JP6928750B1 - Pigment composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment composition having good sharpness, dispersibility and crystal stability. C.I. I. Pigment Red 269, and C.I. I. A pigment composition containing composite pigment particles containing Pigment Red 150, wherein C.I. I. Pigment Red 150 is a pigment composition having a content of 10 to 50 mol%. It is preferable that the powder X-ray diffraction using CuKα rays of the composite pigment particles does not have a maximum peak within the range of the diffraction angle (2θ) = 13.5 to 14.5 °. [Selection diagram] Fig. 1

Description

The present invention relates to a pigment composition containing composite pigment particles and its use.

Organic pigments capable of reproducing magenta hue from red include, for example, soluble azo pigments, insoluble azo pigments, quinacridone pigments, etc., and are used in applications such as plastic products, toners, paints, and printing inks. Of these, soluble azo pigments have the advantages of vivid hue and high coloring power and are inexpensive, but they have insufficient fastness, and depending on the application, they are metals used for rake formation of pigments. There is a problem that the presence of ions adversely affects various printing characteristics. On the other hand, the quinacridone pigment has superior properties to other pigments in terms of fastness and sharpness, but its coloring power and dispersion stability are significantly inferior to those of other pigments, and it is more expensive. On the other hand, naphthol-based azo pigments, which are classified as insoluble azo pigments, have a good balance of manufacturing cost, coloring power, and fastness, and are therefore being studied for use in various applications. However, it has drawbacks in crystal stability, such as insufficient sharpness and dispersibility, and growth of pigment crystals depending on the dispersion medium.
Therefore, for example, in the field of digital printing, the current situation is that naphthol-based azo pigments and quinacridone pigments are used in combination to complement each other in image sharpness and coloring power. (Patent Document 1)

In order to solve these problems, Patent Document 2 discloses a composition containing two or more kinds of naphthol-based azo pigments having a specific structure.

JP-A-2002-156795 Japanese Unexamined Patent Publication No. 2005-107147

However, conventional compositions have problems of lacking clarity, dispersibility and crystal stability.

An object of the present invention is to provide a pigment composition having good sharpness, dispersibility and crystal stability.

The pigment composition of the present invention is C.I. I. Pigment Red 269, and C.I. I. A pigment composition containing composite pigment particles containing Pigment Red 150.
C.I. in 100 mol% of the composite pigment particles. I. The content of Pigment Red 150 is 10 to 50 mol%.

The present invention also relates to the above pigment composition, wherein powder X-ray diffraction using CuKα rays of the composite pigment particles does not have a maximum peak in the range of diffraction angle (2θ) = 13.5 to 14.5 °. ..

The present invention also relates to a coloring composition containing the pigment composition and a dispersion medium.

The present invention also relates to the coloring composition, wherein the dispersion medium contains a resin.

The present invention also relates to a molding resin composition containing the coloring composition.

The present invention also relates to a toner containing the coloring composition.

The present invention also relates to a coating material containing the coloring composition.

The present invention also relates to a printing ink containing the coloring composition.

The present invention also relates to an inkjet ink containing the coloring composition.

According to the above invention, it is possible to provide a pigment composition, a coloring composition, a molding resin composition, a toner, a paint, a printing ink, and an inkjet ink having good sharpness, dispersibility, and crystal stability.

FIG. 1 is a powder X-ray diffraction spectrum of the pigment composition obtained in Example 3 with CuKα rays. FIG. 2 is a powder X-ray diffraction spectrum of the pigment composition obtained in Comparative Example 1 with CuKα rays. FIG. 3 shows C.I. I. It is a powder X-ray diffraction spectrum by CuKα ray of Pigment Red 150 (manufactured by Tokyo color material industry, Toshiki Red 150TR). FIG. 4 is a powder X-ray diffraction spectrum of the pigment composition obtained in Comparative Example 8 with CuKα rays.

The terms defined herein are defined. When written as "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide", unless otherwise specified, they are "(meth) acrylamide", respectively. It means "acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylic acid". Further, "CI" means a color index (CI). A solid solution refers to an embodiment in which X-ray diffraction of a composite pigment containing two pigments shows a crystal lattice of one pigment (host) and the other pigment (guest) is embedded in the crystal lattice of the host component. ..

The pigment composition of the present invention is C.I. I. Pigment Red 269, and C.I. I. A pigment composition containing composite pigment particles containing Pigment Red 150.
C.I. in 100 mol% of the composite pigment particles. I. The content of Pigment Red 150 is 10 to 50 mol%. In the present invention, the composite pigment particles are solid solutions.

