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

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. 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 Formula 9a or a substituent represented by the following Formula 9b.

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

Formula 9a:

[Formula 9a]

(In formula 9a,

n9: The integer of 1-10 is represented.

R ^c9 , R ^d9 : 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 substituent including one of R ^c9 and R ^d9 and containing additional nitrogen, oxygen, or sulfur atom The hetero ring which may be used is shown. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.)

Formula 9b:

[Formula 9b]

(In formula 9b,

R ^e9 : an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

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. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.)

As an acidic or neutral substituent, the substituent represented by following formula (10), formula (11), or formula (12) is mentioned, for example.

Formula 10

(In Formula 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 valence of M ^10. )

Formula 11

(In Formula 11,

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

Formula 12

(In formula 12,

A ¹² : represents a hydrogen atom, a halogen atom, -NO _2- , -NH ₂ , or SO ₃ H.

k ₁₂ : represents an integer from 1 to 4.

Pigment circular compound (G ⁴⁾ is, having a dye skeleton generally known compounds, and does not have an almost absorbed in the visible light region, refers to a compound having a similar skeleton to the dye skeleton.

Examples of the dye-type compound residues include diketopyrrolopyrrole pigment residues, azo pigment residues (e.g., azo, disazo, polyazo, etc.), phthalocyanine pigment residues, and anthraquinone pigment residues (e.g. , Diaminodianthraquinone, anthrapyrimidine, flavantron, ananthrone, indanthrone, pyrantrone, bioanthrone, etc.), quinacridone pigment residue, dioxazine pigment residue, perinone pigment residue, perylene pigment Residues, thioindigo pigment residues, isoindolin-based pigment residues, isoindolinone pigment residues, quinophthalone pigment residues, tren pigment residues, metal complex dye residues, anthraquinone residues, or triazine residues; Can be mentioned.

As the anthraquinone derivative, an anthraquinone having the basic, acidic or neutral substituent can be used. Moreover, as a triazine derivative, an alkyl group (for example, methyl group, an ethyl group etc.), an amino group, an alkylamino group (for example, a dimethylamino group, a diethylamino group, a dibutylamino group etc.), a nitro group, a hydroxyl group, alkoxy Groups (eg, methoxy groups, ethoxy groups, butoxy groups, etc.), or halogens (eg, chlorine, etc.); Phenyl group which may be substituted by methyl group, a methoxy group, an amino group, a dimethylamino group, or a hydroxyl group; Or to 1,3,5-triazine which 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, The derivative which introduce | transduced the said basic, acidic, or neutral substituent can be used.

Although the coloring composition of this invention can be made into a low viscosity with high solid content and high pigment concentration, and can be used for gravure ink, offset ink, an inkjet, or automotive paint, etc., the printed matter and coating material of a high coloring power / high transmittance are obtained. Since it loses, it can use suitably especially for a color filter substrate. Although it can use for an inkjet inkjet ink, a photolithography resist ink, or a transfer ink printing ink etc. as a color filter board | substrate, it can utilize suitably for inkjet ink especially taking advantage of the characteristic of a solvent (A).

Zinc halide phthalocyanine used as the main pigment in the coloring composition of the present invention has a high acidity compared to conventional copper phthalocyanine and has a good affinity for the polar solvent used in the process after the color filter production, and thus, solvent resistance and heat resistance are problematic. There are many cases.

Therefore, when preparing inkjet ink with the coloring composition of this invention, it is preferable to mix | blend binder resin (E) and / or a thermally reactive compound (F).

[About binder resin (E)]

It is preferable to mix | blend binder resin (E) with the inkjet ink manufactured with the coloring composition of this invention. It is preferable that binder resin (E) is a thermoplastic resin.

Examples of the thermoplastic resin that can be used for the binder resin (E) include petroleum resin, maleic acid resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, rubber chloride, alkyd resin, acrylic resin, polyester resin, amino Resins, vinyl resins, butyral resins, and the like.

