Pigment composition and use thereof

Abstract

An object of the present invention is to provide a pigment composition having a high coloring power and a small change in hue when exposed to light for a long time.SOLUTION: A pigment composition comprising at least one pigment (A) selected from the group consisting of an orange pigment, a red pigment and a violet pigment, and a compound (B) represented by the following formula (1): [In the general formula (1), any one of X1 and X2 is a carboxyl group or a carbamoyl group, at least one of Y1, Y2, and Y3 is an alkoxy group or a halogen group, and the remaining X1, X2, Y1, Y2, and are hydrogen atoms. Y3. ] SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to pigment compositions containing naphthol pigments and other pigments. [Background technology]

[0002] Architectural signs, outdoor signs, paints, etc. are used outdoors for long periods of time, so the pigments used for coloring them must have excellent resistance to heat, light, water, etc. (hereinafter collectively referred to as weather resistance). Among pigments, quinacridone pigments are red pigments with excellent weather resistance and have a hue ranging from red to magenta.

[0003] For example, Patent Document 1 discloses an ink using a quinacridone pigment. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2020-050818 [Patent Document 2] Patent Publication No. 2021-014535 Summary of the Invention [Problem to be solved by the invention]

[0005] However, while conventional quinacridone pigments offer good lightfastness and color clarity, they are expensive and have low coloring strength.On the other hand, naphthol azo pigments, which are classified as insoluble azo pigments, have high coloring strength and a good balance between manufacturing cost and fastness, but have the problem of insufficient lightfastness (weather resistance). Patent Document 2 discloses a method of using a quinacridone pigment in combination with a naphthol pigment as a means for improving the coloring strength and adjusting the hue of a quinacridone pigment. However, when multiple pigments are combined, if there is a difference in lightfastness between the pigments, the colorant with low lightfastness will fade and change hue when exposed to visible light, ultraviolet light, etc. for a long period of time, which can result in a significant change from the hue originally intended at the time of printing.

[0006] An object of the present invention is to provide a pigment composition that contains two or more pigments and that can achieve both high tinting power and suppression of change in hue upon fading. [Means for solving the problem]

[0007] <1> The pigment composition of the present invention contains one or more pigments (A) selected from the group consisting of orange pigments, red pigments, and purple pigments, and a compound (B) represented by the following general formula (1). General formula (1) [ka]

[0008] [In general formula (1), R1 is a hydrogen atom, an alkyl group, a halogen group, a nitro group, a carboxy group, a sulfo group, a phosphate group, a sulfamoyl group, a carbamoyl group, an alkylsulfamoyl group, or an alkylcarbamoyl group. R2 and R3 are each independently a hydrogen atom, an alkoxy group, an alkyl group, a halogen group, a nitro group, a carboxy group, a sulfo group, a phosphate group, a sulfamoyl group, a carbamoyl group, an alkylsulfamoyl group, or an alkylcarbamoyl group. One of X1 and X2 is a carboxy group or a carbamoyl group, at least one of Y1, Y2, and Y3 is an alkoxy group or a halogen group, and the remaining ones of X1, X2, Y1, Y2, and Y3 are hydrogen atoms. <2> The pigment (A) includes one or more pigments (A1) selected from the group consisting of compounds represented by general formula (2), general formula (3), general formula (4), general formula (5), general formula (6), and chemical formula (7). <1> Pigment composition. [ka] JPEG2026018200000003.jpg41120JPEG2026018200000004.jpg62150 [In general formula (2), general formula (4), general formula (5), and general formula (6), Q1, Q2, D1, D2, A1 to A5, Ax, and C1 to C12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, a halogen group, a nitro group, an alkoxy group, a carboxy group which may be esterified, a carbamoyl group, a sulfamoyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, or an aryl group, except when general formula (5) has the same structure as general formula (1). In general formula (3), P1 and P2 represent a divalent linking group, and each independently represents an oxygen atom, an imino group, an alkylimino group, or an arylimino group. <3> In the general formula (1), R1 is a hydrogen atom or an alkyl group, and R2 and R3 are hydrogen atoms. <1> or <2> Pigment composition. <4> The compound (B) is contained in an amount of 0.1 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the pigment (A), <1> ~ <3> Any pigment composition. <5> The compound represented by the general formula (2) is at least one selected from the group consisting of CI Pigment Red 122 and CI Pigment Violet 19, The compound represented by the general formula (3) is at least one selected from the group consisting of CI Pigment Red 179 and CI Pigment Violet 29, the compound represented by the general formula (4) is at least one selected from the group consisting of CI Pigment Red 254, 264, and CI Pigment Orange 73; The compound represented by the general formula (5) is a compound in which A1, A2, and A5 are hydrogen atoms or alkyl groups, one of A3 and A4 is a carboxy group or a carbamoyl group, and the remaining is a hydrogen atom, and Ax is an aryl group having at least one alkoxy group or a halogen group, The compound represented by the general formula (6) is one or more compounds selected from the group consisting of CI Pigment Red 166 and 242. <2> ~ <4> Any pigment composition. <6> <1> ~ <5> A coloring composition comprising any one of the pigment compositions and a dispersion medium. <7> <1> ~ <5> A paint comprising any one of the pigment compositions, a resin, and a solvent. <8> <1> ~ <5> An ink comprising any one of the pigment compositions, a resin, and a solvent. <9> <1> ~ <5> An active energy ray-curable ink comprising any one of the pigment compositions and a polymerizable compound. [Effects of the Invention]

[0009] According to the present invention, there is provided a pigment composition containing two or more pigments, which has both high tinting power and suppresses hue change upon fading. The present invention also provides a coloring composition, a paint, an ink, an actinic radiation-curable ink, and the like. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, the embodiments of the present invention will be described in more detail. However, the present invention is not limited to the following embodiments, and various modifications may be made within the scope of solving the problems, and various embodiments are included.

[0011] The pigment composition of the present invention contains one or more pigments (A) selected from the group consisting of orange pigments, red pigments, and purple pigments, and a compound (B) represented by general formula (1).

[0012] The mechanism by which the pigment composition of the present invention solves these problems is presumed to be as follows: The carboxyl or carbamoyl group present in X1 or X2 of compound (B) forms a hydrogen bond with an alkoxy or halogen group present in Y1, Y2, or Y3 of an adjacent molecule in the crystal, thereby strengthening intermolecular interactions and enhancing lattice vibration relaxation, thereby improving lightfastness. The reason for this is that UV-induced pigment decomposition is thought to be caused by electrons excited by UV light, and enhanced lattice vibration relaxation increases the rate at which excited electrons relax to the ground state. This accelerates the transition of compound (B) from a state that could potentially lead to decomposition to a stable state, thereby suppressing decomposition. In other words, lightfastness is improved. As described above, the pigment composition of the present invention achieves lightfastness at the same level as high-quality pigments, which are not available in existing naphthol pigments, and reduces hue change due to fading when used in combination with pigment (A).

[0013] <1> Pigment (A) The pigment (A) is one or more pigments selected from the group consisting of orange pigments, red pigments, and purple pigments. The pigment (A) may be any organic or inorganic pigment as long as it exhibits orange, red, or purple color. In this specification, the pigment (A) preferably includes one or more pigments (A1) selected from the group consisting of compounds represented by the following general formulas (2) to (6) and chemical formula (7). [ka] JPEG2026018200000006.jpg41120JPEG2026018200000007.jpg62150

[0014] [In general formulas (2), (4), (5), and (6), Q1 to Q4, D1, D2, A1 to A5, Ax, and C1 to C12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, a halogen group, a nitro group, an alkoxy group, a carboxy group which may be esterified, a carbamoyl group, a sulfamoyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, or an aryl group, except for the case where general formula (5) has the same structure as general formula (1) below.] In general formula (3), P1 and P2 represent a divalent linking group, and each independently represents an oxygen atom, an imino group, an alkylimino group, or an arylimino group.

[0015] The "alkyl group which may have a substituent" may have 1 to 8 carbon atoms and may have any of a linear structure, a branched structure, and a cyclic structure. In one embodiment, the alkyl group preferably has a linear structure. The number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. The alkyl group may have a substituent, and for example, a halogen group, a nitro group, an alkoxy group, a hydroxyl group, or an aryl group is preferred. Of the alkyl groups having a substituent, a trifluoromethyl group is preferred.

[0016] The "halogen group" includes a fluorine atom, a chlorine atom, or a bromine atom. In one embodiment, a chlorine atom or a fluorine atom is preferred, and a chlorine atom is more preferred.

[0017] The "alkyl" in the "alkylsulfamoyl group" is the same as the alkyl group described above. The same applies to the "alkyl" in the "alkylcarbamoyl group". Although not particularly limited, in one embodiment, the alkyl groups in the alkylsulfamoyl group and the alkylcarbamoyl group are each independently preferably alkyl groups having 1 to 4 carbon atoms.