Composite pigment particles such as a solid solution have the property of complementing each other's shortcomings of the host component and the guest component, and the property of improving the inherent properties of the host component. Since the pigment composition of the present invention contains composite pigment particles, C.I. I. The low dispersibility of Pigment Red 269 was combined with the guest component C.I. I. Pigment Red 150 complemented by C.I. I. Pigment Red 150 with low crystal stability of C.I. I. In addition to being complemented by Pigment Red 269, C.I. I. The sharpness of Pigment Red 269 can be improved. Therefore, C.I. I. When the content of Pigment Red 150 is 10 mol% or more, the dispersibility is improved. In addition, C.I. I. When the content of Pigment Red 150 is 50 mol% or less, the crystal stability is improved. In addition, C.I. I. The content of Pigment Red 150 is preferably 20 to 40 mol%.

Whether or not the pigment forms a solid solution can be easily verified by X-ray diffraction analysis or the like. When a sample is simply a mixture of a plurality of pigments, the obtained X-ray diffraction pattern is a superposition of the X-ray diffraction patterns of each pigment, and the intensity of each diffraction peak is the compounding ratio of each pigment. Depends on. On the other hand, when a plurality of pigments form a solid solution, an X-ray diffraction pattern different from the case where the plurality of pigments are simply mixed can be obtained. Specifically, phenomena such as the intensity of each diffraction peak not depending on the blending ratio of the pigment and the full width at half maximum of the diffraction peak are observed.

C. I. The structure of Pigment Red 269 is shown in the following chemical formula (1). In addition, C.I. I. The structure of Pigment Red 150 is shown in the following chemical formula (2).

In the pigment composition of the present invention, it is preferable that the powder X-ray diffraction using CuKα rays of the composite pigment particles does not have a maximum peak in the range of diffraction angle (2θ) = 13.5 to 14.5 °. Diffraction angle (2θ) = 13.5-14.5 ° C.I. I. This is because the crystal stability is further improved as compared with the case where the maximum peak derived from Pigment Red 150 appears.

Further, the pigment composition of the present invention preferably has a maximum peak in the range of diffraction angle (2θ) = 12.5 to 13.5 °. In the present invention, C.I. I. It means that the peak derived from Pigment Red 150 is not observed even as the shoulder peak (shoulder peak) of the maximum peak appearing in the range of diffraction angle (2θ) = 12.5 to 13.5 °.

The pigment composition of the present invention is C.I. I. Pigment Red 269, and C.I. I. Containing composite pigment particles containing Pigment Red 150, C.I. I. The content of Pigment Red 150 may be 10 to 50 mol%, and the production method is not limited.

A known method for synthesizing an azo pigment can be used for producing the pigment composition of the present invention. Specifically, a diazonium salt obtained by diazotizing 3-amino-4-methoxybenzanilide, which is a base component, and C.I. I. N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide, which are coupler components of Pigment Red 269, and C.I. I. It can be produced by coupling reaction with 3-hydroxy-2-naphthamide, which is a coupler component of Pigment Red 150.

Specifically, the solution containing the diazo component obtained by diazotizing the base component and the solution containing the coupler component are prepared and coupled, respectively. For the solution containing the coupler component, one solution containing both the coupler components N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide and 3-hydroxy-2-naphthamide was prepared. The pigment composition of the present invention can be obtained by using it for coupling. Alternatively, a solution containing only N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide and a solution containing only 3-hydroxy-2-naphthamide are prepared and coupled in stages. Is also good. In the latter case, C.I. I. A pigment composition can be obtained by coupling in order from a solution containing N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide, which is a coupler component of Pigment Red 269.

The solution containing the coupler component can be prepared by dissolving the coupler component in a heated basic aqueous solution. Further, it may be dissolved by mixing water, a water-soluble organic solvent, a coupler component, and a base at room temperature (about 10 ° C. to 30 ° C.). The dissolution temperature varies depending on the amount, type, amount of water, type, and amount of the water-soluble organic solvent to be added, but is preferably about 15 to 50 ° C. when the water-soluble organic solvent is contained. When it does not contain a water-soluble organic solvent, it is preferably 50 to 95 ° C.

The base is preferably, for example, a base that can be dissolved in water to dissolve the coupler component and does not form an insoluble salt when neutralized with an acid in an acid aqueous solution or a solution containing a diazo component described later. As the base, for example, sodium hydroxide and potassium hydroxide are more preferable. As a result, aspects such as cost, dissolving power of the coupler component, and waste liquid treatment are improved.

The solution containing the diazo component is obtained by diazotizing the base component 3-amino-4-methoxybenzanilide. A known method can be used as the diazotization method. For example, diazotization can be performed by adding hydrochloric acid to a solution in which the base component is reslurried in ice water to dissolve it, and then adding sodium nitrite. Further, a water-soluble organic solvent may be added to the solution containing the diazo component.