At 100 ° C. or higher, preferably 150 ° C. or higher, a functional group for self-crosslinking, a functional group for reacting with the thermally reactive compound, a functional group for promoting the crosslinking reaction of the thermally reactive compound (F), and a crosslinking reaction with the thermally reactive compound (F) The resin having at least one functional group selected from the functional groups described above can also be used as long as the inkjet ink can be stored without long-term thickening at room temperature and satisfies the conditions for stable discharge at room temperature for a long time.

Examples of the functional group capable of self-crosslinking 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.

As a functional group which promotes the crosslinking reaction of a thermally reactive compound (F), a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned.

As a functional group which reacts and crosslinks with a thermally reactive compound (F), a hydroxyl group, a carboxyl group, an epoxy group, etc. are mentioned.

As resin which has a crosslinkable functional group, the acrylic resin which has a hydroxyl group and a carboxyl group which does not react at all at normal temperature and which resin crosslinks gently by the esterification reaction at high temperature is preferable. The acrylic resin which has a hydroxyl group and a carboxyl group is obtained by copolymerizing the monomer which has a hydroxyl group, the monomer which has a carboxyl group, and the monomer which does not have a hydroxyl group and a carboxyl group, for example. The hydroxyl group and the carboxyl group can be effectively used not only for self-crosslinking but also as a crosslinking group or crosslinking reaction accelerator in the case of using the thermally reactive compound (F).

[About Reactive Compound (F)]

It is preferable to mix | blend a thermally reactive compound (F) with the inkjet ink prepared with the coloring composition of this invention. The thermally reactive compound (F) can be used alone or in combination with the resin binder (E). Although the thermally reactive compound (F) which can be used for the inkjet ink prepared with the coloring composition of the present invention is non-reactive at room temperature, for example, at a temperature of 100 ° C or higher (preferably 150 ° C or higher), a crosslinking reaction, a polymerization reaction, It is a compound which shows polycondensation reaction or polyaddition reaction. In the case where priority is given to the stability at the time of storage and discharging, and that the reactivity at 150 to 250 ° C is selected, the zinc halide phthalocyanine pigment having a high acidity used in the coloring composition of the present invention becomes a reaction accelerator, Higher durability can be obtained.

Although the molecular weight of the said thermally reactive compound which can be used for the ink composition of this invention is not specifically limited, Preferably it is 50-2000, More preferably, it is 100-1000.

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, and acrylate monomers. Or a silane coupling agent can be used. Moreover, it is preferable to contain at least a melamine compound and / or a benzoguanamine compound as said thermally reactive compound. Since the melamine compound or the benzoguanamine compound is very small in discoloration after heat treatment and can impart high resistance with a small amount of addition, it is possible to reduce the amount of the thermally reactive compound added, thereby to increase the pigment concentration of the ink and to improve the stability over time. Leads to.

In addition, the melamine compound and / or the benzoguanamine compound are remarkably influenced by the hardening of the acidity of the pigment, and can provide a hardened product having high resistance by self-condensation even without a binder resin.

As a melamine compound or a benzoguanamine compound, what has an imino group, a methylol group, or an alkoxy methyl group is mentioned, for example. Especially, the melamine compound or the benzoguanamine compound containing an alkoxyalkyl group is especially preferable. When the melamine compound or the benzoguanamine compound containing an alkoxyalkyl group is used, the storage stability of the coating material or ink containing the colored resin composition of this invention improves remarkably.

As a melamine compound or the benzoguanamine compound containing an alkoxyalkyl group, for example, hexamethoxymethylol melamine, hexabutoxymethylol melamine, tetramethoxymethylol benzoguanamine, tetrabutoxymethylol benzoguanamine, etc. Although these are mentioned, It is not necessarily limited to these.

The following are mentioned as a specific example of the commercial item of a melamine compound. However, it is not necessarily limited to these.

Nicarac MW-30M, MW-30, MW-22, MS-21, 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, Cymel 300, 301, 303 made in Japan Scitex Industries, 350, 370, 325, 327, 703, 712, 01, 285, 232, 235, 236, 238, 211, 254, 204, 202, 207, mycoat 506, 508, 212, 715 and the like.

Among them, Nicarac MW-30M, MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX-43 and MX- manufactured by Nippon Carbide Co., Ltd. are melamine compounds containing an alkoxyalkyl group. 302, Cymel 300, 301, 303, 350, 285, 232, 235, 236, 238 and Mycote 506 made by Scitex Industries, Japan.