[0018] The "alkoxy group" may have 1 to 8 carbon atoms and may have any of a linear, branched, or cyclic structure. In one embodiment, the alkoxy group preferably has a linear structure. The alkoxy group preferably has 1 to 4 carbon atoms, more preferably 1 or 2, and even more preferably 1.

[0019] The "optionally esterified carboxy group" may be esterified with an alcohol having 1 to 8 carbon atoms and may have any of a linear, branched, or cyclic structure. It may also be esterified with a partially chlorinated alcohol.

[0020] The "aryl group" may be an aromatic ring having 6 to 10 carbon atoms, and may be substituted with a hydrogen atom, an alkoxy group, an alkyl group, a halogen group, a nitro group, a carboxy group, a sulfo group, a phosphate group, a sulfamoyl group, a carbamoyl group, an alkylsulfamoyl group, or an alkylcarbamoyl group. The aryl group may also be part of a fused ring compound containing one or more heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur atoms.

[0021] The compound represented by the general formula (2) preferably contains one or more compounds selected from the group consisting of CI Pigment Red 122, 202, and CI Pigment Violet 19, and more preferably contains one or more compounds selected from the group consisting of CI Pigment Red 122 and CI Pigment Violet 19. The compound represented by the general formula (3) preferably contains one or more selected from the group consisting of CI Pigment Red 179, 190, 224, and CI Pigment Violet 29, and more preferably contains one or more selected from the group consisting of CI Pigment Red 179 and CI Pigment Violet 29. The compound represented by the general formula (4) preferably contains one or more compounds selected from the group consisting of CI Pigment Red 254, 255, 264, and CI Pigment Orange 73, and more preferably contains one or more compounds selected from the group consisting of CI Pigment Red 254, 264, and CI Pigment Orange 73. The compound represented by the general formula (5) preferably includes one or more compounds in which A1, A2, and A5 are hydrogen atoms or alkyl groups, one of A3 and A4 is a carboxy group or a carbamoyl group, and the remaining is a hydrogen atom, and Ax is an aryl group having at least one alkoxy group or a halogen group. The compound represented by the general formula (6) preferably contains one or more selected from the group consisting of CI Pigment Red 144, 166, 220, 221, and 242, and more preferably contains one or more selected from the group consisting of CI Pigment Red 166 and 242. The compound represented by the chemical formula (7) represents CI Pigment Red 177. Here, the term "CI" stands for Color Index Number. Hereinafter, "CI Pigment Red" may be abbreviated as "PR," "CI Pigment Orange" as "PO," and "CI Pigment Violet" as "PV." As the pigment (A), commercially available pigments can be used.

[0022] <2> Compound (B) In this specification, the compound (B) is a compound represented by the following general formula (1). General formula (1) [ka]

[0023] In general formula (1), R1 is a hydrogen atom, an alkyl group, a halogen group, a nitro group, a carboxy group, a sulfo group, a phosphate group, a sulfamoyl group, a carbamoyl group, an alkylsulfamoyl group, or an alkylcarbamoyl group. R2 and R3 are each independently a hydrogen atom, an alkoxy group, an alkyl group, a halogen group, a nitro group, a carboxy group, a sulfo group, a phosphate group, a sulfamoyl group, a carbamoyl group, an alkylsulfamoyl group, or an alkylcarbamoyl group. Either X1 or X2 is a carboxy group or a carbamoyl group, at least one of Y1, Y2 and Y3 is an alkoxy group or a halogen group, and the remainder of X1, X2, Y1, Y2 and Y3 are hydrogen atoms.

[0024] In general formula (1), the "alkyl group" and "alkoxy group" may have 1 to 8 carbon atoms and may have any of a linear structure, a branched structure, and a cyclic structure. In one embodiment, the alkyl group and alkoxy group preferably have a linear structure. The number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0025] The "halogen group" includes a fluorine atom, a chlorine atom, or a bromine atom. In one embodiment, a chlorine atom or a fluorine atom is preferred, and a chlorine atom is more preferred.

[0026] In the general formula (1), R1 is preferably a hydrogen atom or an alkyl group, and R2 and R3 are preferably hydrogen atoms.

[0027] <3> Method for producing compound (B) The compound (B) represented by general formula (1) in the above embodiment can be synthesized by a coupling reaction between a base component and a coupler component. For example, the synthesis method involves preparing a solution (C) containing a coupler component represented by general formula (8). Separately, an aromatic amine represented by the following general formula (9) is diazotized as a base component to synthesize a solution (D) containing a diazonium salt represented by the following general formula (10). Next, these solutions (C) and (D) are mixed to carry out a coupling reaction between the diazonium salt and the coupler component, thereby synthesizing the compound represented by general formula (1).

[0028] [ka]

[0029] In the above general formulae (8), (9), and (10), R1 to R3, X1, X2, and Y1 to Y3 are as already explained. [Z n- ] 1 / nis an anion of any valence n (n is an integer of 1 to 3). Any anion can be used as long as the diazonium salt is stable and soluble in water, but chloride ion, bromide ion, nitrate ion, nitrite ion, acetate ion, sulfate ion, and phosphate ion are preferred.

[0030] The solution (C) containing the coupler component contains the coupler component, a base, and water, and may further contain a water-soluble organic solvent as required. The solution containing the coupler component is prepared, for example, by dissolving the coupler component in a heated basic aqueous solution. Alternatively, the solution can be prepared by mixing water, a water-soluble organic solvent, the coupler component, and a base at room temperature (approximately 10°C to 30°C) and dissolving the coupler component and the base. The dissolution temperature can be adjusted depending on the type and amount of the water-soluble organic solvent, the amount of water, and the type and amount of the base to be added. For example, when the solution contains a water-soluble organic solvent, the temperature is preferably approximately 15 to 50°C. When the solution does not contain a water-soluble organic solvent, the temperature is preferably approximately 20 to 95°C.

[0031] The base is, for example, a compound that dissolves in water and dissolves the coupler component. Furthermore, a base that does not form an insoluble salt when neutralized with an acid in an aqueous acid solution or a solution containing a diazonium salt, which will be described later, is preferred. Such a base is advantageous in terms of cost, dissolving power of the coupler component, waste liquid treatment, etc. The base is preferably, for example, sodium hydroxide or potassium hydroxide.

[0032] The solution (D) containing the diazonium salt contains a diazonium salt and water, and may contain a reaction mixture of the base component used in preparing the diazonium salt, an acid component, and aqueous sodium nitrite. Diazonium salts can be obtained by diazotizing the base component of the general formula (9) above. Known methods can be used for diazotization. For example, hydrochloric acid or sulfuric acid is added to a solution of the base component slurried in ice water, and the solution is dissolved, followed by the addition of sodium nitrite to perform diazotization. Sulfamic acid may be added to eliminate excess sodium nitrite used for diazotization. A water-soluble organic solvent may also be added to the solution containing the diazonium salt.

[0033] The water-soluble organic solvent that can be used in the coupling reaction is not particularly limited. The water-soluble organic solvent may be any organic solvent that is miscible with water. The water-soluble organic solvent may be used to obtain a solution containing a coupler component and / or a solution containing a diazonium salt. Examples of water-soluble organic solvents include aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone; ketones such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; dihydric alcohols such as ethylene glycol, diethylene glycol, and polyethylene glycol; and monohydric alcohols such as methanol, ethanol, and isopropanol.

[0034] The water-soluble organic solvent may be one of the above solvents used alone or a combination of two or more of them. Although not particularly limited, the water-soluble organic solvent is preferably one or more selected from the group consisting of aprotic polar solvents, ketones, monohydric alcohols, and cyclic ethers. Furthermore, the boiling point of the water-soluble organic solvent is preferably 100°C or lower. Such water-soluble organic solvents with a boiling point of 100°C or lower are advantageous in terms of solvent recovery from waste liquid. For example, one or more selected from the group consisting of acetonitrile, acetone, methyl ethyl ketone, methanol, and isopropanol are preferred.

[0035] The amount of water-soluble organic solvent added can be adjusted depending on the type of water-soluble organic solvent. In one embodiment, when a water-soluble organic solvent is added to either the solution containing the coupler component or the solution containing the diazonium salt, the amount added is preferably 3% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on 100% by mass of the total of water and water-soluble organic solvent contained in the slurry after coupling. The amount is also preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0036] Examples of the coupling method include reverse coupling, forward coupling, acid precipitation forward coupling, etc. Among these, reverse coupling, which will be described later, is preferred from the viewpoints of particle size control and reaction yield.