The water-soluble organic solvent that can be used in the solution containing the coupler component and the solution containing the diazo component may be, for example, any water-soluble organic solvent as long as it can be freely mixed with water. The sex organic solvent is, for example, an aproton polar solvent such as dimethyl sulfoxide, N, N-dimethylformamide, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, and ethylene. Examples thereof include dihydric alcohols such as glycol, diethylene glycol and polyethylene glycol, and monohydric alcohols such as methanol, ethanol and isopropanol.

The amount of the water-soluble organic solvent added depends on the type of the water-soluble organic solvent, but when it is added to either the solution containing the coupler component or the solution containing the diazo component, 1 to 1 in 100% by mass of the entire slurry after coupling. 50% by mass is preferable.

Examples of the coupling method include reverse coupling, positive coupling, acidification positive coupling and the like. Among these, reverse coupling or acidification positive coupling, which will be described later, is preferable from the viewpoint of particle size control and reaction yield.

As a method of reverse coupling, for example, a known method can be used, and examples thereof include a method of adding a solution containing a coupler component to a solution containing a diazo component. The temperature at the time of coupling is preferably 0 to 50 ° C, and particularly preferably 10 to 30 ° C from the viewpoint of suppressing alteration and decomposition of the diazo component and reaction rate.
A buffer solution may be added in advance to the solution containing the diazo component. As the type of buffer solution, for example, any one having a buffering ability may be used, but it is preferable to use an aqueous solution of acetic acid-sodium acetate. When adding a buffer solution, it is desirable to adjust the pH of the solution containing the diazo component to the range of 3.0 to 6.5. From the viewpoint of improving the reaction rate and the dispersibility, it is preferable to heat the slurry after coupling, if necessary.

As a method of acidification positive coupling, for example, a known method can be used, and after reacting a solution containing a coupler component with an acid aqueous solution to obtain an acid analysis coupler slurry, the obtained acid analysis coupler slurry is used. A method of adding a solution containing a diazo component and causing a coupling reaction can be mentioned. The temperature of the aqueous acid solution during acidification can be selected from any temperature, but is preferably 0 to 30 ° C. From the viewpoint of improving the reaction rate, it is preferable to heat the acid analysis coupler slurry, if necessary, before adding the solution containing the diazo component. However, if the temperature becomes too high, the diazo component is likely to be deteriorated and decomposed. Therefore, the temperature of the acid-deposited coupler slurry at the time of the coupling reaction is preferably 50 ° C. or lower.
The pH of the acid analysis coupler slurry before adding the solution containing the diazo component is preferably in the range of 2.0 to 6.5. If the pH is less than 2.0, the reaction rate after adding the solution containing the diazo component becomes extremely slow, and if the pH exceeds 6.5, the diazo component is likely to be denatured, which is not preferable. The acid used for adjusting the pH may be any acid as long as it is soluble in water, but it is preferable to use either hydrochloric acid or acetic acid, or a mixture of hydrochloric acid and acetic acid.
The acid may be added in excess of the base equivalent of the solution containing the coupler component in advance, may be added in advance when the base is dissolved, or may be added to the diazo solution. , A required amount may be added to the acidified coupler slurry later. Further, from the viewpoint of improving the reaction rate and the dispersibility, it is preferable to heat the slurry after coupling as necessary.

When producing the pigment composition of the present invention, various additives can be used as needed. Examples of the additive include a surfactant and a resin. The additive may be used in advance in addition to a solution containing a coupler component, a solution containing a diazo component, or an acid solution for acid analysis, or may be used in addition to the slurry after the coupling reaction, or may be used in addition to the slurry after the coupling reaction. The pigment press cake obtained by filtering and washing the subsequent pigment may be added to the slurry again. Further, it may be added when a known dissolution precipitation method typified by acid pacing described later or a solvent salt milling method is performed. When added to a solution containing a coupler component, it may be added before the coupler is dissolved, or after acid analysis.

Surfactants include, for example, anionic, nonionic or amphoteric surfactants. When a surfactant is added to a solution containing a coupler component, an anionic or amphoteric surfactant is preferable. When a surfactant is added to the acid solution for acid analysis or the acid analysis coupler slurry, a nonionic surfactant is also preferable.

Anionic surfactants include, for example, fatty acid salts, alkyl sulfates, alkylaryl sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, Alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phosphate ester salt, glycerol volate Examples thereof include fatty acid ester and polyoxyethylene glycerol fatty acid ester.

Examples of amphoteric surfactants include betaine, sulfobetaine, alkylbetaine, alkylamine oxide and the like.

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid. Examples thereof include esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines and the like.
Among these, a combination of an amphoteric surfactant and an anionic surfactant is preferable.

