JP2016147982A - Method for producing color chip - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color chip having excellent temporal stability and a method for producing the same; and to provide a dispersion paste which shows a suitable viscosity range and exhibits excellent glossiness and color development (color tone, jet-blackness and the like), when the dispersion paste is produced by mixing a color chip and an organic solvent.SOLUTION: In a method for producing a color chip which includes kneading a mixture containing amine that may have a pigment and a hydroxyl group and has an aliphatic hydrocarbon group, and a resin by a roll, a carbon number of the aliphatic hydrocarbon group is 2 to 8.SELECTED DRAWING: None

Description

  The present invention relates to a color chip, a manufacturing method thereof, and a dispersion paste using the same. More specifically, the present invention relates to a low-viscosity paint having excellent glossiness and color development, a color chip that gives printing ink, a method for producing the same, and a dispersion paste using the same.

  In the fields of paints, printing inks, and the like, pigment dispersions in which pigments are dispersed together with resins, solvents and the like by a dispersing machine such as a bead mill have been used. However, if the pigment dispersion obtained by dispersion with a bead mill is not dispersed for a long time, the paint and printing ink cannot be said to have sufficient glossiness, color development and the like. In order to improve glossiness, color development, etc., it is necessary to disperse for a long time with a bead mill, which is very uneconomical. However, in the dispersion by the bead mill, the pigment cannot be sufficiently dispersed unless a low-viscosity pigment dispersion with a low pigment concentration is used because of the dispersion mechanism. Therefore, the pigment dispersion with a high pigment concentration (high pigment content) is not possible. There are problems in industrial use, such as being unable to obtain a body and possibly increasing the transportation cost. Also, generally, it takes a long time to disperse, and without using a pigment dispersion that has been dispersed for a long time, the coating film of the paint or printing ink obtained by using it has sufficient glossiness, color development, etc. There is a problem that it cannot be obtained (for example, Patent Document 1).

  By the way, a color chip is known as a pigment dispersion having a high pigment concentration. The color chip is manufactured by kneading a mixture having a high pigment concentration composed of a pigment and a resin with a disperser such as a roll. In the case of pigment dispersion by rolls, a very large shearing force is applied to the mixture of pigment, resin, etc., so that it is easy to disperse pigment sufficiently in a short time, and paints and printing inks obtained using color chips Such a coating film has an advantage that excellent glossiness, color development, and the like are easily obtained. For example, Patent Document 2 discloses a method for producing a color chip in which a thermoplastic resin, a pigment, and a plasticizer are kneaded by a roll mill together with an amine cationic activator and a pigment derivative.

  However, it is empirically known that a dispersion paste obtained using a color chip generally tends to have a very high viscosity. In the field of paints and printing inks, it is necessary to achieve both a suitable pigment concentration and a viscosity range, but if it is intended to fall within the suitable viscosity range, it is necessary to dilute with a large amount of solvent, etc. There was a problem that the pigment concentration was lowered.

  In addition, when a color chip is mixed with a solvent immediately after production to produce a dispersion paste, a dispersion paste within a suitable viscosity range is obtained, and coating films such as paints and printing inks obtained using the paste are also glossy. The degree and color development are often good. However, when a dispersion paste is produced using a color chip that has passed for a long time after the production of the color chip, a dispersion paste within a suitable viscosity range cannot be obtained (generally a high viscosity). There was a problem that the glossiness and color development (hue, jetness, etc.) of the coating film obtained in this way were significantly lowered.

JP 2006-225465 A Japanese Patent Publication No. 8-19367

  The problem to be solved by the present invention is to provide a color chip with good temporal stability and a method for producing the same. Another object of the present invention is to provide a dispersion paste that exhibits a suitable viscosity range and exhibits excellent gloss and color (hue, jetness, etc.) when a dispersion paste is produced by mixing a color chip and an organic solvent.

  As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by kneading a mixture containing a pigment, an amine having a specific structure, and a resin with a roll.

  That is, an embodiment of the present invention is a method for producing a color chip in which a mixture containing a pigment, an amine having an aliphatic hydrocarbon group which may have a hydroxyl group, and a resin is kneaded by a roll, The present invention relates to a method for producing a color chip, wherein the hydrocarbon group has 2 to 8 carbon atoms.

  In addition, an embodiment of the present invention relates to the method for producing a color chip, wherein the mixture further contains a dispersant.

  In addition, an embodiment of the present invention relates to the method for producing a color chip, wherein the mixture further contains a plasticizer.

  An embodiment of the present invention also relates to a color chip manufactured by the above manufacturing method.

  An embodiment of the present invention also relates to a dispersion paste obtained by mixing the color chip with an organic solvent.

  According to the present invention, it is possible to provide a color chip having good temporal stability and a method for manufacturing the color chip. In addition, when a dispersion paste is produced by mixing a color chip and an organic solvent, a dispersion paste that exhibits a suitable viscosity range and exhibits excellent gloss and color (hue, jetness, etc.) can be provided. became. Accordingly, it is possible to provide a color chip excellent in long-term storage stability and a coating film that gives a high gloss and color development with a low viscosity when it is used as a dispersion paste. As a result, it can be suitably used in industrial fields such as building materials and interior / exterior of automobiles.