[0037] The reverse coupling can be carried out by a known method. For example, a method of adding a solution containing a coupler component to a solution containing a diazonium salt can be used. The temperature during coupling is preferably 0 to 50°C. From the viewpoints of preventing alteration and decomposition of the diazonium salt and of reaction rate, a temperature of 10 to 30°C is particularly preferred.

[0038] A buffer solution may be added to the solution containing the diazonium salt beforehand. The type of buffer solution is not particularly limited, and any buffer solution with buffering capacity may be used. For example, an aqueous solution of acetic acid and sodium acetate is preferred. When adding a buffer solution, it is desirable to adjust the pH of the solution containing the diazonium salt to a range of 3.0 to 6.5. To improve the reaction rate and dispersibility, the slurry after coupling may be heated as needed. The heating temperature is preferably 50°C to 100°C.

[0039] The slurry of compound (B) obtained by the coupling reaction can be filtered using a known suction filter, filter press, ultrafilter, etc. to remove water, solvent, water-soluble salts, etc. In this way, a wet cake of compound (B) is obtained. The wet cake can be washed with water, an organic solvent, or other solvent, as needed. The wet cake can be dried and pulverized according to known methods to produce powdered compound (B).

[0040] In one embodiment, when compound (B) is produced, a well-known technique for producing an azo pigment can be applied. For example, when producing compound (B), components well known to those skilled in the art may be used in addition to the raw materials for compound (B), as needed. For example, well-known components such as a resin and / or a surfactant can be used to coexist with compound (B).

[0041] If components such as resins and / or surfactants are used during the production of compound (B), these remain on the surface of compound (B) even after production. Therefore, it is preferable that the resins and surfactants be hydrophilic or soluble in basic conditions. The use of such resins and surfactants can improve dispersibility by alleviating aggregation of compound (B) and can impart affinity of compound (B) to dispersing resins and solvents selected depending on the application. Furthermore, the use of these components can also improve reactivity by promoting the dissolution of coupler components and inhibit crystal growth of compound (B).

[0042] Examples of the resin include styrene-(meth)acrylic acid copolymers, (meth)acrylic acid-(meth)acrylic acid alkyl ester copolymers, styrene-(meth)acrylic acid-(meth)acrylic acid alkyl ester copolymers, styrene-α-methylstyrene-(meth)acrylic acid copolymers, styrene-α-methylstyrene-(meth)acrylic acid-(meth)acrylic acid alkyl ester copolymers, polyacrylic acid, polymethacrylic acid, vinylnaphthalene-(meth)acrylic acid copolymers, styrene-maleic acid (anhydride) copolymers, maleic acid-maleic anhydride copolymers, vinylnaphthalene-maleic acid (anhydride) copolymers, α-olefin-maleic acid (anhydride) copolymers, α-olefin-maleic acid alkyl ester copolymers, and resins having acid groups such as polyester-modified acrylic acid polymers, acrylic copolymers, and salts thereof. The resins may be used alone or in combination of two or more.

[0043] When the resin is used, a compound capable of forming a salt with the resin can be further used, such as a basic compound such as an inorganic base or an organic base. Examples of inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal salts of silicic acid such as sodium orthosilicate, sodium metasilicate, and sodium sesquisilicate; alkali metal salts of phosphoric acid such as trisodium phosphate; alkali metal salts of carbonate such as disodium carbonate, sodium hydrogencarbonate, and dipotassium carbonate; alkali metal salts of boric acid such as sodium borate; and ammonia.

[0044] Examples of organic bases include alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and triethylamine; alkanolamines such as aminoethanol, methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, butylaminoethanol, diethylaminoethanol, dibutylaminoethanol, diethanolamine, and triethanolamine; and amines having a nonionic group such as methoxypoly(oxyethylene / oxypropylene)-2-propylamine. The basic compounds may be used alone or in combination of two or more.

[0045] In yet another embodiment, a surfactant can be used in the preparation of compound (B). The surfactant can be, for example, an anionic, nonionic, or amphoteric surfactant.

[0046] Examples of anionic surfactants include fatty acid salts, alkyl sulfate ester salts, alkylaryl sulfonates, alkylnaphthalenesulfonates, alkyl sulfates, dialkylsulfonates, dialkylsulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, naphthalenesulfonate-formalin condensates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phosphate ester salts, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters.

[0047] Examples of amphoteric surfactants include betaine, sulfobetaine, alkylbetaine, and alkylamine oxide.

[0048] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

[0049] In one embodiment, the surfactant is preferably an amphoteric surfactant or an anionic surfactant. Although not particularly limited, when the surfactant is added to a solution containing the coupler components, an anionic or amphoteric surfactant is preferred. When the surfactant is added to a slurry obtained after the coupling reaction, a nonionic surfactant may be used. The surfactants may be used alone or in combination of two or more.

[0050] <4> pigment composition The pigment composition of the present invention can be obtained by mixing pigment (A) and compound (B). The mixing method may be a conventionally known method, and the powders may be mixed using a Nauta mixer or the like, or the crude pigments before pulverization may be mixed and then co-pulverized using a hammer mill or the like.

[0051] The pigment composition of the present invention preferably contains 0.1 to 100 parts by mass of the compound (B) relative to 100 parts by mass of the pigment (A). When the content of compound (B) is 0.1 parts by mass or more, the high coloring power of compound (B) provides an improved coloring power effect. Furthermore, when the content is 100 parts by mass or less, it is possible to adjust the color while taking advantage of the hue of pigment (A). In one embodiment, the content of compound (B) is more preferably 0.5 to 75 parts by mass, and even more preferably 1 to 50 parts by mass.

[0052] The average major axis of the primary particles of the pigment composition (hereinafter sometimes referred to as "average primary particle size") can be appropriately adjusted depending on the transparency required for the intended use. The average primary particle size is preferably 50 nm or more and 700 nm or less. Furthermore, a narrow distribution of the average primary particle sizes of the pigment (A) and compound (B) is preferable because it results in an ink or paint with high viscosity stability of the dispersion containing the pigment composition. In this specification, the distribution of the average primary particle sizes of the pigment (A) and compound (B) is considered narrow when the coefficient of variation of the primary particle sizes of the pigment composition (standard deviation of primary particle sizes divided by average primary particle size, hereinafter sometimes referred to as CV value) is 0.3 or less. The average primary particle size and standard deviation of the primary particle sizes can be determined by measuring the longest diameter of 100 or more primary particles of pigment particles extracted from multiple photographs taken at 10,000x magnification using a transmission electron microscope. When the coefficient of variation of the primary particle size of the pigment composition is within the above range, an ink or paint with high viscosity stability and transparency appropriate for the intended use can be obtained. The method for measuring the major axis of the primary particles is described in detail in the Examples.

[0053] <5> coloring composition One embodiment of the present invention is a coloring composition comprising the pigment composition and a dispersion medium. The dispersion medium comprises at least one or more compounds selected from the group consisting of a resin and a polymerizable compound. The dispersion medium may further comprise a solvent.

[0054] The content of the pigment composition is preferably from 0.1 to 50 mass %, more preferably from 1 to 30 mass %, of the nonvolatile content of the coloring composition.

[0055] The content of the dispersion medium is preferably from 10 to 1000% by mass, more preferably from 20 to 300% by mass, based on the mass of the pigment composition in the coloring composition.

[0056] The dispersion medium is selected depending on the application of the coloring composition. In one embodiment, the coloring composition includes a pigment and a resin, and may further include a solvent as needed. In another embodiment, the coloring composition includes a pigment and a polymerizable compound, and may further include at least one of a resin and a solvent as needed. The coloring compositions of the above embodiments may each include various additives as needed. Examples of applications of the coloring composition include pigment dispersions, resin colored materials, paints, and printing inks. Other examples include printed materials, coated materials, and resin molded products colored with the pigment dispersions, resin colored materials, paints, and inks. More specific embodiments of the coloring composition will be described below.

[0057] <Pigment dispersion> In one embodiment, the coloring composition may be in the form of a pigment dispersion containing the pigment composition of the above embodiment as a main component and further containing a dispersion medium for dispersing the pigment composition. The dispersion medium contains at least a resin and may further contain a solvent depending on the application. In other words, the coloring composition may be referred to as a pigment dispersion. The main component refers to the component with the highest content among the nonvolatile components. The pigment dispersion can be suitably used as an intermediate for paints, inks, etc. The pigment dispersion used as the intermediate may contain a pigment, a resin, and a solvent. The resin contained in the pigment dispersion is preferably a resin-type dispersant.

[0058] When the pigment dispersion contains a solvent, the solvent can be selected from water, a water-soluble solvent, and a water-insoluble solvent. When the solvent contains at least water, an aqueous pigment dispersion is obtained. The water-soluble solvent and the water-insoluble solvent are not particularly limited. For example, they may be the same as the water-soluble solvent and the water-insoluble solvent that constitute the paint described below.