The surfactant can be used alone or in combination of two or more.

The amount of the surfactant used is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on 100% by mass of the pigment composition.

The resin is, for example, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid alkyl ester. Copolymer, styrene-α-methylstyrene- (meth) acrylic acid copolymer, styrene-α-methylstyrene- (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, polyacrylic acid, polymethacryl Acid, vinylnaphthalene- (meth) acrylic acid copolymer, styrene- (anhydrous) maleic acid copolymer, maleic acid-maleic anhydride copolymer, vinylnaphthalene- (anhydrous) maleic acid copolymer, α-olefin- Examples thereof include (anhydrous) maleic acid copolymers, α-olefin-maleic acid alkyl ester copolymers, resins having an acid group such as polyester-modified acrylic acid polymers, acrylic copolymers and salts thereof.

The resin can be used alone or in combination of two or more.

The amount of the resin used is preferably 0.1 to 100% by mass, more preferably 1 to 50% by mass, based on 100% by mass of the pigment composition.

Examples of the compound capable of forming a salt with the resin include basic compounds such as an inorganic base and an organic base.
Inorganic bases include, for example, 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, and trisodium phosphate. Alkali metal salts of phosphoric acid, alkali metal salts of carbonic acid such as disodium carbonate, sodium hydrogen carbonate, dipotassium carbonate, alkali metal salts of boric acid such as sodium borate, ammonia;
Organic bases include, for example, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and triethylamine, aminoethanol, methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, butylaminoethanol, diethylaminoethanol, and dibutylaminoethanol. Examples thereof include alkanolamines such as diethanolamine and triethanolamine, and amines having a nonionic group such as methoxypoly (oxyethylene / oxypropylene) -2-propylamine.

The basic compound can be used alone or in combination of two or more.

A known dissolution-precipitation method typified by acid pacing can be used in the production of the pigment composition of the present invention. Specifically, pigments (CI Pigment Red 269 and CI Pigment Red 150) are dissolved in a good solvent and mixed with a large excess of a poor solvent to precipitate pigment composition particles, which are used as a solvent. The pigment composition can be produced by filtering or distilling off.

Here, the good solvent is not particularly limited as long as it can dissolve the pigment, but it is an inorganic acid (sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, hydrochloric acid, phosphoric acid, etc.), an aqueous solution thereof, and an organic acid (dichloroacetic acid, methanesulfone, etc.). Acids, etc.), inorganic bases (sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.) and their aqueous solutions, organic bases (triethylamine, diazabicycloundecene, sodium methoxydo, etc.), alcohol solvents (methanol, n-propanol, etc.) , Turt-amyl alcohol, etc.), Ketone solvents (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (tetratetra, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (dimethyl sulfoxide, hexamethylene, etc.) Sulfoxide, sulfolane, etc.), ester solvents (ethyl acetate, -n-butyl acetate, ethyl lactate, etc.), amide solvents (N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbons Solvents (toluene, xylene, etc.), aliphatic hydrocarbon solvents (octane, etc.), nitrile solvents (acetriform, etc.), halogen-based solvents (carbon tetrachloride, dichloromethane, etc.), ionic liquids (1-ethyl-3-methyl, etc.) Imidazolium tetrafluoroborate, etc.), carbon disulfide solvent, etc. can be mentioned. The amount of the good solvent used is not particularly limited as long as it can dissolve the pigment, but from the viewpoint of industrial economy, 100 to 5000 parts by mass is preferable with respect to 100 parts by mass of the pigment, and 500 to 3000 parts by mass is preferable. Is more preferable.

The temperature at which the pigment is dissolved is preferably -10 to 200 ° C, more preferably -10 to 130 ° C, and even more preferably -10 to 100 ° C.

The poor solvent is not particularly limited as long as the pigment precipitates when mixed with a solution containing a pigment dissolved in a good solvent, but an aqueous solvent (water, hydrochloric acid, sodium hydroxide aqueous solution, etc.) or the like is used. Is preferably mentioned. The amount of the poor solvent used is preferably 50 to 5000 parts by mass, more preferably 100 to 3000 parts by mass with respect to 100 parts by mass of the solution containing the pigment from the viewpoint of industrial economy.

The precipitation temperature is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and even more preferably 0 to 100 ° C.

The method for mixing the pigment solution and the poor solvent is not particularly limited, and any method may be used as long as the pigment can be completely precipitated. For example, the composite pigment particles can be precipitated by a method of injecting a pigment solution into ice water prepared in advance, a method of continuously injecting a pigment solution into running water using an device such as an aspirator, or the like.