As a specific example of the commercial item of a benzoguanamine compound, For example, Nicarac BX-4000, SB-401, BX-37, SB-355, SB-303, SB-301, BL-60, SB-255 made by Nippon Carbide SB-203, SB-201, Cymel 1123 by Japan Scitex Industries, Mycote 105, 106, 1128, etc. are mentioned.

Among them, Nicarac BX-4000 manufactured by Nippon Carbide, SB-401 and Cymel 1123 manufactured by Nippon Scitex Industries Co., Ltd., which are alkoxyalkyl group-containing benzoguanamine compounds, are suitable.

In addition, although an effective thermally reactive compound is given to the following, it is not necessarily limited to these.

As an epoxy compound, for example, bisphenol fluorene diglycidyl ether, biscresol fluorene diglycidyl ether, bisphenoxy ethanol 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 Although glycidyl ether of a polyol, polyglycidyl isocyanurate, etc. are mentioned, It is not necessarily limited to these.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [[(3-ethyloxetan-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- (cyclo Hexyloxy) methyloxetane, oxetanylsilsesquioxane, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetan-3-yl) methoxy] benzene, 1, 4-bis [[(3-ethyloxetan-3-yl) methoxy] methyl] biphenyl, 1-ethyl-3-oxetanylmethyl methacrylate, or benzene-1,4-dicarboxylic acid bis Although [1-ethyl (3-oxetanyl) methyl] ester etc. are mentioned, It is not necessarily limited to these.

As the phenol compound, for example, both a novolak phenol compound obtained by reacting phenols and aldehydes under an acidic catalyst and a resol phenol compound reacted under a basic catalyst can be used. Examples of the phenols include orthocresol, paracresol, paraphenylphenol, paranonylphenol, 2,3-xylenol, phenol, metacresol, 3,5-xylenol, resorcinol, catechol, hydroquinone, Although bisphenol A, bisphenol F, bisphenol B, bisphenol E, bisphenol H, bisphenol S, etc. are mentioned, It is not necessarily limited to these. Examples of the aldehydes include formaldehyde or acetaldehyde, but are not necessarily limited to these. Phenols and aldehydes are used individually by 1 type or in mixture of 2 or more types, respectively.

As a specific example of the commercial item of a benzoxazine compound, although the benzoxazine P-d type, the benzoxazine F-a type, etc. made by Shikoku Chemical Co., Ltd. are mentioned, it is not necessarily limited to these, for example.

As a blocking carboxylic acid compound, the combination of the following carboxylic acid compounds and a blocking agent is mentioned.

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, succinic acid, Adipic acid, butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid, C1-CIC acid, CIC acid, C3-CIC acid, or Bis-CIC acid, and the like, but are not necessarily limited thereto.

As a blocking agent, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, etc. are mentioned, for example. However, it is not necessarily limited to this. In addition, 1 type is used individually or in combination of 2 or more types.

As a blocking isocyanate compound, the combination of the following isocyanate compounds and a blocking agent is mentioned.

As a blocked isocyanate compound, it is a diisocyanate compound, for example, hexamethylene diisocyanate, isophorone diisocyanate, toluidine isocyanate, diphenylmethane-4,4'- diisocyanate, diphenylmethane-2,4'- Diisocyanate such as diisocyanate, bis (4-isocyanatecyclohexyl) methane, or tetramethylxylylene diisocyanate, or isocyanurate of these diisocyanates, trimethylolpropane adduct type, biuret type, or isocyanate residue Although prepolymer (low polymer obtained from diisocyanate and a polyol) which has, and uretdione which has an isocyanate residue, etc. are mentioned, It is not necessarily limited to this.

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

As a specific example of the commercial item of a carbodiimide compound, Although carbodilite V-01, V-03, V-05, etc. by Nisshinbo Corporation are mentioned, it is not necessarily limited to these, for example.

As an acrylate monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acryl Rate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, triethylene glycol di (meth) acrylic Rate, tripropylene glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropanedi (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 diglyci Of dil ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine Various acrylic esters or methacrylic acid esters, such as (meth) acrylic acid ester, epoxy (meth) acrylate, or urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, Pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, an acrylonitrile, etc. are mentioned, but it is not necessarily limited to these.