Hereinafter, the present invention will be specifically described based on embodiments. Unless otherwise specified, “CI” in this specification means a color index (CI).
<Pigment>
The pigments used in the present invention are roughly classified into organic pigments and inorganic pigments. Organic pigments include azo lake, hansa, benzimidazolone, diarylide, pyrazolone, benzidine yellow, and disazo azo pigments; phthalocyanine, quinacridone, perylene, perinone, dioxazine, anthraquinone And condensed polycyclic pigments such as isoindolinone and aniline black.

  Examples of inorganic pigments include titanium oxide, zinc oxide, titanium yellow, iron oxide, yellow iron oxide, ultramarine, bitumen, cobalt blue, chromium oxide green, yellow lead, cadmium yellow, cadmium red, iron black, and carbon black. it can. As carbon black, BLACK PEARLS-2000, 1400, 1300, 1100, 1000, 900, 800, 700, MONARCH1400, 1300, 1100, 1000, 900, 800, EMPEROR-2000, 1800, 1600, 1200, manufactured by Cabot, RAVEN-7000 manufactured by ADITYA BIRLA, 5000 Ultra II, 5000 Ultra III, 3500, 2500, 2300, 2000, 1255, 1250, 1200, 1180, 1170, 1000, 900, 880, COLOUR BLACK FW manufactured by Orion Engineered Carbons -285, 255, 200, 182, S170, 2, 1, # 2650, # 2600, # 2350, manufactured by Mitsubishi Chemical Corporation # 2300, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MA100, MA7, and the like.

<Aliphatic amine optionally having a hydroxyl group>
The amine having an aliphatic hydrocarbon group which may have a hydroxyl group used in the present invention is an amine having 2 to 8 carbon atoms of the aliphatic hydrocarbon group (hereinafter referred to as “having a hydroxyl group”). Also, “amine having good aliphatic hydrocarbon group” may be abbreviated as “aliphatic amine”). Here, the aliphatic hydrocarbon group means a monovalent, divalent or trivalent residue of a saturated or unsaturated aliphatic hydrocarbon.

  Examples of the monovalent residue of the saturated aliphatic hydrocarbon include an alkyl group and a cycloalkyl group. Examples of the alkyl group include ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group and the like. can give. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a norbornyl group.

  Examples of the monovalent residue of the unsaturated aliphatic hydrocarbon include an alkenyl group, an alkadienyl group, an alkynyl group, and a cycloalkenyl group. Examples of the alkenyl group include allyl group and 2-butenyl group. Examples of the alkadienyl group include 2,4-pentadien-1-yl group and 2,4-hexadien-1-yl group. Examples of the alkynyl group include 2-propynyl group and 2-butynyl group. Examples of the cycloalkenyl group include a 2-cyclopentenyl group and a 2-cyclohexenyl group.

  Examples of the divalent residue of the saturated aliphatic hydrocarbon include an alkylene group and an alkylidene group. Examples of the alkylene group include ethylene group, 1,2-propylene group, 1,3-propylene group (trimethylene group), 1,4-butylene group (tetramethylene group) and the like. Examples of the alkylidene group include an ethylidene group and a propylidene group.

  Examples of the divalent residue of the unsaturated aliphatic hydrocarbon include an alkenylene group, an alkadienylene group, an alkynylene group, and a cycloalkenylene group. Examples of the alkenylene group include 2-butene-1,4-nylene group.

  Examples of the trivalent residue of the saturated aliphatic hydrocarbon include an alkanetriyl group and an alkylidyne group. Examples of the alkanetriyl group include 1,2,3-propanetriyl group and 1,3,5-pentanetriyl group. Examples of the alkylidine group include an ethylidyne group and a propyridine group.

  Examples of the trivalent residue of the unsaturated aliphatic hydrocarbon include an alkene triyl group. Examples of the alkenetriyl group include 2-pentane-1,3,5-pentanetriyl group.

  In the above aliphatic hydrocarbon group, a part of hydrogen atoms in the aliphatic hydrocarbon group may be substituted with a hydroxyl group. The number of hydroxyl group substitutions may be one or two or more. For example, the monovalent residue of a saturated aliphatic hydrocarbon substituted with a hydroxyl group includes a hydroxyalkyl group, and examples thereof include a 2-hydroxyethyl group and a 4-hydroxybutyl group.

  Carbon number of the said aliphatic hydrocarbon group is 2-8, Preferably it is 2-7, More preferably, it is 2-6.

  The aliphatic amine used in the present invention is not limited in the amine series, and may be any of primary amine, secondary amine, and tertiary amine. Further, it may be a monoamine or a polyvalent amine such as diamine, triamine, or tetramine. Furthermore, you may use individually or in combination of 2 or more types.

  Carbon number of the said aliphatic hydrocarbon group is 2-8, Preferably it is 2-7, More preferably, it is 2-6. Therefore, the aliphatic amine which may have a hydroxyl group used in the present invention has 2 to 8 carbon atoms in the case of a primary monoamine and 4 to 16 in the case of a secondary monoamine. In the case of a tertiary monoamine, it is 6 to 24. In the case of a polyvalent amine, the carbon number of the amine varies greatly depending on the series of the amino group and the structure of the amine. For example, in the case of a diamine, if the two amino groups are both primary, 2 It can be in the range of 10 to 40 if both amino groups are tertiary. In order to solve the problem to be solved by the present invention, the aliphatic amine has preferably 2 to 21 carbon atoms, more preferably 2 to 18 carbon atoms.

  The aliphatic amine used in the present invention preferably has a molecular weight of 45 to 320, more preferably 45 to 270.