[0059] Examples of dispersers used to prepare the aqueous pigment dispersion include horizontal sand mills, vertical sand mills, annular bead mills, attritors, microfluidizers, high-speed mixers, homomixers, homogenizers, high-pressure homogenizers, ball mills, paint shakers, roll mills, stone mills, ultrasonic dispersers, high-pressure dispersers, opposed collision dispersers, and oblique collision dispersers.

[0060] Furthermore, prior to dispersion, pre-dispersion using a milling mixer such as a kneader or a three-roll mill, or solid dispersion using a two-roll mill, etc. may be performed. After dispersion using various dispersers, post-treatments such as storing the mixture in a heated state at 30 to 80°C for several hours to about a week, and post-treatments using an ultrasonic disperser or a collision-type beadless disperser improve the dispersion stability of the pigment dispersion.

[0061] <Paint> In one embodiment, the pigment composition can be used as a paint. The paint can contain the pigment composition, a resin, and a solvent.

[0062] The content of the pigment composition is preferably 0.1 to 40 mass %, more preferably 0.5 to 30 mass %, of the nonvolatile content of the coating material.

[0063] The other resins include thermosetting resins and thermoplastic resins. The thermosetting resins preferably have a glass transition temperature of 10°C or higher. The thermosetting resins include self-curing resins and resins that are cured by the combined use of a curing agent. Examples of thermosetting resins include acrylic resins, polyester resins, polyurethane resins, and melamine resins. Furthermore, the thermosetting resin preferably has a functional group capable of reacting with a curing agent. Examples of the functional group include a carboxyl group and a hydroxyl group. Examples of the curing agent include an isocyanate curing agent, an epoxy curing agent, an aziridine curing agent, and an amine curing agent. The thermoplastic resin is preferably a resin having a glass transition temperature of 30° C. or higher. Examples of the thermoplastic resin include nitrocellulose resin, acrylic resin, polyester resin, etc. A thermosetting resin and a thermoplastic resin may be used in combination.

[0064] The content of the resin in the nonvolatile matter of the coating material is preferably 60 to 99.9 mass %, more preferably 70 to 99.5 mass %.

[0065] The solvent can be selected from water, non-water-soluble solvents, and water-soluble solvents. When the solvent contains at least water, it can constitute a water-based paint. Examples of the non-water-soluble solvent include toluene, xylene, butyl acetate, methyl acetate, methyl isobutyl ketone, and aliphatic hydrocarbons. The water-soluble solvent may be, for example, a monohydric alcohol, a dihydric alcohol, etc. Examples of the water-soluble solvent include monohydric alcohols such as ethanol, n-propanol, isopropanol, and isobutanol; dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol; and trihydric or higher polyhydric alcohols such as glycerin. The water-soluble solvent may be a water-dilutable monoether derived from a polyhydric alcohol, such as methoxypropanol or methoxybutanol. Other examples include water-dilutable glycol ethers such as butyl glycol and butyl diglycol.

[0066] In one embodiment, the paint can further contain a lustrous material. Examples of the lustrous material include metal flakes, mica, and coated glass flakes. Examples of metal flakes include aluminum flakes and gold powder. Examples of mica include regular mica and coated mica. Examples of coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide. The content of the lustrous material is preferably 0.1 to 10 mass% relative to 100 mass% of the paint. The lustrous material is preferably particles having an average thickness of 0.5 to 10 μm and an average particle size of 5 to 50 μm.

[0067] The paint may further contain other components, such as dispersants, color pigments, and additives. The method for producing the paint and the methods for applying and drying the paint are not particularly limited, and methods well known in the art can be applied. Examples of uses of the paint include paint for metals and paint for plastics.

[0068] In one embodiment, the paint can be suitably applied to substrates such as metals, resins, wood, concrete, and stone. Examples of metals include iron, aluminum, stainless steel, silver, copper, and gold, as well as alloys containing these. Examples of the shape of the substrate include flat or curved plates, rods, cylinders, and spheres. Examples of resin substrates include molded bodies formed by known methods. Examples of types of resin include polyolefin resins, polyacrylic resins, polycarbonate resins, polystyrene resins, acrylonitrile-styrene copolymer resins, polyvinyl chloride resins, acetate resins, ABS resins, polyester resins, and polyamide resins.

[0069] <Ink> In one embodiment, the pigment composition can be suitably used in ink applications. The ink contains the pigment composition of the above embodiment and a solvent, and is also called a printing ink. Depending on the type of ink, a dispersion medium can be further appropriately selected. Examples of the dispersion medium include the resins and dispersants already described. Inks can be broadly classified into solvent-based printing inks, water-based printing inks, and actinic radiation-curable printing inks depending on the presence or absence of a solvent and the type of dispersion medium. Furthermore, inks can be classified into, for example, offset printing inks, flexographic printing inks, gravure printing inks, color filter inks, inkjet printing inks, etc. depending on the printing format. The pigment of this embodiment has excellent dispersibility, coloring power, clarity, and transparency, and can therefore be suitably used in a variety of printing ink applications. Representative printing inks are exemplified below.

[0070] <Ink for inkjet printing> In one embodiment, the pigment composition can be used for inkjet printing ink (hereinafter referred to as IJ ink). In one embodiment, the IJ ink contains a pigment and a resin. In another embodiment, the IJ ink preferably contains a pigment, a resin, and a solvent. The IJ ink is preferably prepared using a pigment dispersion containing a pigment, a resin, and, if necessary, a solvent. In another embodiment, the IJ ink may be a composition in which the resin in the IJ ink of the previously described embodiment is replaced with a polymerizable compound, or a composition in which a resin and a polymerizable compound are used in combination. For example, an IJ ink can be prepared by mixing a pigment dispersion with an IJ ink resin, where the resin in the pigment dispersion and the resin used to prepare the IJ ink can be the same or different.

[0071] Inkjet inks can be broadly classified into (solvent-based) inkjet inks, water-based inkjet inks, and actinic radiation-curable inkjet inks, depending on the presence or absence of a solvent and the type of solvent, as well as the type of resin or polymerizable compound used as the dispersion medium. Actinic radiation-curable inkjet inks can be further classified into photocurable inkjet inks and electron beam-curable inkjet inks, depending on the curing method used to cure the polymerizable compound. Although not particularly limited, the coloring composition of the above embodiment can be suitably used as an aqueous inkjet ink. Below, an aqueous inkjet ink will be described as an example of an inkjet ink.

[0072] The content of the pigment in the water-based IJ ink is preferably 0.5 to 30% by mass, and more preferably 1 to 15% by mass, based on 100% by mass of the total mass of the water-based IJ ink.

[0073] The resin used in water-based inkjet ink is important for ensuring the ink adheres well to the substrate. Examples of resins include acrylic resins, olefin-maleic acid resins, styrene-acrylic resins, polyester resins, polyamide resins, and polyurethane resins. The resin may be in the form of, for example, a water-soluble resin or emulsion particles. Of these, emulsion particles are preferred. The emulsion particles may be, for example, particles of a single composition or core-shell particles, and can be selected and used as desired. When emulsion particles are used, it is easy to reduce the viscosity of the aqueous inkjet ink, and printed matter with excellent water resistance can be easily obtained.

[0074] The resin content in the aqueous IJ ink is preferably 2 to 30% by mass, and more preferably 3 to 20% by mass, based on 100% by mass of the nonvolatile content. When the IJ ink contains a resin within the above range, the ejection stability and fixability tend to be improved.

[0075] From the viewpoint of forming a water-based inkjet ink, the solvent contains at least water. The solvent may further contain either a water-insoluble solvent or a water-soluble solvent. In one embodiment, the solvent preferably contains both water and a water-soluble solvent. Examples of the water-soluble solvent include glycol ethers, diols, etc. These solvents penetrate into the substrate very quickly, even into substrates with low liquid absorption.

[0076] Examples of low-absorbency substrates include coated paper, art paper, vinyl chloride, plastic film, and leather. When a solvent with excellent permeability to the substrate is used as described above, drying during printing is fast, and accurate printing can be easily achieved. Furthermore, when a water-soluble solvent with a high boiling point is used, the solvent also acts as a wetting agent.

[0077] The water-soluble solvent is important for preventing the water-based inkjet ink from drying and solidifying in the nozzle of the printer head, and for ensuring ink ejection stability. Examples of water-soluble solvents include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohols, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, and 4-methoxy-4-methylpentanone.

[0078] In one embodiment, the total content of water and the water-soluble solvent is preferably 30 to 70% by mass relative to 100% by mass of the IJ ink. Here, the content of the water-soluble solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, relative to the total mass of water and the water-soluble solvent.