When using an acrylate monomer, a polymerization initiator can be used for the purpose of further improving sclerosis | hardenability. As a polymerization initiator, you may use a thermal polymerization initiator for the purpose of improving sclerosis | hardenability at the time of heating. As a thermal polymerization initiator, an organic peroxide type initiator, an azo type initiator, etc. are mentioned.

Examples of the silane coupling agent include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, or vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Meta) acrylsilanes, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl ) Epoxysilanes, such as ethyl triethoxysilane, (beta)-(3, 4- epoxycyclohexyl) methyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, or (gamma)-glycidoxy propyl triethoxysilane. N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, or N-phenyl-γ- 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.

It is preferable that a melamine compound or a benzoguanamine compound is contained in these thermally reactive compounds in the quantity of 1 weight%-40 weight% in the ink composition of this invention. The epoxy compound, phenol compound, blocked isocyanate compound, acrylate monomers and the like are preferably contained in an amount of 1% by weight to 40% by weight in the ink composition of the present invention. Moreover, it is preferable that a silane coupling agent is contained in the quantity of 0.1 weight%-40 weight% in the ink composition of this invention. When content is insufficient, heat resistance or chemical resistance may be inferior. Moreover, when content exceeds 40%, the increase of a viscosity or the fall of storage stability may arise.

[About physical properties]

In the coloring composition of this invention, solid content is preferably 3 to 60 weight%, more preferably 4 to 40 weight% with respect to the total weight of the composition. When solid content is less than 3 weight%, the density | concentration and tolerance of the ink film prepared with the coloring composition run short, and when it exceeds 60 weight%, the viscosity of a coloring composition may rise and stability with time may fall.

As a viscosity of the coloring composition of this invention, 2 mPa * s or more and 100 mPa * s or less are preferable at 25 degreeC, 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. When the viscosity of a coloring composition is too big | large, the viscosity of the inkjet ink prepared with the coloring composition also becomes large, and when discharging this ink continuously, stable discharge is impossible. Moreover, as a viscosity of the inkjet ink prepared with the coloring composition of this invention, 3 mPa * s or more and 40 mPa * s or less are preferable.

As average dispersion particle diameter of the coloring composition of this invention, 5 nm or more and 200 nm or less are preferable, and 10 nm or more and 100 nm or less are more preferable. When the average dispersion particle size of a coloring composition is too big | large, when discharging the inkjet ink prepared with the coloring composition, a head will be easy to be clogged and stable discharge is impossible. If the average dispersed particle size is too small, reagglomeration tends to occur, resulting in deterioration of stability over time.

As surface tension of the inkjet ink prepared with the coloring composition of this invention, 20 mN / m or more and 40 mN / m or less are preferable, and 24 mN / m or more and 35 mN / m or less are more preferable. If the surface tension is too high, ink cannot be stably discharged from the head. On the contrary, if the surface tension is too low, the ink cannot be formed after discharge from the head.

In 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 thermally reactive compound, the organic solvent, and the binder resin and / or the pigment derivative are optionally used. It can carry out by putting into a dispersing machine and disperse | distributing until a desired average particle diameter and particle size distribution are carried out. The raw materials of a coloring composition and an inkjet ink may be mixed and disperse | distributed collectively, and may be mixed and disperse | distributed separately in consideration of the characteristic and economical efficiency of each raw material. If the viscosity of the inkjet ink is too high and dilution is required, it is also possible to add the dilution liquid medium to the ink stock solution and stir uniformly to prepare the inkjet ink.

As a disperser, a sand mill, a bead mill, an agitator mill, a dyno mill, a coball mill, etc. are suitable. When there is a viscosity range suitable for pigment dispersion in each disperser, the viscosity can be adjusted by changing the ratio of various resin components and pigments. It is preferable to disperse | distribute a coloring composition and inkjet ink with a disperser, and to filter by a filter or a centrifugal method for the purpose of removing a coarse particle and a foreign material.