Specific examples of the aliphatic amine that can be used in the present invention are listed below.
Examples of monoamines: hexylamine, octylamine, cyclohexylamine, dibutylamine, 1-butylhexylamine, triethylamine, 2-aminoethanol (2-hydroxyethylamine), N-ethylethanolamine, diethanolamine, 2- (diethylamino) ethanol, Triethanolamine etc.
Examples of diamines: ethylenediamine, 1,3-diaminopropane (1,3-propanediamine), 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 , 8-diaminooctane, N, N′-diethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine and the like.
Examples of triamine: diethylenetriamine, 1,5-bis (N-ethylamino) -3-azapentane, 1,5-bis (N, N-diethylamino) -3-azapentane, 1,2,5-pentanetriamine and the like.

<Resin>
The resins that can be used in the present invention are roughly classified into natural polymer resins and synthetic polymer resins, and are not particularly limited. Specifically, natural polymer resins include proteins such as glue, gelatin, casein, and albumin, natural rubbers such as gum arabic, tragacanth and xanthan gum, glucosides such as saponin, alginic acid and propylene glycol alginate, Examples include alginic acid derivatives such as triethanolamine alginate and ammonium alginate, cellulose derivatives such as methylcellulose, nitrocellulose, carboxymethylcellulose, hydroxymethylcellulose, and ethylhydroxycellulose, and shellac resin.

  Examples of synthetic polymer resins include acrylic copolymers, styrene / acrylic acid copolymers, alkyd resins, epoxy resins, polyester resins, urethane resins, cellulose resins, polyvinylpyrrolidone resins, acrylic acid-acrylonitrile copolymers. , Acrylic potassium-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene acrylic acid copolymer Styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer Polymer, vinyl acetate-fatty acid vinyl Examples thereof include a ruethylene copolymer, a vinyl acetate-maleic acid ester copolymer, a vinyl acetate-crotonic acid copolymer, a vinyl acetate-acrylic acid copolymer, and salts thereof.

  The resin is preferably an acrylic resin, a urethane resin, an epoxy resin, a fiber reinforced resin, a fluororesin, a cellulose resin, an acrylic emulsion, or the like. Among these, a cellulose resin is more preferable. Examples of the cellulose resin include Eastman's CAB-551-0.2, CAB-381-0.5, and the like.

  The amount of resin used is determined by the pigment type and particle size, the desired paint and printing ink design. In general, if the proportion of the resin in the color chip is too large, the degree of freedom in designing the paint is reduced and the coloring power is low. On the other hand, if the proportion of the resin is too small, the stability of the color chip is impaired, resulting in deterioration of quality and pigments. This causes problems such as aggregation. 5-90 mass% is preferable and, as for the ratio of resin in a color chip, 10-70 mass% is more preferable.

<Dispersant>
The color chip of the present invention may further contain a dispersant. Dispersants are roughly classified into surfactants, resin-type dispersants, and pigment derivatives, and are not particularly limited. Surfactants are mainly classified into anionic, cationic and nonionic, and suitable types and blending amounts can be appropriately selected and used according to required properties.

  The anionic surfactant is not particularly limited, and specifically, fatty acid salt, polysulfonate, polycarboxylate, alkyl sulfate ester salt, alkylaryl sulfonate, alkylnaphthalene sulfonate, dialkyl Sulfonates, dialkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl aryl ether sulfates, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl phosphate sulfonates, glycerol Late fatty acid esters, polyoxyethylene glycerol fatty acid esters and the like, specifically, sodium dodecylbenzenesulfonate, sodium laurate sulfate, sodium polyoxyethylene lauryl ether sulfate, Polyoxyethylene nonylphenyl ether sulfate, sodium salt of β- naphthalenesulfonic acid formalin condensate and the like.

  Examples of cationic surfactants include alkylamine salts and quaternary ammonium salts. Specifically, stearylamine acetate, trimethyl cocoammonium chloride, trimethyl tallow ammonium chloride, dimethyldioleyl ammonium chloride, methyl oleyl diethanol chloride, tetra Examples include methylammonium chloride, laurylpyridinium chloride, laurylpyridinium bromide, laurylpyridinium disulfate, cetylpyridinium bromide, 4-alkylmercaptopyridine, poly (vinylpyridine) -dodecylbromide, dodecylbenzyltriethylammonium chloride.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyethylene phenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, alkylallyl ethers, and the like. Examples include ethylene lauryl ether, sorbitan fatty acid ester, polyoxyethylene octyl phenyl ether, and the like.

  The selection of the surfactant is not limited to one type, and two or more surfactants such as an anionic surfactant and a nonionic surfactant, and a cationic surfactant and a nonionic surfactant are used. It can also be used in combination. In this case, the blending amount is preferably set to the blending amount described above for each activator component. Preferably, an anionic surfactant and a nonionic surfactant are used in combination. The anionic surfactant is preferably a polycarboxylate and the nonionic surfactant is preferably polyoxyethylene phenyl ether.

  The resin-type dispersant has an affinity part that has the property of adsorbing to the pigment and a compatible part with the dispersion medium, and functions to adsorb to the pigment and stabilize dispersion in the dispersion medium. is there. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Among the above-mentioned dispersants, a resin-type dispersant having a basic functional group is preferable because the dispersion composition has a low viscosity and exhibits a high spectral transmittance with a small addition amount. The resin-type dispersant is preferably used in an amount of about 3 to 200% by weight, more preferably about 5 to 100% by weight, from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

As the pigment derivative, a pigment derivative represented by the following general formula (1) can be used.
General formula (1)
G ^1- (E) _q
(In the formula, G ¹ is a chromogenic compound residue, E is a basic substituent, an acidic substituent, or a neutral substituent, and q is an integer of 1 to 4.)