A known solvent salt milling method can be used for producing the pigment of the present invention. Specifically, a clay-like mixture consisting of at least three components of a pigment (CI Pigment Red 269 and CI Pigment Red 150), a water-soluble inorganic salt and a water-soluble solvent is prepared using a kneader or the like. Knead strongly. The mixture after kneading is put into water and stirred with various stirrers to form a slurry. By filtering the obtained slurry, the water-soluble inorganic salt and the water-soluble solvent are removed to obtain composite pigment particles.

As the water-soluble inorganic salt, sodium chloride, sodium sulfate, potassium chloride and the like can be used. These inorganic salts are used in a range of 1 mass times or more, preferably 20 mass times or less of the pigment. When the amount of the inorganic salt is 1 mass times or more, the pigment can be sufficiently finely divided. Further, when the amount of the inorganic salt is 20 times by weight or less, a large amount of labor for removing the water-soluble inorganic salt and the water-soluble solvent after kneading is not required, and at the same time, the amount of pigment that can be processed at one time is increased. It is preferable from the viewpoint of productivity because it does not decrease.

In solvent salt milling, heat is often generated during kneading, so from the viewpoint of safety, it is preferable to use a water-soluble solvent having a boiling point of about 120 to 250 ° C. The water-soluble solvent is, for example, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Examples thereof include ether and low molecular weight polypropylene glycol.

The amount of the water-soluble solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment. By appropriately selecting the amount of the water-soluble solvent used, the kneaded product can have a viscosity suitable for the solvent salt milling treatment.

The kneading temperature at the time of solvent salt milling is preferably −10 ° C. to 300 ° C., more preferably 30 ° C. to 90 ° C. The kneading time for solvent salt milling is preferably 0.1 to 100 hours, more preferably 3 to 24 hours.

When the dissolution precipitation method and the solvent salt milling method are carried out, commercially available C.I. I. Pigment Red 269 and C.I. I. Pigment Red 150 may be used, or the pigment composition obtained by the method for synthesizing the azo pigment may be used.

In naphthol-based azo pigments, aromatic amines and coupler components often resulting from raw materials often remain in the composition, which may cause deterioration of sharpness and coloring power, and problems in printability and safety and hygiene. Therefore, it is preferable to suppress the contents of the aromatic amine and the coupler component in the pigment.
The total content of the aromatic amine is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less in 100% by mass of the pigment composition. The total content of the coupler component is preferably 30,000 ppm or less, more preferably 20,000 ppm or less, and even more preferably 10,000 ppm or less in 100% by mass of the pigment composition.

The coloring composition of the present invention includes the above pigment composition and a dispersion medium.

<Dispersed medium>
The dispersion medium is a resin and a solvent. The dispersion medium can be appropriately selected depending on the use of the coloring composition. Applications of the coloring composition include, for example, a resin composition for molding, a molded product, a toner, a pigment dispersion, a paint, a printing ink, an inkjet ink, and the like.
The coloring composition is preferably prepared by mixing the pigment composition and the dispersion medium and subjecting them to a dispersion treatment according to a method known in the art.

For the dispersion treatment, for example, a disperser such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor can be used.

The ratio of the pigment composition to the dispersion medium is preferably 0.001 to 0.7 times by mass, more preferably 0.01 to 0.6 times by mass, based on 100 parts by mass of the dispersion medium.

The resin as the dispersion medium may be, for example, a polyolefin resin, a polyester resin, a styrene copolymer, an acrylic resin, or a modified resin thereof. Specifically, polyethylenes such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), and low-density polyethylene (LDPE), polyolefin resins such as polypropylene; polyester resins such as polyethylene terephthalate; styrene-p. -Chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylate copolymer, styrene-α-chloromethylmethacrylate copolymer Polymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers , Styrene copolymers such as styrene-acrylonitrile-indene copolymers; acrylic resins such as acrylic resins and methacrylic resins; polyvinyl chlorides, phenolic resins, naturally modified phenolic resins, natural resin modified maleic acid resins, polyvinylacetates, silicones. Examples thereof include resins, polyurethanes, polyamide resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, kumaron inden resins, alkyd resins, amino resins, epoxy resins, petroleum resins, and modified resins thereof.

As the dispersion medium, the solvent may be water, an aromatic hydrocarbon-based organic solvent, or an aliphatic hydrocarbon-based organic solvent. Specifically, water such as ion-exchanged water and distilled water; aromatic hydrocarbon-based organic solvents such as toluene and xylene; aliphatic hydrocarbon-based organic solvents such as acetate-based organic solvents, ketone-based organic solvents, and alcohol-based organic solvents. Solvents can be mentioned. More specifically, acetate-based organic solvents such as butyl acetate and methyl acetate; ketone-based organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, diethylene glycol, Triethylene glycol, propylene glycol, methoxypropanol, methoxybutanol, 1-ethoxy-2-propanol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol , Glycerin, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid Examples thereof include alcohol-based organic solvents such as polypropylene glycol, butyl glycol, and butyl diglycol.