When manufacturing the coloring composition of this invention, surfactant type dispersing agent, anthraquinone derivative, and / or triazine derivative can be used further. As surfactant type pigment dispersing agent, naphthalene sulfonic-acid formalin condensate salt, aromatic sulfonic-acid formalin condensate, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl phenyl ether, stearylamine acetate, etc. are mentioned, for example.

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

The inkjet ink of the present invention may be added with 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, average particle diameter, or surface tension. .

Since the inkjet ink prepared with the coloring composition of the present invention has high pigment concentration and low viscosity, the inkjet ink is excellent in ejection stability, and the amount of the pigment can be reduced because the pigment content is higher than that of the ordinary inkjet ink, and thus, for color filter substrates, In addition, it is possible to improve the productivity and the quality of printed matter for which high printing concentration is desired. In particular, the ink composition for inkjet recording of the present invention is suitable for the production of color filter substrates requiring high productivity and quality.

In addition, since the pigment is dispersed at a high concentration, the inkjet ink prepared by the coloring composition of the present invention has a high printing concentration even if the ink composition penetrates in the depth direction or plastic, glass, or metal that wets in the horizontal direction. can do. In addition, since the ejection amount can be suppressed, it is also possible to avoid the fact that ink flows out due to exceeding the ink capacity of the receiving layer and is mixed, or the dot shape does not become a circle, which is limited in conventional inkjet printing. It can also be used for other purposes.

[About color filter board]

The green inkjet ink prepared with the coloring composition of this invention can be used with a red inkjet ink and a blue inkjet ink, and a color filter substrate can be manufactured by the inkjet method. The color filter substrate can be used for, for example, a liquid crystal display panel used for a thin television.

The color filter substrate is provided with a filter segment of a desired color, and the filter segment is formed by discharging each color of the ink jet ink for color filters by the inkjet method in an area divided by the black matrix of the substrate on which the black matrix is formed.

Red inkjet ink and blue inkjet ink other than the green inkjet ink using the coloring composition of this invention are prepared with the 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: 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.

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, 36, 36 : 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147 , 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 Yellow pigments such as 181, 182, 185, 187, 188, 193, 194, 199, and / or CI, for example Pigment orange 36, 43, 51, 55, 59, 61 etc. Orange pigments can be used together.

In blue inkjet inks, for example, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like can be used. Blue inkjet inks contain C.I. Purple pigments, such as pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, can be used together.

As a board | substrate, resin plates, such as a glass plate, a polycarbonate, polymethyl methacrylate, and a polyethylene terephthalate, can be used. The black matrix is formed on the substrate by, for example, a photolithography method of coating, exposing, developing and patterning a radically polymerized black resist, a printing method of printing black ink, or a deposition method of depositing and etching metals. can do.

EXAMPLE

Hereinafter, although an Example demonstrates this invention concretely, these do not limit the scope of the present invention. In the following Examples and Comparative Examples, parts and percentages indicate parts by weight and weight percent. The pigment, pigment derivative, solvent, and resin solution used in the Example and the comparative example are shown below. In addition, the dispersion prescription and final ink composition in an Example and a comparative example are shown to Tables 1-7.

[A] solvent

Solvent (A-1) whose boiling point in 760 mmHg is 170 degreeC or more

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) 15 PtGDA: 1,5-pentanediol diacetate

Solvent (A-2) having a boiling point of less than 170 ° C. at 760 mmHg

9) PGMAc: Propylene Glycol Monomethyl Ether Acetate

Solvent (A-2) whose boiling point in 760 mmHg is 170 degreeC or more

10) DPMA: Dipropylene Glycol Methyl Ether Acetate

Solvent whose boiling point in 760 mmHg other than solvent (A-1) and solvent (A-2) is 170 degreeC or more

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 whose boiling point in 760 mmHg other than a solvent (A-1) and a solvent (A-2) is less than 170 degreeC

16) Anon: Cyclohexanone

17) butyl acetate

[B] Pigment

Pigment (B)

1) PG58: C.I. Pigment other than Pigment Green 58 (galvanized zinc phthalocyanine pigment), halogenated zinc phthalocyanine

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

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

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

[C] dispersants

Basic Dispersant (C)

(C-1) Comb basic obtained by condensation reaction of the hydroxycarboxylic acid polymer chain which has a carboxyl group in one terminal, and the polyallylamine chain or polyethyleneimine chain which has two or more primary or secondary amino groups in a principal chain. Dispersant (Cc)

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

2) SP32000: Solsperse-32000 (solid content 100%) made by Abicia

Basic dispersant except (C-2) (Cc)

3) EFKA4300: EFKA-4300 (solid content 81% PGMAc) made by Ciba Specialty Chemicals Co., Ltd.