  As a preferable aspect of the basic substituent in E, the substituent shown by following General formula (2), General formula (3), General formula (4), or General formula (5) can be mentioned.

General formula (2)

(X ¹ represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond. P represents an integer of 1 to 10. R ¹ and R ² each represent Independently, it represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group, R ¹ and R ² may combine with each other to form a ring. The alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.)

General formula (3)

(R ³ and R ⁴ each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. R ³ and R ⁴ are bonded to each other. (The number of carbon atoms of the alkyl group and alkenyl group is preferably 1 to 10.)

General formula (4)

(X ² represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond. R ⁵ represents an optionally substituted alkyl group or optionally substituted. Represents an alkenyl group or an optionally substituted phenyl group, wherein the alkyl group and the alkenyl group preferably have 1 to 10 carbon atoms, R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom, Represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group, and the adjacent groups of R ^{5 to} R ⁹ may be bonded to each other to form a ring; The alkyl group and alkenyl group preferably have 1 to 5 carbon atoms.)

General formula (5)

(X ³ represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond. Y represents —NR ³⁰ —Z—NR ³¹ — or a direct bond. R ³⁰ and R ³¹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group, the number of carbon atoms of the alkyl group and the alkenyl group. Is preferably 1 to 5. Z represents an optionally substituted alkylene group, an optionally substituted alkenylene group or an optionally substituted phenylene group, wherein the alkylene group and the alkenylene group have 1 to 1 carbon atoms. P is preferably a substituent represented by formula (6) or a substituent represented by formula (7), Q is a hydroxyl group, an alkoxyl group, a substituent represented by formula (6) or General formula (It represents the substituent represented by (7).)

General formula (6)

(R represents an integer of 1 to ^10. R ¹⁰ and R ¹¹ each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. The alkyl group and the alkenyl group preferably have 1 to 10 carbon atoms.)

General formula (7):

(R ¹⁶ represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. The alkyl group and the alkenyl group preferably have 1 to 10 carbon atoms. ^13, R ^14, R ¹⁵ and R ¹⁶ are each independently, .R ¹² represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl or optionally substituted phenyl group The groups adjacent to R ¹⁶ may be bonded to each other to form a ring. The alkyl group and the alkenyl group preferably have 1 to 5 carbon atoms.)

As a preferable aspect of the acidic substituent or neutral substituent in E, the substituent shown by General formula (8), General formula (9), and General formula (10) can be mentioned.
General formula (8)
-SO ₃ M / l
(M represents a hydrogen atom, an alkali metal atom, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom. L represents the valence of M.)

General formula (9)

(R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, except when all are hydrogen atoms.)

General formula (10)

(A ¹ represents a hydrogen atom, a halogen atom, —NO ₂ , —NH ₂ or SO ₃ H. k represents an integer of 1 to 4.)

Examples of the chromophoric compound residue of G ¹ include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinones, anthrapyrimidines, flavantrons, anthanthrones, and indans. Anthraquinone dyes such as Throne, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, Alternatively, various dye residues of metal complex dyes, and further anthraquinone residues or triazine residues can be exemplified.

  As an anthraquinone residue, the anthraquinone residue which has the said basic substituent, an acidic substituent, or a neutral substituent is mentioned. Examples of the triazine residue include an alkyl group such as a methyl group or an ethyl group, an alkylamino group such as an amino group, a dimethylamino group, a diethylamino group, or a dibutylamino group, a nitro group, a hydroxyl group, a methoxy group, or an ethoxy group. Group, an alkoxy group such as a butoxy group, or a halogen such as chlorine or a methyl group, a methoxy group, an amino group, a dimethylamino group, a phenyl group optionally substituted with a hydroxyl group, or the like, or a methyl group, an ethyl group, a methoxy group, Residue of 1,3,5-triazine which may have a substituent such as phenylamino group which may be substituted with ethoxy group, amino group, dimethylamino group, diethylamino group, nitro group or hydroxyl group Further, triazine residues into which the basic substituent, acidic substituent or neutral substituent is introduced are listed. It is.

  Among these, a pigment derivative containing a triazine residue or an anthraquinone residue is more preferable. A pigment derivative having a triazine residue or an anthraquinone residue exhibits a higher adsorptivity to the pigment, provides a high dispersibility, and at the same time, causes a curing reaction of the thermoreactive compound more effectively and has a high resistance. Further improvement can be expected.

<Plasticizer>
The color chip of the present invention may further contain a plasticizer. Examples of the plasticizer include phthalic acid esters, phosphoric acid esters, acyclic (aliphatic) dicarboxylic acid esters, and fatty acid esters.

  Examples of the phthalic acid ester include dioctyl phthalate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, and diphenyl phthalate.

  Examples of the phosphate ester include tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, diphenyl-2-ethylhexyl phosphate, tri (2-ethylhexyl) phosphate, and tris (butoxyethyl) phosphate.

  Acyclic (aliphatic) dicarboxylic acid esters include butyl oleate, butyl stearate, methyl and butyl esters of acetylated ricinol fatty acid, fatty acid glycol ester, triethylene glycol oxy (2-ethylbutyrate), epoxy stearin Acid esters, citrate esters such as acetyltributyl citrate, acetyltriethylene citrate and the like can be mentioned.