[0079] IJ inks can further contain additives such as drying accelerators, penetrants, preservatives, chelating agents, pH adjusters, antifoaming agents, wetting agents, and surfactants.

[0080] In this specification, the active energy ray-curable ink preferably contains a pigment composition and a polymerizable compound, and further preferably contains a photopolymerization initiator, etc. The active energy ray-curable ink can be used, for example, as an active energy ray-curable inkjet ink, an active energy ray-curable offset ink, etc.

[0081] The active energy ray-curable inkjet ink will be explained below. The content of the pigment composition is preferably from 0.5 to 30% by mass, and more preferably from 1 to 15% by mass, with the total mass of the active energy ray-curable IJ ink being 100% by mass.

[0082] The polymerizable compound used in actinic radiation-curable inkjet inks is used to ensure ink fixation to the printed material (substrate). There are no particular limitations on the polymerizable compound, so long as it undergoes a polymerization reaction and hardens when some kind of energy is applied. Monomers, oligomers, and polymers can be used regardless of their type, but radically polymerizable monomers are preferred. Polymerizable monomers can be used alone or in combination to adjust the reaction rate, physical properties of the cured film, physical properties of the ink, etc. Furthermore, the polymerizable monomer may be a monofunctional monomer or a polyfunctional monomer with two or more functionalities, with a combination of monofunctional and polyfunctional monomers being preferred. Examples of the polymerizable compound include (meth)acrylate compounds, vinyl ether compounds, compounds having a (meth)acrylate group and a vinyl ether group, allyl compounds, N-vinyl compounds, unsaturated carboxylic acids, etc. Among these, one or more compounds selected from (meth)acrylate compounds, compounds having a (meth)acrylate group and a vinyl ether group, and N-vinyl compounds are preferred.

[0083] In one embodiment, the content of the polymerizable compound is preferably 30 to 99 mass %, more preferably 50 to 95 mass %, and even more preferably 60 to 90 mass %, based on the total mass of the active energy ray-curable IJ ink.

[0084] The active energy ray-curable inkjet ink can contain a photopolymerization initiator. In one embodiment, the photopolymerization initiator can be a molecular cleavage-type or hydrogen abstraction-type photopolymerization initiator that generates radicals. In one embodiment, the photopolymerization initiators can be used alone or in combination of two or more. Alternatively, a photopolymerization initiator that generates radicals and a photopolymerization initiator that generates cations can be used in combination. Examples of the photopolymerization initiator include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, benzophenone-based photopolymerization initiators, etc. Among these, from the viewpoint of curability and storage stability, at least one selected from the group consisting of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one is preferred.

[0085] The content of the photopolymerization initiator is preferably 2 to 30 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 10 to 20 parts by mass, relative to 100 parts by mass of the polymerizable compound. When the content of the photopolymerization initiator is 2 parts by mass or more, good curability can be easily obtained. On the other hand, when the content is 20 parts by mass or less, the curing speed is efficiently increased relative to the amount of photopolymerization initiator added, and good ink jet ejection properties can easily be obtained.

[0086] The active energy ray-curable IJ ink may contain additives such as a polymerization inhibitor, an organic solvent, a surface conditioner, and a pigment dispersant, as needed.

[0087] In one embodiment, the inkjet ink is particularly suitable for use as a red or orange ink. The inkjet ink may be combined with inks of colors other than red or orange to form an ink set. Examples of colors that can be combined with the inkjet ink include cyan, yellow, black, white, magenta, green, blue, violet, pink, gold, silver, and bronze.

[0088] The ink set may be, for example, a five-color ink set that adds cyan, yellow, magenta, and black to the red or orange inks using the inkjet inks of the above-described embodiment. In other embodiments, it may be suitable for use as an ink set of six or more colors by adding special colors such as green and violet. The pigment concentration, viscosity, dynamic viscoelasticity, surface tension, application order, evaporation rate of volatile components, and other factors of each ink are design factors and can be adjusted appropriately depending on the desired properties.

[0089] The inkjet ink of the above embodiment can be applied to a variety of conventionally known substrates, including highly water-absorbent substrates such as plain paper, fabric, and knitted fabric, low-absorbent substrates such as art paper, coated paper, vinyl chloride, wood, concrete, polyethylene film, polypropylene film, polyethylene terephthalate film, natural leather, and artificial leather, and non-water-absorbent substrates such as metals (aluminum, stainless steel, etc.). [Example]

[0090] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass."

[0091] The abbreviations and product names used in the following examples are as follows: <Pigments> PR122: FASTOGEN SUPER MAGENTA RGT (DIC) PV19: INK JET MAGENTA E5B 02 (Heubach) PR179: Paliogen Red L3875 (DIC) PV29: Perrindo VIOLET 29 229-4050 (DIC) PR254: Cinilex DPP Red SR2P (manufactured by Cinilex) PR264:Cinilex DPP Rubine SR6T (manufactured by Cinic) PO73:Cinilex DPP Orange SJ1C (manufactured by Cinic) PR166: Cromophtal Scarlet D 3540 (DIC) PR242:PV FAST SCARLET 4RF (Heubach) PR177:Cinilex RED SR3C (manufactured by Cinic) PR176: Noveperm Carmine HF3C (Heuback) PR150: TOSHIKI RED 150TR (Tokyo Color Co., Ltd.)

[0092] <Coupler> Naphthol AS-RL: 3-hydroxy-4'-methoxy-2-naphthanilide (Sigma-Aldrich) Naphthol AS-E: 4'-chloro-3-hydroxy-2-naphthanilide (Sigma-Aldrich)

[0093] <Bass> M-60: 3-amino-4-methylbenzamide (Tokyo Chemical Industry Co., Ltd.) M-70: 4-aminobenzamide (Tokyo Chemical Industry Co., Ltd.) 4-Aminobenzoic acid (Tokyo Chemical Industry Co., Ltd.)

[0094] <Compound (B)> [ka] JPEG2026018200000011.jpg48109JPEG2026018200000012.jpg4745

[0095] <1> Manufacture of pigment (A) (Production Example A1) Production of Pigment PO73 150 parts of PO73, 1350 parts of sodium chloride, and 240 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) to a capacity of about 50%, and kneaded at 50°C for 8 hours. The resulting kneaded product was added to 7,000 parts of ion-exchanged water, stirred, filtered, and washed with water. This process was repeated to remove the sodium chloride and diethylene glycol, producing a wet cake. This wet cake was dried at 80°C for 24 hours and then pulverized to obtain pigment PO73 with an average primary particle size of 144 nm.

[0096] <2> Preparation of Compound (B) (Production Example B1) Production of Compound (B)-1 A suspension was prepared by adding 18.02 parts of M-60 as a base component to 267 parts of water and stirring. 55.6 parts of 30% hydrochloric acid was added thereto and stirred for 15 minutes. 57.2 parts of ice was then added and stirred until the temperature reached -5°C to 5°C, and 21.4 parts of a 40% aqueous sodium nitrite solution was added over 20 minutes. Diazotization was carried out by stirring at 5°C or below for 90 minutes. Sulfamic acid was added to the reaction mixture obtained by the diazotization to eliminate excess nitrous acid. Sulfamic acid was added until no free nitrous acid was detected using potassium iodide paper. 24.9 parts of sodium acetate and 2.75 parts of 80% acetic acid were added to the mixture to obtain a solution containing a diazonium salt. Separately, a mixture of 280 parts of water and 30.9 parts of 30.5% aqueous sodium hydroxide solution was adjusted to 20 to 30°C. 35.92 parts of naphthol AS-RL was added and dissolved therein as a coupler component to prepare a coupler solution. This solution was added to the solution containing the diazonium salt over 20 minutes to carry out a coupling reaction. The slurry obtained by the coupling reaction was stirred at 25°C for 30 minutes. The slurry was then heated to 70°C and stirred for 60 minutes. The slurry was filtered and washed with water at 60°C to obtain a wet cake. The wet cake was dried at 80°C for 24 hours and then pulverized to obtain 53.3 parts of compound (B)-1 represented by chemical formula (11).

[0097] (Production Example B2) Production of Compound (B)-2 Compound (B)-2 represented by chemical formula (12) was obtained in the same manner as in Production Example 1, except that the base component was changed from 18.02 parts of M-60 to 16.34 parts of M-70.