4) BYK161: Disperbyk-161 (solid content 30% PGMAc / butyl acetate) made by BIC Chem Corporation

Acid Dispersant

5) PA111: Aji Spa PA-111 (100% of solids) made by Ajinomoto Fine Techno Co., Ltd.

6) BYK111: Big Chemical Company Disperbyk-111 (solid content> 90%)

7) SP24000: Solsperse-24000 (solid content 100%) made by Abisia

8) J678: John Krill-678 (100% of solids) made in BASF Japan

When using Azispa PB-821, EFKA-4300, Solsperse-32000, Azispa PA-111, Disperbyk-111, Solsperse-24000, and John Krill-678, it is dissolved in the main solvent of the coloring composition and dissolved in a solution having a solid content of 30%. Was used.

[D] pigment derivative

Pigment derivative (D)

Pigment Derivative [BD-1]

Formula 13:

Compound represented by.

[E] binder resin

Binder Resin (E)

1) J804: Acrylic resin Joncryl-804 made from BASF Japan (acid value 15, OH group 45, weight average molecular weight 12,500, solid content 100%)

It melt | dissolved in the main solvent of a coloring composition, and used as a solution of 30% of solid content.

[F] Thermally Reactive Compounds

Thermally Reactive Compound (F)

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

2) MX-417: Melamine compound-containing nickelamine MX-417 made by Nippon Carbide Co., Ltd.

3) SB-401: Alkoxyalkyl group-containing benzoguanamine compound made by Nippon Carbide Co., Ltd.

Nikalak SB-401

4) BL-60: Imino group and methylol group containing benzoguanamine compound made by Nippon Carbide Co., Ltd.

Nikalak BL-60

5) M-400: Acrylic Monomer Alonex M-400 manufactured by Toagosei Co., Ltd.

6) BL-4265: isocyanate compound death module BL-4265 made by Sumika Bayer Urethane Co., Ltd.

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

<< Example 1 >>

100 parts of PG85 as a pigment (B), 133 parts of PB-821 (30% solids solution) as a basic dispersant (C), and 307 parts of EGDA as a solvent (A-1) were mixed in a mixer and further dispersed in a sand mill. Was performed, and the coloring composition was obtained. Further, 20 parts of melamine compound (MX-43) as the thermally reactive compound (F) and 250 parts of 15 PtGDA as the solvent (A-1) were added and mixed with homodisper. Dust and coarse matter were filtered out and inkjet ink having a pigment concentration of 20% was obtained.

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

It carried out similarly to Example 1, disperse | distributed and the crude liquid so that it might become a composition of Examples 2-34 and Comparative Examples 1-26 in the composition table of Tables 1-9, and obtained the coloring composition and inkjet ink.

Moreover, it carried out similarly to Example 1, disperse | distributed and the crude liquid so that it might become a composition of Examples 35-42 in the composition table of Table 19, and obtained the coloring composition and the inkjet ink.

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

That is, in Example 1, in Example 1, the pigment (B) PG85 is 100 (part by weight), the basic dispersant (C) PB-821 is 40 (part by weight), and the solvent (A-1) EGDA is 400 (weight). (Part) and the thermally reactive compound (F) MX-43 are represented by 20 (part by weight) and solvent (A-1) 15 PtGDA by 250 (part by weight).

The viscosity and fluidity, stability with time, average particle diameter, and haze of the coloring composition obtained in Examples 1-42 and Comparative Examples 1-26 were evaluated by the following method. The results are shown in Tables 10-18 and 20. Moreover, the ink obtained in Examples 1-42 and Comparative Examples 1-26 was discharged with the inkjet printer which has the piezo head which can change the frequency of 4-10 Hz, and discharge stability was evaluated by the following method. The results are shown in Tables 21 to 30.