  The plasticizer is preferably a phthalate ester or a fatty acid ester. Of the phthalate esters, dioctyl phthalate and diphenyl phthalate are particularly preferred, and among the acyclic (aliphatic) dicarboxylic acid esters, acetyltributyl citrate is particularly preferred.

<Organic solvent>
In producing the color chip of the present invention, an organic solvent can be used. An organic solvent is also used to obtain a dispersion paste from the color chip produced by the method for producing a color chip of the present invention. Examples of the organic solvent include ketones, esters, hydrocarbon solvents, alcohols, ethers, and the like. Preferably, it is at least one organic solvent selected from the group consisting of ketones, esters and hydrocarbon solvents.

  Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisobutyl ketone, cyclohexanone, and isophorone.

  Esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, 3-ethoxyethanol acetate, methyl propionate, and ethyl propionate. , Propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methoxypropyl propionate, methoxybutyl propionate, cellosolve propionate, amyl propionate, 3-ethoxyethanol propionate, methyl butyrate, ethyl butyrate, propyl butyrate , Isopropyl butyrate, butyl butyrate, isobutyl butyrate, methoxypropyl butyrate, methoxybutyl butyrate, cellosolve butyrate, amyl butyrate, 3-ethoxyethanol butyrate, methyl isobutyrate , Ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, butyl isobutyrate, isobutyl isobutyrate, methoxypropyl isobutyrate, methoxybutyl isobutyrate, cellosolve isobutyrate, amyl isobutyrate, 3-ethoxyethanol isobutyrate, methyl lactate, lactic acid Examples include ethyl, butyl lactate, and 1-methoxypropyl-2-acetate.

  Examples of the hydrocarbon solvent include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, styrene and the like.

  Examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, t-amyl alcohol, ethylene glycol, propylene glycol, Examples include diethylene glycol and dipropylene glycol.

  Examples of ethers include isopropyl ether, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether Le, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, and dioxane.

  Furthermore, organic solvents other than those described above can be used in combination as required. These include, for example, petroleum benzine, mineral spirits, solvent naphtha and the like. The above organic solvents may be used alone or in combination of two or more for the purpose of obtaining a desired color chip or dispersion paste.

  Furthermore, when obtaining a dispersion paste from the color chip of the present invention, not only an organic solvent but also a resin may be mixed. Examples of the resin include those described above, and may be the same as or different from the resin used when manufacturing the color chip.

  In the present invention, a conventionally known mixer can be used to obtain a mixture comprising a pigment, an aliphatic amine and a resin, a mixture containing a dispersant, a mixture containing a plasticizer, and a mixture containing an organic solvent. A conventionally known mixer is not particularly limited, and examples thereof include a kneader, a pressure kneader, a Henschel mixer, a Banbury mixer, and a Brabender mixer.

  When an organic solvent is mixed with the color chip of the present invention to obtain a dispersion paste, the solid content, which is the sum of the pigment content and the resin content in the dispersion paste, is preferably 5 to 90%, and 10 to 70%. It is more preferable. Furthermore, the pigment content in the solid content is preferably 5 to 90%, and more preferably 10 to 70%. In addition, when the dispersion paste was produced at these concentrations, the viscosity of the dispersion paste was measured using a Stormer viscometer KU-2 (manufactured by Brookfield) based on JIS K5600-2-2 (Krebs value, KU Value) is preferably 45 to 65 KU, and more preferably 50 to 60 KU.

  In the present invention, when a color paste is mixed with an organic solvent to obtain a dispersion paste, both may be simply mixed by disper stirring or mixed while being dispersed using a conventionally known dispersion device. Conventionally known dispersing devices are not particularly limited. For example, a paint conditioner (manufactured by Red Devil), a ball mill, a sand mill (such as “Dynomill” manufactured by Shinmaru Enterprises), an attritor, a pearl mill (Eirich) "DCP mill", Coball mill, basket mill, homomixer, sand grinder, disperse mat, SC mill, spike mill, nanomizer, homogenizer (such as "Clairemix" manufactured by M Technique Co., Ltd.), wet jet mill (Genus) “Genus PY” manufactured by the company, “Nanomizer” manufactured by Nanomizer, etc.) can be used. In consideration of cost and processing capability, it is preferable to use a media type dispersing machine. As the media, glass beads, zirconia beads, alumina beads, magnetic beads, stainless beads, plastic beads, titania beads, and the like can be used.

  In the dispersion composition of the present invention, various additives may be further blended in order to impart suitability as a composition and a paint. Specific types of additives include thickeners, pH adjusters, anti-drying agents, antiseptic / antifungal agents, chelating agents, UV absorbers, antioxidants, antifoaming agents, rheology control agents, etc. It is done.

  The use of the color chip obtained by the production method of the present invention is not particularly limited, but it can be used for building materials requiring high glossiness and color development, for paints such as automobiles, and for printing inks.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. In the examples, “part” and “%” represent “part by mass” and “% by mass”, respectively, unless otherwise specified.
First, materials used in Examples and Comparative Examples are shown below.