[0098] (Production Example B3) Production of Compound (B)-3 A suspension was prepared by adding 18.02 parts of M-60 as a base component to 267 parts of water and stirring. 55.6 parts of 30% hydrochloric acid was added thereto and stirred for 15 minutes. 57.2 parts of ice was then added and stirred until the temperature reached -5°C to 5°C, and 21.4 parts of a 40% aqueous sodium nitrite solution was added over 20 minutes. Diazotization was carried out by stirring at 5°C or below for 90 minutes. Sulfamic acid was added to the reaction mixture obtained by the diazotization to eliminate excess nitrous acid. Sulfamic acid was added until no free nitrous acid was detected using potassium iodide paper. 24.9 parts of sodium acetate and 2.75 parts of 80% acetic acid were added to the mixture to obtain a solution containing a diazonium salt. Separately, a mixture of 190 parts of methanol as a water-soluble organic solvent and 30.9 parts of 30.5% aqueous sodium hydroxide solution was adjusted to 15 to 25°C. 35.92 parts of naphthol AS-RL as a coupler component was added and dissolved therein to prepare a coupler solution. This solution was added to the solution containing the diazonium salt over 20 minutes to carry out a coupling reaction. The slurry obtained by the coupling reaction was stirred at 25°C for 30 minutes. The slurry was then heated to 70°C and stirred for 60 minutes. The slurry was filtered and washed with water at 60°C to obtain a wet cake. The wet cake was dried at 80°C for 24 hours and then pulverized to obtain 53.9 parts of compound (B)-3 represented by chemical formula (11).

[0099] (Production Examples B4 to B7) Production of Compounds (B)-4 to (B)-7 Compounds (B)-4 to (B)-7 were obtained in the same manner as in Production Example 3, except that the base component was changed from M-60 to the corresponding base type and base mass part in Table 1, and the coupler component was changed from Naphthol AS-RL to the corresponding coupler type and coupler mass part in Table 1.

[0100] [Table 1]

[0101] <3> Preparation of comparative compound (B) (Production Example B8) Production of PR150 (large) 100 parts by weight of PR150 was added to 1000 parts by weight of N,N-dimethylformamide and stirred for 3 hours. This mixture was added to 4000 parts by weight of water and stirred for 10 minutes, then filtered, washed with water, dried, and pulverized to obtain PR150 (large). The average primary particle diameter was 307 nm.

[0102] <4> Preparation of pigment composition (Example 1) Preparation of pigment composition (1) 97 parts by mass of PR122 as pigment (A) and 3 parts by mass of compound (B)-4 produced in Production Example B4 as compound (B) were weighed and thoroughly mixed to obtain 100 parts by mass of pigment composition (1).

[0103] (Examples 2 to 13) Preparation of pigment compositions (2) to (13) Pigment compositions (2) to (13) were obtained in the same manner as in Example 1, except that PR122 was replaced with the corresponding pigment type and parts by mass in Table 2 as pigment (A), and Production Example B4 was replaced with the corresponding compound type and parts by mass in Table 2 as compound (B).

[0104] (Comparative Examples 1 to 13) Preparation of Pigment Compositions (101) to (113) Pigment compositions (101) to (113) were obtained in the same manner as in Example 1, except that PR122 was replaced with the corresponding pigment type and parts by mass in Table 2 as pigment (A), and Production Example B4 was replaced with the corresponding compound type and parts by mass in Table 2 as compound (B).

[0105] <5> Particle size measurement The average primary particle size and standard deviation of the primary particle size of the pigment compositions of the Examples and Comparative Examples were determined by observation with a transmission electron microscope (TEM) as follows. For 100 or more primary particles of the pigment composition randomly selected from multiple photographs taken at 10,000x magnification using a transmission electron microscope, a rectangle with the smallest area circumscribing the particle image was drawn, and the length of the long side of the rectangle was taken as the major axis. The average value of the major axes was taken as the average primary particle diameter, the standard deviation of the major axes was taken as the standard deviation of the primary particle diameters, and the standard deviation of the primary particle diameters divided by the average primary particle diameter was taken as the coefficient of variation (CV value).

[0106] In Examples 1 to 13 and Comparative Examples 1 to 13, the pigments and compounds used in the production of the pigment compositions, as well as their average primary particle diameters and CV values ​​of the primary particle diameters, are summarized in Table 2. [Table 2]

[0107] <6> coloring composition The following relates to specific examples of coloring compositions containing the pigment compositions prepared above.

[0108] paint (A1) Preparation of paint (Example A-1) Preparation of paint a-1 Pigment composition (1): 9 parts Acrylic resin (DIC Corporation, Acrydic 47-712): 7.7 parts Dispersion medium (a mixed solvent of toluene, xylene, butyl acetate, and T-SOL150FLUID manufactured by ENEOS Corporation in a mass ratio of 3:3:2:2): 40.7 parts The above materials and 230 parts of steel beads were placed in a sealable glass container, sealed, and dispersed for 60 minutes using a paint shaker manufactured by Red Devil Co., Ltd. 75.4 parts of Acrydic 47-712 and 17.2 parts of melamine resin (DIC Corporation, Amidia L-117-60) were then added and dispersed for another 10 minutes. The steel beads were then removed to obtain paint a-1.

[0109] (Examples A-2 to A-13, Comparative Examples A-1 to A-12) Preparation of paints a-2 to a-13 and a-101 to a-112 The same procedure as in Example A-1 was carried out except that the pigment composition (1) in Example A-1 was changed as shown in Table 3, to obtain paints a-2 to a-13 and a-101 to a-112.

[0110] (A2) Paint evaluation <Initial viscosity and viscosity over time> The resulting paint was placed in a sealable glass bottle, sealed, and immersed in a thermostatic bath at 25°C for 1 hour to maintain a constant temperature. The viscosity (referred to as "initial viscosity") was measured at 25°C and 6 rpm using a B-type viscometer (a BII-type viscometer manufactured by Toki Sangyo Co., Ltd.). The viscosity was also measured again in the same manner after storage at 40°C for 1 week (referred to as "viscosity over time"). The results are shown in Table 3. A rating of "4" or "3" on the following evaluation criteria indicates a practical level.

[0111] (Evaluation criteria for initial viscosity and viscosity over time) 4: Viscosity is less than 4000 mPa·s, very good. 3: Viscosity is 4000 mPa·s or more and less than 10000 mPa·s, good. 2: Viscosity is 10,000 mPa·s or more and less than 13,000 mPa·s, defective. 1: Viscosity is 13,000 mPa·s or more, or gelation has occurred, extremely poor.

[0112] (A3) Preparation of light-colored paint (Preparation of white paint) Titanium oxide (Tipake CR90 titanium oxide manufactured by Ishihara Sangyo Kaisha) 66.6 parts Acrylic resin (DIC Corporation, Acrydic 47-712) 101.7 parts Melamine resin (DIC Corporation, Amidia L-117-60) 21.3 parts Dispersion solvent (a mixed solvent of toluene, xylene, butyl acetate, and Solvesso 150 manufactured by TonenGeneral Sekiyu Corporation in a mass ratio of 3:3:2:2) 20.9 parts 900 parts of steel beads were placed in a 900 ml glass bottle and dispersed for 60 minutes using a Red Devil paint shaker. The steel beads were then removed from the dispersion to obtain a white paint.

[0113] (Preparation of Light-Colored Paint) Paints a-1 to a-13 and a-101 to a-112 of Example A were mixed with a white paint in a mass ratio of 1:1 to obtain light-colored paints a'-1 to a'-13 and a'-101 to a'-112.

[0114] (A4) Preparation of top coat clear paint Acrylic resin (DIC Corporation, Acrydic 44-179): 120 parts Melamine resin (DIC Corporation, Amidia L117-60): 30 parts Dilution solvent (a mixed solvent of toluene, xylene, T-SOL150FLUID manufactured by ENEOS Corporation, ethyl 3-ethoxypropionate, and ethyl acetate in a mass ratio of 3:2:2:1:2): 50 parts The above materials were mixed and stirred in a high-speed mixer to obtain a top coat clear paint.

[0115] (A5) Preparation of painted board Preparation of painted plate a''-1 Light-colored paint a'-1 was sprayed onto a primer-treated steel plate using a spray gun. To adjust the viscosity to make it easier to spray, a dilution solvent (a mixed solvent consisting of toluene, xylene, ENEOS T-SOL150FLUID, ethyl 3-ethoxypropionate, and ethyl acetate in a mass ratio of 3:2:2:1:2) was appropriately mixed with the light-colored paint, approximately 10 to 20% by mass. The painting was done in nine separate coats, followed by six separate coats of top coat clear paint. After drying at 25°C for 1 hour, the coated plate was dried at 140°C for 30 minutes to obtain a coated product, coated plate a''-1.

[0116] Preparation of painted plates a''-2 to a''-13, a''-101 to a''-112 In preparing coated plate a''-1, the same procedure was followed as for preparing coated plate a''-1, except that the light-colored paint a'-1 was changed as shown in Table 3, to obtain coated plates a''-2 to a''-13, a''-101 to a''-112.