[Viscosity]

By the dynamic viscoelasticity measuring device, the viscosity ((eta: mPa * s)) of the shear rate 100 (1 / s) was measured, and the following references | standards evaluated.

○: η <40

△: 40≤η <50

×: 50≤η

[liquidity]

A dynamic viscoelasticity measuring device measures the viscosity (ηa: mPa · s) at a shear rate of 10 (1 / s) and measures the ratio ηa to the viscosity (η: mPa · s) at a shear rate of 100 (1 / s) previously measured. / η was calculated | required, the fluidity | liquidity was evaluated by the following reference | standard, and the following reference | standard evaluated.

○: 0.9≤ηa / η <1.5

×: 1.5≤ηa / η

[Storage Stability]

After heating for 7 days in 45 degreeC oven, the viscosity was measured and the following references | standards evaluated.

○: thickening ratio ≤ 10% compared to the viscosity before heating

X: Thickening rate> 10% compared with the viscosity before heating

[Average particle diameter]

The average particle diameter [D] dilutes 0.001 g of the coloring composition with 30 g of the main solvent of this coloring composition to prepare a measurement sample, using a laser Doppler method particle size distribution measuring apparatus (manufactured by Nikkiso Corporation, UPA-EX150). It measured and evaluated on the following references | standards.

○: 10 nm ≤ [D] <100 nm

△: 100 nm ≤ [D] <200 nm

×: [D] ≥200 nm

[Haze]

Using a spin coater, the substrate coated on the glass at 1500 rpm was dried at 100 ° C. for 3 minutes with a hot plate, and the haze of the coated surface was measured by a haze meter (manufactured by Nippon Denshoku Industrial Co., Ltd.) and evaluated according to the following criteria. It was.

○: [haze] <3

△: 3≤ [haze] <4.5

×: [haze] ≥4.5

[Discharge Stability A]

The ink obtained in Examples 1-22, 25-42, and Comparative Examples 1-26 was discharged and dried by using the said inkjet printer at the predetermined position of a glass substrate, and it thermosetted for 20 minutes at 230 degreeC, A coating film was formed and the coating film reliability was evaluated by the following method.

The printing state was visually observed and the discharge stability was evaluated based on the following criteria.

(Circle): After discharge | separation for 15 minutes of continuous nozzle ejection is 5% or less.

(Triangle | delta): After discharge | release for 15 minutes of continuous nozzle ejection is 10% or less.

X: After discharge | separation for 15 minutes continuously, nozzle pull out is 50% or more.

[Discharge Stability B]

In addition, the inkjet printer was used to discharge the ink obtained in Examples 1 to 22, Examples 25 to 42 and Comparative Examples 1 to 26 using a corrugated cardboard, followed by drying at room temperature to form a coating film. It evaluated by the method.

The printing state was visually observed and the discharge stability was evaluated based on the following criteria.

(Double-circle): When ejecting after the intermittent time (15 minutes) which interrupts dispensing, the nozzle pull-out is 5% or less.

(Circle): When discharge | emission is made after the intermittent time (15 minutes) which interrupts dispensing, nozzle ejection is 10% or less.

(Triangle | delta): When discharge | emission is made after the intermittent time (15 minutes) which interrupts discharge | emission, nozzle ejection is 20% or less.

X: When ejecting after the intermittent time (15 minutes) which interrupts ejection passes, nozzle ejection is 50% or more.

[Chemical Resistance]

The glass substrate in which the coating film was formed was immersed in N-methylpyrrolidone, the color change (DELTA) E of the coating film before and behind immersion was measured, and the following references | standards evaluated.

○: ΔE≤2.5

Δ: 2.5 <ΔE≤5

×: ΔE> 5

When used as a paint or ink, the coloring composition of the present invention can be made into a low viscosity despite high pigment concentration, and thus produces a package, outdoor signage, automobile paint, color filter, etc. more efficiently than the conventional one. It becomes possible. In addition, when the coloring composition of the present invention is used as an inkjet ink, in spite of good chemical resistance and high pigment concentration, it is possible to obtain an ink having low viscosity, excellent stability over time, and excellent ejection stability. Compared to the method, it is possible to produce a high performance color filter much more efficiently.