<Pigment>
-RAVEN5000 (RAVEN 5000 Ultra II Beads (CI Pigment Black 7 (PB7)), manufactured by ADITYA BIRLA)
・ BLACK PEARLS 1300 (BLACK PEARLS 1300 (CI Pigment Black 7 (PB7), manufactured by Cabot))

<Resin>
CAB-551-0.2 (cellulose acetate butyrate resin, manufactured by Eastman)
・ Solvine TAO (vinyl chloride / vinyl acetate modified resin, manufactured by Nissin Chemical Industry Co., Ltd.)
・ PIG-VARNISH VC02 (Vinyl chloride / vinyl acetate modified resin, manufactured by Toyo Ink)

<Aliphatic amines and amine cationic activators>
・ Diethylenetriamine (aliphatic hydrocarbon group has 4 carbon atoms)
・ Ethylenediamine (aliphatic hydrocarbon group has 2 carbon atoms)
・ Triethanolamine (aliphatic hydrocarbon group has 6 carbon atoms)
・ Aniline (aliphatic hydrocarbon group with 0 carbon atoms)
・ N-undecylglycine (the aliphatic hydrocarbon group has 11 carbon atoms)
・ Hexadecyl ammonium chloride (aliphatic hydrocarbon group with 16 carbon atoms)

<Dispersant>
SOLPERSE 24000 (resin-type dispersant, manufactured by Lubrizol)

<Plasticizer>
・ Citroflex (Citroflex A-4, manufactured by Vertellus)
・ DBP (diphenyl phthalate)

<Organic solvent>
・ Toluene ・ IPA (Isopropyl alcohol)
・ PMA (propylene glycol monoethyl ether acetate)
・ MIBK (methyl isobutyl ketone)
・ Butyl acetate

<Production of color chips>
Example 1
RAVEN5000 28.20 parts CAB-551-0.2 59.40 parts Diethylenetriamine 1.69 parts Citroflex A-4 4.70 parts Toluene 2.81 parts IPA 3.20 parts

The above components were mixed so as to be uniform, and kneaded with an 8-inch two-roll (heated by Inoue Seisakusho) heated to 60 ° C. The interval between the two rolls was 1 mm, and the mixture was kneaded for 12 minutes after the mixture became a sheet. The obtained sheet-like mixture was put in a polyethylene bag, and then pulverized by hitting with a hammer from above the bag to obtain a color chip 1.

(Examples 2-7, Comparative Examples 1-5)
In the same manner as in Example 1, except that the pigment, resin, aliphatic amine or amine-based cation activator, dispersant, plasticizer, and organic solvent used were changed to the combinations shown in Table 1, color chips 2 to 12 were used. Obtained. However, in Example 2, the amount of resin used was changed from 59.4 parts to 64.1 parts, and in Example 5, 1.41 parts of SOLPERSE24000 was further used, and the amount of resin used was changed from 59.4 parts to 57. 5 parts. In Comparative Examples 1 and 5, the amount of resin used was changed from 59.4 parts to 61.09 parts.

<Preparation of dispersion paste>
(Example 8)
Color chip 1 8.33 parts CAB-551-0.2 14.17 parts PMA 9.00 parts Butyl acetate 9.50 parts MIBK 9.00 parts

The above components were put in a glass bottle with a lid having a capacity of 140 mL, sealed, and shaken and stirred at 25 ° C. for 30 minutes with a paint shaker (manufactured by Asada Tekko Co., Ltd.) to obtain dispersion paste 1. The color chip 1 used was just manufactured.

(Examples 9 to 13)
Dispersion pastes 2 to 6 were obtained in the same manner as in Example 8, except that the color chip 1 was changed to the color chips 2 to 6, respectively. The color chips used were those immediately after production.

(Example 14)
Color chip 7 8.33 parts PIG-VARNISH VC02 27.79 parts Toluene 6.94 parts MEK 6.94 parts

A dispersion paste 7 was obtained in the same manner as in Example 8, except that the components were changed to the above components. Note that the color chip 7 used was just manufactured.

(Comparative Examples 6-9)
Dispersion pastes 8 to 11 were obtained in the same manner as in Example 8 except that the color chip 1 was changed to the color chips 8 to 11, respectively. The color chips used were those immediately after production.

(Comparative Example 10)
A dispersion paste 12 was obtained in the same manner as in Example 14 except that the color chip was changed to 12. In addition, the color chip 12 used just after manufacture was used.

  Table 2 shows the evaluation method of the viscosity, brightness, jetness and gloss of the dispersion paste, and the evaluation results.

<Measurement and evaluation method of viscosity>
Dispersion pastes 1 to 12 were adjusted to 25 ° C. in a thermostatic bath and stirred with a disper (3000 rpm × 2 minutes). Immediately thereafter, the viscosity (Krebs value, KU value) was measured based on JIS K5600-2-2 using a Stormer viscometer KU-2 (manufactured by Brookfield). If the KU value is 60 or less, it can be said that the dispersion paste has a low viscosity. As is apparent from Table 2, all of the dispersion pastes 1 to 7 of the present invention have a KU value of 60 or less, and can be said to be excellent without any practical problems. On the other hand, the dispersion pastes 8 to 12 of Comparative Examples 6 to 10 all had a high KU value of 60 or more, and it was revealed that the viscosity was inferior.