[Dye derivative]
The pigment composition and the coloring composition can contain a pigment derivative. The inclusion of a dye derivative improves the dispersion stability of the composite pigment particles.

A dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. The dye derivative is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group or a phosphoric acid group, an amine salt thereof, a sulfonamide group or a compound having a basic substituent such as a tertiary amino group at the terminal. Examples thereof include compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo. ..

The dye derivative can be used alone or in combination of two or more.

The coloring composition may contain a known material such as a dispersant.

Hereinafter, uses of the coloring composition will be illustrated.
<Resin composition for molding>
The molding resin composition of the present invention contains a coloring composition (pigment composition, resin). The molding resin composition preferably contains a thermoplastic resin in the resin. It is preferable that the molding resin composition containing the thermoplastic resin is melted and kneaded and molded into a desired shape to prepare a molded product. The resin is not limited to the thermoplastic resin.

Examples of the thermoplastic resin include homopolymers and copolymers using ethylene, propylene, butylene, styrene and the like as monomer components. More specifically, polyethylene such as high density polyethylene (HDPE), linear low density polyethylene (L-LDPE) and low density polyethylene (LDPE), and polyolefin resins such as polypropylene and polybutylene can be mentioned. Specific examples of other useful resins include polyester resins such as polyethylene terephthalate, polyamide resins such as nylon 6 and nylon 66, polystyrene resins, and thermoplastic ionomer resins. Among these, polyolefin resin and polyester resin are preferable. The number average molecular weight of the thermoplastic resin is preferably more than 30,000 and preferably 200,000 or less.

The polyolefin resin preferably has an MFR (melt flow rate, so-called melt viscosity) in the range of 0.001 to 30. When the MFR is 0.001 or more, the molding processability of the plastic molding material is good, and weld marks or flow marks are unlikely to occur on the molded body. On the other hand, when the MFR is 30 or less, excellent mechanical properties can be easily obtained in the molded product. In particular, when high density polyethylene (HDPE) is used, the MFR is preferably in the range of 0.005 to 10. When low density polyethylene (LDPE), polypropylene, or polybutene is used, the MFR is preferably in the range of 0.005 to 20.

The content of the thermoplastic resin is preferably 10,000 to 10,000,000 parts by mass, more preferably 10,000 to 2,000,000 parts by mass with respect to 100 parts by mass of the pigment composition.

The molding resin composition may contain wax. The wax is preferably a low molecular weight polyolefin. The low molecular weight polyolefin is a polymer of olefin monomers such as ethylene, propylene and butylene, and may be a block, random copolymer or terpolymer. Specifically, it is a polymer of α-olefins such as low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene (PP).

The number average molecular weight of the wax is preferably 1,000 to 30,000, more preferably 2,000 to 25,000. Within this range, the wax is appropriately transferred to the surface of the molded product, so that the balance between slidability and bleed-out suppression is excellent.

The melting point of the wax is preferably 60 to 150 ° C, more preferably 70 to 140 ° C. Within this range, the processability when the thermoplastic resin and the wax are melt-kneaded is improved.

The melt flow rate (MFR) determined in accordance with JIS K-7210 of wax is preferably larger than 100 g / 10 minutes.

The amount of wax blended is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

The molding resin composition may contain other additives. Other additives are materials generally used in the technical field of molded products, and are other than antioxidants, light stabilizers, dispersants, metal soaps, antistatic agents, flame retardants, lubricants, fillers, and the above-mentioned composite pigment particles. Coloring agents and the like.

The molding resin composition can be produced, for example, by the composition ratio of the molded product. Alternatively, it can be produced as a master batch containing a high concentration of composite pigment particles. In the present specification, the masterbatch is preferable in terms of easily uniformly dispersing the composite pigment particles in the molded product.
In the masterbatch, for example, it is preferable that the thermoplastic resin and the pigment composition are melt-kneaded and then molded into an arbitrary shape so as to be easy to use in the next step. Next, the masterbatch and the diluted resin (for example, the thermoplastic resin used in the masterbatch) are melt-kneaded to form a molded product having a desired shape. Examples of the shape of the masterbatch include pellets, powders, plates and the like. In order to prevent agglomeration of the pigment composition, it is preferable to produce a dispersion in which the pigment composition and wax are melt-kneaded in advance, and then melt-kneaded with the thermoplastic resin to produce a masterbatch. As the apparatus used for the dispersion, for example, a blend mixer, a three-roll mill, or the like is preferable.