As mentioned above, although this invention was demonstrated according to 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 (19)

As a coloring composition containing a solvent (A), a pigment (B), and a basic dispersing agent (C), The solvent (A) is represented by the formula 1: [Formula 1]

[Wherein C _n H _2n is a straight or branched alkylene chain, 1 ≦ m ≦ 3, and 2 ≦ _n ≦ 5). Solvent represented by (A-1), and Formula 2: [Formula 2]

[Wherein R is an alkyl group having 1 to 8 carbon atoms, C ₃ H ₆ is a straight or branched propylene chain and 1 ≦ p ≦ 3.] One or more types of solvents selected from the group consisting of a solvent (A-2) represented by the above, and the pigment (B) containing a phthalocyanine pigment represented by the following formula (3) The coloring composition, characterized in that. Formula 3: [Formula 3]

[In the formula, the central metal element M is Zn, and X ₁ to X ₁₆ are each independently an element selected from the group consisting of H, Cl, and Br.] The method of claim 1, The coloring composition in which one or more types of solvents chosen from the group which consists of a solvent (A-1) and a solvent (A-2) occupy 60 weight% or more in the whole solvent. The method of claim 1, The coloring composition in which the 1 or more types of solvent chosen from the group which consists of a solvent (A-1) and a solvent (A-2) contains the solvent whose boiling point in 760 mmHg is 170 degreeC or more. The method of claim 1, A mixture of one or more solvents selected from the group consisting of a solvent (A-1) and a solvent (A-2) having a boiling point of less than 170 ° C at 760 mmHg and a solvent having a boiling point of at least 170 ° C at 760 mmHg. As a coloring composition, the weight mix ratio of the solvent whose boiling point in 760 mmHg is less than 170 degreeC, and the solvent whose boiling point in 760 mmHg is 170 degreeC or more is 0: 100-70: 30. The method of claim 1, The solvent (A-1) is 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. The coloring composition which is one or more types of solvents chosen. The method of claim 1, The coloring composition whose solvent (A-1) is 1 or more types of solvents chosen from the group which consists of diethylene glycol diacetate, a propylene glycol diacetate, and butylene glycol diacetate. The method of claim 1, The coloring composition whose solvent (A-2) is propylene glycol monomethyl ether acetate and / or dipropylene glycol monomethyl ether acetate. The method of claim 1, The coloring composition whose solvent (A-2) is dipropylene glycol monomethyl ether acetate. The method of claim 1, The basic dispersant (C) is 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 substructure selected from the group consisting of polyallylamine chains, polyethyleneimine chains, cationic polyurethane chains, and cationic acrylic polymer chains A coloring composition which is a basic dispersing agent (Ca) containing. The method of claim 1, Further comprising a pigment derivative (D) represented by the following formula (4). Formula 4: [Formula 4]

(In the formula 4, G ⁴ is a q-valent dye circular compound residue, J ⁴ is a basic substituent, acid value group, or a neutral substituent, q is an integer of 1 to 4.) The method of claim 1, The coloring composition whose solid content is 3-60 weight% with respect to the coloring composition total weight. The method of claim 1, The coloring composition whose content of pigment (B) is 1-30 weight% with respect to the coloring composition total weight. The method of claim 1, The coloring composition whose weight ratio of a pigment (B) and a basic dispersing agent (C) is 100: 3-100: 150. An inkjet ink comprising the coloring composition of any one of claims 1 to 13. The inkjet ink containing the coloring composition of any one of Claims 1-13, binder resin (E), and / or a thermally reactive compound (F). The method of claim 15, 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, a blocked isocyanate compound, an acrylate monomer, And a silane coupling agent and at least one compound selected from the group consisting of inkjet inks. The method of claim 15, An inkjet ink wherein the thermally reactive compound (F) comprises at least a melamine compound and / or a benzoguanamine compound. The inkjet ink according to claim 14, which is for a color filter substrate. A color filter substrate supporting a printed layer formed by at least the inkjet ink of claim 14 on a substrate.