<Measurement and evaluation method of brightness>
The dispersion pastes 1 to 12 obtained in Examples 8 to 14 and Comparative Examples 6 to 10 were each applied to art paper (Oji Paper Co., Ltd., OK Kanto single side) with a 4 mil applicator (film thickness at the time of coating of 100 μm). After using, it dried and obtained the coating film, respectively. The drying conditions were 10 minutes at 25 ° C. and then 30 minutes at 105 ° C. About the obtained coating film, the brightness (L in Lab color space) was measured from the surface of the coating film using the spectrocolorimeter SE2000 (made by Nippon Denshoku Industries Co., Ltd.). The measurement was performed using a D65 light source and the measurement wavelength range was 380 nm to 780 nm. The lower L, the lower the brightness and the higher jetness. Moreover, the difference (ΔL) in brightness from the standard (reference) was calculated for each example. The ΔL of the coating film obtained using the dispersion pastes 1 to 6 and 9 to 11 was obtained using the dispersion pastes 1 to 6 and 9 to 11 with the coating film L obtained using the dispersion paste 8 as a standard. It calculated by calculating | requiring the difference with L of the obtained coating film. ΔL of the coating film obtained using the dispersion paste 7 is obtained by using the L of the coating film obtained using the dispersion paste 12 as a standard and the difference from the L of the coating film obtained using the dispersion paste 7 Was calculated. If ΔL is lower than −0.5, the lightness is low and it can be said that there is a difference in jetness. As is clear from Table 2, ΔL of the coating film obtained by using the dispersion pastes 1 to 7 of the present invention is lower than −0.5, and it can be said that jet blackness is excellent without any practical problem. On the other hand, ΔL of the coating films obtained using the dispersion pastes 9 to 11 of Comparative Examples 7 to 9 was all greater than −0.5, and it was revealed that the jetness was inferior.

<Evaluation method for jetness>
Jetness was evaluated using Mc. About the coating film obtained by the above-mentioned method, chromaticity (X, Y, Z in XYZ color space) was measured from the surface of the coating film using the spectrocolorimeter SE2000 (made by Nippon Denshoku Industries Co., Ltd.). Mc of each coating film was computed based on the following formula 1.

Formula 1 Mc = 100 [log (Xn / X) -log (Zn / Z) + log (Yn / Y)]

X: X of the coating film
Xn: X of irradiation light source
Y: Y of irradiation light source
Yn: Y on the coating film surface over time
Z: Z of the coating film
Zn: Z of irradiation light source

  If Mc is 150 or more, it can be said that jetness is high. As is apparent from Table 2, the Mc of the coating film obtained using the dispersion pastes 1 to 7 of the present invention is 150 or more, and it can be said that the jetness is excellent without any practical problem. On the other hand, Mc of the coating film obtained using the dispersion pastes 8 to 12 of Comparative Examples 6 to 10 was all 150 or less, and it was revealed that jetness was inferior.

<Measurement and Evaluation Method of Glossiness (Gs60 °)>
The dispersion pastes 1 to 12 obtained in Examples 8 to 14 and Comparative Examples 6 to 10 were applied to a transparent polyethylene terephthalate film (PET film, Lumirror 100T60 manufactured by Panac Co., Ltd.) with a 4 mil applicator (the film thickness at the time of coating was 100 μm). ) And then dried to obtain a coating film. The drying conditions were 10 minutes at 25 ° C. and then 30 minutes at 105 ° C. As for the glossiness of the obtained coating film, the glossiness at 60 ° angle (Gs60 °) was measured using a gloss meter VG2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The higher the glossiness, the higher the gloss of the coating film. Further, a difference in glossiness (ΔGs60) from the standard (reference) was calculated for each example. The ΔGs60 ° of the coating film obtained using the dispersion pastes 1 to 6 and 9 to 11 is the dispersion paste 1 to 6 and 9 to 11 with the Gs60 ° of the coating film obtained using the dispersion paste 8 as a standard. It calculated by calculating | requiring the difference with Gs60 degree of the coating film obtained by using. The ΔGs60 ° of the coating film obtained using the dispersion paste 7 is based on the Gs60 ° of the coating film obtained using the dispersion paste 12 and the Gs60 ° of the coating film obtained using the dispersion paste 7 as a standard. Calculated by determining the difference. It can be said that the larger the ΔGs60 °, the higher the glossiness than the standard. As is clear from Table 2, the coating films obtained using the dispersion pastes 1 to 7 of the present invention all have large ΔGs60 °, and it can be said that the glossiness is excellent without any practical problem. On the other hand, it became clear that the glossiness of the coating film obtained using the dispersion pastes 9-11 of Comparative Examples 7-9 was small and the glossiness was inferior.

  Table 3 shows the evaluation method of the stability with time of the color chip and the evaluation results. The temporal stability of the color chip was evaluated for viscosity, jet blackness, hue, and gloss.

<Evaluation method of stability over time (viscosity)>
The color chips 1 to 12 produced by the above method were each stored in an oven at 40 ° C. for 30 days. Thereafter, a dispersion paste was prepared by the above-described method (referred to as “aging dispersion pastes 1 to 12”), and the viscosity (Krebs value, KU value) of each of the dispersion pastes with time was measured with a Stormer viscometer KU-2. The temporal stability (viscosity) of the color chip was evaluated by determining ΔKU (aging) of the time-dispersed paste. ΔKU (temporal) of the time-dispersed pastes 1 to 12 is the KU value of each of the time-dispersed pastes 1 to 12 with the KU value of each of the dispersed pastes 1 to 12 produced using the color chips just manufactured as a standard. It calculated by calculating | requiring the difference of. The smaller the absolute value of ΔKU (aging), the higher the temporal stability (viscosity) of the color chip. As is clear from Table 3, the time-dispersed pastes 1 to 7 obtained using the color chips 1 to 7 of the present invention all have small ΔKU (time), and stability over time (viscosity) has no practical problem. It can be said that it is excellent. On the other hand, the time-dispersed pastes 8 to 12 obtained using the color chips 8 to 12 of Comparative Examples 1 to 5 all have large ΔKU (aging) and are inferior in stability over time (viscosity). It became clear.