[0117] (A6) Evaluation of painted boards <Coloring power> The color of the coated panels was measured using a Konica Minolta color difference meter CM-700d and evaluated according to the following criteria. The results are shown in Table 3. As a standard, a paint and coated product were prepared in which the pigment composition of each example was replaced with only the corresponding pigment (A), and ΔL* was calculated by subtracting the L* of the standard coated panel from the L* of the example. The smaller the ΔL*, the higher the coloring strength, which is preferable. A rating of "3" or "2" on the following criteria is considered to be at a practical level. (Evaluation criteria for coloring strength) 3: ΔL*≦-0.5 (higher coloring strength than the standard painted board) 2: -0.5<ΔL*≦0.5 (same coloring strength as the standard painted board) 1:0.5<ΔL* (lower coloring strength than standard painted board)

[0118] <Weather resistance: Color change before and after exposure> The weather resistance test was carried out on the above painted panels using an accelerated weather resistance tester (Iwasaki Electric Co., Ltd., iSuper Xenon Tester SUV-W151) at 90 mW / cm 2 The test was conducted under conditions of 96 hours (four 12-hour day / night cycles), and the hue difference (ΔH*) before and after the weathering test was evaluated using a Konica Minolta CM-700d colorimeter. As a standard, paints and coated objects were prepared by replacing the pigment composition of each example with the corresponding pigment (A), and similar weathering tests were conducted. Evaluation was conducted according to the absolute value (|ΔΔH*|) of the difference between the ΔH* of pigment (A) and the ΔH* of the example, based on the following criteria. The smaller this value, the smaller the change in hue before and after exposure, and the more preferable it is. For calculation convenience, when H* was 270 or greater but less than 360, the value obtained by subtracting 360 from the H* value was used as H*. The results are shown in Table 3. A rating of "3" or "2" on the following criteria is considered practical. (Weather resistance evaluation criteria) 3: The absolute value of the difference in hue change from the standard (|ΔΔH*|) is less than 0.5, good 2: The absolute value of the difference in hue change from the standard (|ΔΔH*|) is 0.5 or more and less than 1.0, suitable for practical use 1: The absolute value of the difference in hue change from the standard (|ΔΔH*|) is 1.0 or more, poor

[0119] [Table 3]

[0120] Water-based inkjet ink (B1) Preparation of Water-Based Inkjet Ink (Water-Based IJ Ink) (Example B-1) Preparation of Water-Based IJ Ink b-1 200 parts of zirconia beads with a diameter of 1.25 mm and the following raw materials were placed in a 200 ml glass bottle and dispersed for 6 hours using a paint shaker manufactured by Red Devil. Pigment composition (1): 19.0 parts Styrene-acrylic acid copolymer (BASF Japan, JONCRYL 61J): 16.4 parts Surfactant (Kao Corporation, Emulgen 420): 5.0 parts Ion-exchanged water: 59.6 parts Next, the zirconia beads were removed from the dispersion to obtain a pigment dispersion.

[0121] Next, the pigment dispersion and the following raw materials were mixed and stirred for 30 minutes using a high-speed mixer to obtain a mixture. Obtained pigment dispersion: 12.5 parts Styrene-acrylic acid copolymer (BASF Japan, JONCRYL 60): 3.3 parts Surfactant (Kao Corporation, Emulgen 420): 2.0 parts Ion-exchanged water: 64.9 parts Next, diethylene glycol monobutyl ether was added to the above mixture to adjust the viscosity at 25°C to 2.5 mPa·s (25°C) and the surface tension to 40 mN / m. The mixture was then filtered using a 1.0 μm membrane filter and then further filtered using a 0.45 μm membrane filter to obtain water-based IJ ink b-1.

[0122] (Examples B-2 to B-3, Comparative Examples B-1 to B-3) Preparation of Water-Based IJ Inks b-2 to b-3, b-101 to b-103 The same procedure as in Example B-1 was carried out except that the pigment composition (1) in Example B-1 was changed as shown in Table 4, to obtain water-based IJ inks b-2 to b-3 and b-101 to b-103.

[0123] (B2) Evaluation of water-based inkjet ink <Viscosity stability> The initial viscosity of each water-based inkjet ink was measured at 25°C using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). In the same manner, the viscosity was measured after aging at 70°C for two weeks. Using each measured value, the viscosity increase rate relative to the initial viscosity was calculated, which was used as an index of viscosity stability and evaluated according to the following criteria. The results are shown in Table 4. The smaller the viscosity increase rate, the better the viscosity stability is considered to be, and a rating of "3" on the following evaluation criteria is considered to be at a practical level. (Evaluation criteria for viscosity stability) 3: Viscosity increase rate is less than 15% 2: Viscosity increase rate is 15% or more but less than 30% 1: Viscosity increase rate is 30% or more

[0124] <Coloring power> The prepared aqueous inkjet ink was filled into the cartridge of a Seiko Epson PX-105 printer (piezo inkjet printer), and a solid print was made on A4-sized plain paper. The print was measured using an X-rite eXact colorimeter and evaluated according to the following criteria. The print of Comparative Example B-1 was used as the reference print, and ΔL* was calculated by subtracting the L* of the example from the L* of the reference print. The results are shown in Table 4. A rating of "3" or "2" on the following criteria is considered to be at a practical level. (Evaluation criteria for coloring strength) 3: ΔL*≦-0.5 (higher coloring strength than the reference print) 2: -0.5<ΔL*≦0.5 (coloring strength is similar to the reference print) 1:0.5<ΔL* (coloring strength is lower than the reference print)

[0125] <Lightfastness: Color change before and after exposure> The inkjet ink prints prepared above were subjected to a lightfastness test using a Suga Test Instruments Xenon Weather Meter SX75 under conditions of 60 W irradiance, 63°C black panel temperature, and 50% RH. The hue difference (ΔH*) before and after the weatherfastness test was evaluated using a Konica Minolta CM-700d colorimeter. As a standard, inkjet inks and prints were prepared by replacing the pigment composition of each example with the corresponding pigment (A), and similar weatherfastness tests were conducted. Evaluation was conducted based on the absolute value (|ΔΔH*|) of the difference between the ΔH* of pigment (A) and the ΔH* of the example, using the following criteria. The smaller this value, the smaller the hue change before and after exposure, and the more preferable it is. For calculation convenience, when the H* value was 270 or greater but less than 360, the value obtained by subtracting 360 from the H* value was used as the H* value. The results are shown in Table 4. A rating of "3" or "2" on the following criteria is considered practical. (Weather resistance evaluation criteria) 3: The absolute value of the difference in hue change from the standard (|ΔΔH*|) is less than 0.5, good 2: The absolute value of the difference in hue change from the standard (|ΔΔH*|) is 0.5 or more and less than 1.0, suitable for practical use 1: The absolute value of the difference in hue change from the standard (|ΔΔH*|) is 1.0 or more, poor

[0126] In addition, when the substrate was changed from A4 size plain paper to coated paper, polypropylene film (OPP film), aluminum foil, and artificial leather (polyurethane sheet), the same results were obtained when the coloring power was evaluated. When the substrate was not paper, the substrate was attached to A4 size plain paper. In addition, when a tank filled with the prepared water-based inkjet ink was installed as magenta ink in a Canon MAXIFYMB5430 (thermal inkjet printer), the coloring power was evaluated, and similar results were obtained.

[0127] [Table 4]

[0128] <c>Active energy ray curable inkjet ink (active energy ray curable IJ ink) (C1) Preparation of active energy ray curable inkjet ink (Example C-1) Preparation of active energy ray-curable IJ ink c-1 The following materials were mixed and stirred in a high-speed mixer until uniform, and the resulting mill base was dispersed in a horizontal mill for 1 hour to obtain a pigment dispersion. Pigment composition (1): 5 parts Pigment dispersant (Lubrizol, Solsperse 32000): 1 part Polymerizable compound (dipropylene glycol diacrylate, Miramer M222, manufactured by BASF Japan): 19 parts Next, to 25 parts of the obtained pigment dispersion, the following materials were added in order with stirring, and stirring was continued until the photopolymerization initiator was dissolved to obtain a mixture. Polymerizable compound (lauryl acrylate, manufactured by Osaka Organic Industry Co., Ltd.): 30 parts Polymerizable compound (dipropylene glycol diacrylate, Miramer M222, manufactured by BASF Japan): 5.2 parts Polymerizable compound (2-(2-vinyloxyethoxy)ethyl acrylate, VEEA-AI, manufactured by Nippon Shokubai Co., Ltd.): 30 parts Photopolymerization initiator (4-benzoyl-4'-methyl-diphenyl sulfide, KAYACURE BMS, manufactured by Nippon Kayaku Co., Ltd.): 3.0 parts Photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide, Irgacure TPO, manufactured by BASF Japan): 3.0 parts Polymerization accelerator (Thought ethyl-4-(dimethylamino)-benzoate, SB-PI-704): 3.0 parts DEDG (Diethylene glycol diethyl ether, manufactured by Nippon Nyukazai Co., Ltd.): 0.5 parts Polymerization inhibitor (Seiko Chemical Co., Ltd., phenothiazine): 0.1 parts Surface conditioner (BYK Chemie polyether-modified polydimethylsiloxane, BYK-UV3510): 0.2 parts The resulting mixture was then filtered through a membrane filter with a pore size of 1 μm to remove coarse particles, yielding active energy ray-curable IJ ink c-1.