When the molding resin composition is produced as a masterbatch, it is preferable to mix 1 to 200 parts by mass of the pigment composition with respect to 100 parts by mass of the thermoplastic resin, and more preferably 5 to 100 parts by mass. The mass ratio of the master batch (X) to the diluted resin (Y) used as the base resin of the molded product is preferably X / Y = 1/1 to 1/100, more preferably 1/3 to 2/100. .. Within this range, the composite pigment particles can be easily dispersed uniformly in the molded product, and good coloring can be easily obtained.

As the diluted resin (Y), it is preferable to use the thermoplastic resin used in the masterbatch, but if there is no problem with compatibility, another thermoplastic resin may be used.

Examples of the melt kneading include a single-screw kneading extruder, a twin-screw kneading extruder, and a tandem twin-screw kneading extruder. The melt-kneading temperature varies depending on the type of the thermoplastic resin, but is usually about 150 to 300 ° C.

Applications of the molding resin composition include, for example, molded bodies, sheets, films and the like.

Examples of the molding method include blow molding, inflation molding, extrusion molding, engel molding, vacuum molding and the like.

<Toner>
The toner of the present specification contains a coloring composition (pigment composition, resin). As the toner resin, a thermoplastic resin called a binder resin is preferable. Examples of the toner include dry toner and wet toner. Of these, dry toner is preferable. For example, in the dry toner, the pigment composition and the binder resin are melt-kneaded, cooled, and then pulverized and classified. Next, a post-treatment step of blending and mixing the additives can be performed to produce the product.

The binder resin is, for example, a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, a styrene-acrylic acid ester copolymer, or a styrene-methacrylic acid ester copolymer. , Styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene Copolymer, Styrene-Isoprene Copolymer, Styrene-Acrylonitrile-Inden Copolymer, Polyvinyl Chloride, Phenolic Resin, Naturally Modified Phenolic Resin, Natural Resin Modified Maleic Acid Resin, Acrylic Resin, Methacrylic Resin, Polyvinyl Acetate, Silicone Examples thereof include resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpen resins, kumaron inden resins, petroleum resins and the like.

Among these, polyester resins and styrene-based copolymers are preferable, and polyester resins are more preferable. Since the pigment composition of the present specification is particularly excellent in compatibility with the polyester resin, the composite pigment particles are uniformly and finely dispersed in the toner, so that a high quality toner can be obtained.

The weight average molecular weight (Mw) of the polyester resin is preferably 5,000 or more, more preferably 10,000 to 1,000,000, and even more preferably 20,000 to 100,000. When a polyester resin having an appropriate Mw is used, a toner having good offset resistance and low temperature fixability can be obtained.

The acid value of the polyester resin is preferably 10 to 60 mgKOH / g, more preferably 15 to 55 mgKOH / g. When a polyester resin having an appropriate acid value is used, it is easy to suppress the release of the release agent, and it is difficult for the image density to decrease in a high humidity environment.

The hydroxyl value of the polyester resin is preferably 20 mgKOH / g or less, more preferably 15 mgKOH / g or less. When a polyester resin having an appropriate hydroxyl value is used, the image density is unlikely to decrease in a high humidity environment. The lower limit of the hydroxyl value is 0.1 mgKOH / g.

The glass transition temperature (Tg) of the polyester resin is preferably 50 to 70 ° C, more preferably 50 to 65 ° C. Agglutination of toner can be suppressed by an appropriate Tg. Tg can be measured with a differential scanning calorimeter (device: DSC-6, manufactured by Shimadzu Corporation).

The toner can further contain a charge control agent. When a charge control agent is used, it is easy to obtain a toner having a stable charge amount. As the charge control agent, a positive or negative charge control agent can be appropriately selected and used.

When the toner is a positively chargeable toner, the positive charge control agent is, for example, a styrene dye having a niglosin dye, a triphenylmethane dye, an organic tin oxide, a quaternary ammonium salt compound, and a quaternary ammonium salt as functional groups. Examples thereof include styrene / acrylic polymers copolymerized with an acrylic resin. Among these, a quaternary ammonium salt compound is preferable. Examples of the quaternary ammonium salt compound include a salt-forming compound of a quaternary ammonium salt and an organic sulfonic acid or molybdic acid. The organic sulfonic acid is preferably naphthalene sulfonic acid.

When the toner is a negatively charged toner, the negative charge control agent is, for example, a metal complex of a monoazo dye, a styrene / acrylic polymer copolymerized with a styrene / acrylic resin using sulfonic acid as a functional group, or an aromatic hydroxycarboxylic acid. Examples thereof include metal salt compounds of the above, metal complexes of aromatic hydroxycarboxylic acids, phenolic condensates, and phosphonium-based compounds. The aromatic hydroxycarboxylic acid is preferably salicylic acid, 3,5-di-tert-butyl salicylic acid, 3-hydroxy-2-naphthoic acid, or 3-phenylsalicylic acid. Examples of the metal used for the metal salt compound include zinc, calcium, magnesium, chromium, and aluminum.