<Evaluation method for stability over time (blackness)>
Using the above-described time-dispersed paste, coating films were prepared in the same manner as the lightness measurement (referred to as “time-lapse coating film”). About each time-lapse coating film, the chromaticity (X, Y, Z) was measured with the spectrocolorimeter SE2000. Mc of each time-lapse coating film was calculated by the above-mentioned formula 1. The temporal stability (blackness) of the color chip was evaluated by determining ΔMc (temporal) of the temporal coating. ΔMc (aged) of the time-varying coating film is determined by using the Mc of the coating film (referred to as the “initial coating film”) obtained from the dispersion paste prepared using each color chip immediately after manufacture as a standard. It calculated by calculating | requiring the difference with Mc of. The smaller ΔMc (time), the higher the temporal stability (blackness) of the color chip. As is clear from Table 3, the time-varying coatings obtained from the time-dispersed pastes 1 to 7 obtained using the color chips 1 to 7 of the present invention all have a small ΔMc (time-lapse) and stability over time (jet blackness). ) Is excellent in practical use. On the other hand, the time-varying coatings obtained from the time-dispersed pastes 8 to 12 obtained using the color chips 8 to 12 of Comparative Examples 1 to 5 all have a large ΔMc (time) and stability over time (blackness). ) Was found to be inferior.

<Evaluation method of temporal stability (hue)>
The hue of the above-mentioned time-lapse coating film was measured with a spectrocolorimeter SE2000. The temporal stability (hue) of the color chip was evaluated by determining the hue difference (ΔE (aging)) of the temporal coating film. The hue difference (ΔE (time)) of the coating film over time was calculated by the following formula 2. The smaller ΔE (temporal), the higher the temporal stability (hue) of the color chip. As is clear from Table 3, the time-varying coatings obtained from the time-dispersed pastes obtained using the color chips 1 to 7 of the present invention all have small ΔE (time) and practical stability (color). It can be said that it is excellent without problems. On the other hand, the time-varying coating films obtained from the time-dispersed pastes obtained using Comparative Examples 1 to 5 of 8 to 12 all have large ΔE (time) and inferior temporal stability (hue). Became clear.
Formula 2

L ₁ : Lightness of the initial coating surface L ₂ : Brightness of the time-lapse coating surface a ₁ : a of the initial coating surface
a ₂ : a on the coating film surface over time
b ₁ : b of the initial coating film surface
b ₂ : b on the coating film surface over time

<Evaluation method of stability over time (glossiness)>
Using the above-mentioned time-dispersed paste, coating films were prepared in the same manner as the glossiness measurement (referred to as “time-lapse coating film”). About each time-lapse coating film, 60 degree square glossiness (Gs60 degree) was measured using gloss meter VG2000 (made by Nippon Denshoku Industries Co., Ltd.). The temporal stability (glossiness) of the color chip was evaluated by determining ΔGs 60 ° (aging) of the coating film over time. The ΔGs60 ° (time) of the time-varying coating film is determined based on the Gs60 ° of each coating film (referred to as “initial coating film”) obtained from the dispersion paste prepared using the color chips immediately after production, as a standard. It calculated by calculating | requiring the difference with Gs60 degrees of a coating film. The smaller ΔGs60 ° (time), the higher the temporal stability (glossiness) of the color chip. As is clear from Table 3, the time-varying coating obtained from the time-dispersed paste obtained using the color chips 1 to 7 of the present invention has a small ΔGs of 60 ° (time) and the stability over time (glossiness). It can be said that it is excellent in practical use. On the other hand, the time-varying coatings obtained from the time-dispersed pastes obtained using the color chips 8 to 12 of Comparative Examples 1 to 5 all have a large ΔGs of 60 ° (temporal) and are stable over time (glossiness). It became clear that it was inferior.

  As described above, the color chips 1 to 7 of the present invention have the temporal stability (viscosity), temporal stability (blackness), temporal stability (hue), temporal stability of the respective time-dispersed pastes 1 to 7. (Gloss) was excellent in all items, and it was revealed that the stability over time was excellent. On the other hand, the color chips 8 to 12 of Comparative Examples 1 to 5 have the temporal stability (viscosity), temporal stability (blackness), temporal stability (hue), temporal characteristics of the respective temporal dispersion pastes 8 to 12. It was found that the stability (gloss) was inferior in all items, and the stability over time was inferior.

Claims (5)

  A method for producing a color chip in which a mixture containing a pigment, an amine having an aliphatic hydrocarbon group which may have a hydroxyl group, and a resin is kneaded by a roll, wherein the aliphatic hydrocarbon group has 2 carbon atoms. The manufacturing method of the color chip characterized by being -8.   The method for producing a color chip according to claim 1, wherein the mixture further contains a dispersant.   The method for producing a color chip according to claim 1, wherein the mixture further contains a plasticizer.   The color chip manufactured by the manufacturing method in any one of Claims 1-3.   A dispersion paste obtained by mixing an organic solvent with the color chip according to claim 4.