[0129] (Examples C-2 to C-3, Comparative Examples C-1 to C-3) Preparation of active energy ray-curable IJ inks c-2 to c-3 and c-101 to c-103 Except for changing the pigment composition (1) of Example C-1 as shown in Table 5, the same procedure as in Example C-1 was carried out to obtain active energy ray-curable IJ inks c-2 to c-3 and c-101 to c-103.

[0130] (C2) Evaluation of active energy ray curable inkjet ink <Viscosity stability> The ink was filled into a sealable storage bottle to 90% capacity and left at 60°C for 2 weeks. The rate of change in viscosity before and after leaving the bottle was evaluated based on the following evaluation criteria to evaluate storage stability. The evaluation results are shown in Table 5. A rating of "3" on the following criteria is considered to be at a practical level. 3: The rate of change is less than 15% of the initial value. 2: The rate of change is 15% or more but less than 25% of the initial value. 1: The rate of change is 25% or more compared to the initial value.

[0131] (E3) Preparation of active energy ray curable inkjet prints The prepared ink was printed under the following printing conditions: Using an ink jet ejection device (Tritec OnePassJET) equipped with a Kyocera head (resolution 600 dpi x 600 dpi), 100% solid images were printed on a Lintec PET K2411 substrate under printing conditions of an ink droplet volume of 14 pL. The film thickness of each ink was approximately 8 μm. The conveyor speed was 50 m / min, and a 160 W / cm metal halide lamp (365 nm) manufactured by Harrison Toshiba Lighting Co., Ltd. was used as the radiation source. The ink was cured in the atmosphere to obtain an inkjet print.

[0132] <Coloring power> The printed matter was measured using an X-rite eXact colorimeter and evaluated according to the following criteria. The printed matter of Comparative Example C-1 was used as the reference printed matter, and ΔL* was calculated by subtracting the L* value from the reference L* value. The results are shown in Table 5. A rating of "3" or "2" on the following criteria is considered to be at a practical level. (Evaluation criteria for coloring strength) 3: ΔL*≦-0.5 (higher coloring strength than the reference print) 2: -0.5<ΔL*≦0.5 (coloring strength is similar to the reference print) 1:0.5<ΔL* (coloring strength is lower than the reference print)

[0133] <Lightfastness: Color change before and after exposure> The inkjet ink prints prepared above were subjected to a lightfastness test using a Suga Test Instruments Xenon Weather Meter SX75 under conditions of 60 W irradiance, 63°C black panel temperature, and 50% RH. The hue difference (ΔH*) before and after the weatherfastness test was evaluated using a Konica Minolta CM-700d colorimeter. As a standard, inkjet inks and prints were prepared by replacing the pigment composition of each example with the corresponding pigment (A), and similar weatherfastness tests were conducted. Evaluation was conducted based on the absolute value (|ΔΔH*|) of the difference between the ΔH* of pigment (A) and the ΔH* of the example, using the following criteria. The smaller this value, the smaller the hue change before and after exposure, and the more preferable it is. For calculation convenience, when the H* value was 270 or greater but less than 360, the value obtained by subtracting 360 from the H* value was used as the H* value. The results are shown in Table 5. A rating of "3" or "2" on the following criteria is considered practical. (Weather resistance evaluation criteria) 3: The absolute value of the difference in hue change from the standard (|ΔΔH*|) is less than 0.5, good 2: The absolute value of the difference in hue change from the standard (|ΔΔH*|) is 0.5 or more and less than 1.0, suitable for practical use 1: The absolute value of the difference in hue change from the standard (|ΔΔH*|) is 1.0 or more, poor

[0134] [Table 5]

[0135] From the results in Tables 3 to 5, it can be seen that when the pigment composition of the present invention is used, paints and inks can be obtained that have high tinting power and that show little change in hue when faded due to long-term exposure to light. On the other hand, when combined with a naphthol pigment other than the compound (B) represented by general formula (1), as in Comparative Examples A-1, A-3 to A-11, B-1, and C-1, the hue change upon fading due to prolonged exposure to light was significant. Furthermore, when combined with a quinacridone pigment, as in Comparative Examples A-2, B-2, and C-2, the tinting strength was insufficient. Furthermore, even when attempts were made to improve lightfastness by increasing the primary particle size of a naphthol pigment other than the compound (B) represented by general formula (1), as in Comparative Examples A-12, B-3, and C-3, controlling the primary particle size alone was not enough to achieve lightfastness comparable to that of the Examples. Furthermore, there was a trade-off between viscosity stability and tinting strength, and no pigment composition was obtained that achieved both high tinting strength and suppressed hue change upon fading.< / c>

Claims

1. A pigment composition comprising one or more pigments (A) selected from the group consisting of orange pigments, red pigments, and purple pigments, and a compound (B) represented by the following general formula (1): General formula (1) 【Chemistry 1】 In general formula (1), R1 represents a hydrogen atom, an alkyl group, a halogen group, a nitro group, a carboxy group, a sulfo group, a phosphate group, a sulfamoyl group, a carbamoyl group, an alkylsulfamoyl group, or an alkylcarbamoyl group. R2 and R3 each independently represent a hydrogen atom, an alkoxy group, an alkyl group, a halogen group, a nitro group, a carboxy group, a sulfo group, a phosphate group, a sulfamoyl group, a carbamoyl group, an alkylsulfamoyl group, or an alkylcarbamoyl group. One of X1 and X2 is a carboxy group or a carbamoyl group, at least one of Y1, Y2, and Y3 is an alkoxy group or a halogen group, and the remaining ones of X1, X2, Y1, Y2, and Y3 are hydrogen atoms.

2. 2. The pigment composition according to claim 1, wherein the pigment (A) comprises one or more pigments (A1) selected from the group consisting of compounds represented by general formula (2), general formula (3), general formula (4), general formula (5), general formula (6), and chemical formula (7). 【Chemistry 2】 【change】 【change】 [In general formula (2), general formula (4), general formula (5), and general formula (6), Q1, Q2, D1, D2, A1 to A5, Ax, and C1 to C12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, a halogen group, a nitro group, an alkoxy group, a carboxy group which may be esterified, a carbamoyl group, a sulfamoyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, or an aryl group, except for the case where general formula (5) has the same structure as general formula (1). In general formula (3), P1 and P2 represent a divalent linking group, and each independently represents an oxygen atom, an imino group, an alkylimino group, or an arylimino group.

3. 2. The pigment composition according to claim 1, wherein in the general formula (1), R1 is a hydrogen atom or an alkyl group, and R2 and R3 are hydrogen atoms.

4. The pigment composition according to claim 1 , comprising 0.1 parts by mass or more and 100 parts by mass or less of the compound (B) relative to 100 parts by mass of the pigment (A).

5. The compound represented by the general formula (2) is at least one selected from the group consisting of C.I. Pigment Red 122 and C.I. Pigment Violet 19, The compound represented by the general formula (3) is one or more selected from the group consisting of C.I. Pigment Red 179 and C.I. Pigment Violet 29, The compound represented by the general formula (4) is one or more selected from the group consisting of C.I. Pigment Red 254, 264, and C.I. Pigment Orange 73, The compound represented by the general formula (5) is a compound in which A1, A2, and A5 are hydrogen atoms or alkyl groups, one of A3 and A4 is a carboxy group or a carbamoyl group, and the remaining is a hydrogen atom, and Ax is an aryl group having at least one alkoxy group or a halogen group, 3. The pigment composition according to claim 2, wherein the compound represented by the general formula (6) is one or more compounds selected from the group consisting of C.I. Pigment Red 166 and 242.

6. A coloring composition comprising the pigment composition according to any one of claims 1 to 5 and a dispersion medium.

7. A paint comprising the pigment composition according to any one of claims 1 to 5, a resin, and a solvent.

8. An ink comprising the pigment composition according to any one of claims 1 to 5, a resin, and a solvent.

9. An active energy ray-curable ink comprising the pigment composition according to any one of claims 1 to 5 and a polymerizable compound.

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