The toner can contain a release agent. Examples of the release agent include hydrocarbon waxes such as polypropylene wax, polyethylene wax and fishertroph wax, synthetic ester waxes, carnauba wax, natural ester waxes such as rice wax and the like.

If necessary, a lubricant, a fluidizing agent, an abrasive, a conductivity-imparting agent, an image peeling inhibitor, and the like can be added to the toner.

Examples of the lubricant include polyvinylidene fluoride, zinc stearate and the like. Examples of the fluidizing agent include silica, aluminum oxide, titanium oxide, silicon-aluminum co-oxide, and silicon-titanium co-oxide produced by a dry method or a wet method, and a hydrophobized product thereof. Among these, hydrophobized silica, silicon-aluminum co-oxide, and silicon-titanium co-oxide fine powder are preferable. Examples of the method for hydrophobizing these fine powders include treatment with silicone oil or a silane coupling agent such as tetramethyldisilazane, dimethyldichlorosilane, or dimethyldimethoxysilane.
Examples of the abrasive include silicon nitride, cerium oxide, silicon carbide, strontium titanate, tungsten carbide, calcium carbonate, and hydrophobized products thereof. Examples of the conductivity-imparting agent include tin oxide.

Further, in the present specification, the toner can be used as a one-component developer or a two-component developer. The two-component developer can further contain carriers.

Examples of the carrier include magnetic powders such as iron powder, ferrite powder, and nickel powder, and a product whose surface is coated with a resin or the like. The resin that coats the carrier surface is, for example, a styrene-acrylic acid ester copolymer, a styrene-methacrylate ester copolymer, an acrylic acid ester copolymer, a methacrylate ester copolymer, a fluorine-containing resin, a silicone-containing resin, and the like. Examples thereof include polyamide resin, ionomer resin, and polyphenylene sulfide resin. Among these, a silicone-containing resin in which less spent toner is formed is preferable. The weight average particle size of the carrier is preferably 30 to 100 μm.

The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner: carrier = 1: 100 to 30: 100.

<Pigment dispersion>
Since the coloring composition is used for paints, printing inks, inkjet inks, and the like, an intermediate pigment dispersion can be produced. The pigment dispersion preferably contains a pigment composition, a resin as a dispersion medium, and a solvent.

When the pigment dispersion is used for various purposes, it is preferable to prepare the pigment dispersion so that the viscosity does not easily increase and the pigment dispersion stability is excellent.
The pigment dispersion of the present invention has excellent dispersibility, low initial viscosity, crystal stability, and storage stability that cannot be obtained with a conventional pigment dispersion containing a naphthol azo pigment.

In the present specification, when the pigment dispersion is prepared as an aqueous pigment dispersion, it is preferable to use a cross-linking agent.

For example, when the resin-coated composite pigment particles in which the composite pigment particles are coated with a resin are produced, the cross-linking agent reacts with the functional groups of the resin to form a strong three-dimensional structure on the surface of the pigment particles. This improves ejection stability, for example, when used in inkjet ink applications. The temperature at which the cross-linking agent is added can be arbitrarily selected according to the reactivity of the cross-linking agent. For example, a method of adding and stirring the cross-linking agent below the reaction temperature of the cross-linking agent and the resin and then raising the temperature above the reaction temperature, a method of adding the cross-linking agent above the reaction temperature of the cross-linking agent and the resin, and the like can be mentioned. ..

Examples of the cross-linking agent include compounds having an epoxy group, an oxetanyl group, an isocyanate group, an ammonia, an amino group, a quaternary ammonium salt, a thiol group, an aziridinyl group, a carbodiimide group, an oxazoline group and the like. In particular, when the resin has a carboxy group, it is preferable to use a compound having a bifunctional or higher functional epoxy group in one molecule because it reacts with the carboxy group in the resin to form a strong three-dimensional structure. The weight average molecular weight or formula weight of the cross-linking agent is preferably 100 to 2,000, more preferably 120 to 1,500, still more preferably 150 to 1,000.

The amount of the cross-linking agent added is, for example, preferably 0.1 to 1.5 equivalents, more preferably 0.5 to 1.2 equivalents, relative to the number of moles of acid groups in the resin. It is preferable that the amount of the cross-linking agent added is within the above range because a stronger three-dimensional structure can be formed.

Examples of the epoxy compound among the cross-linking agents include Denacol EX321 and EX321L (manufactured by Nagase ChemteX Corporation).

Dispersers used to prepare aqueous pigment dispersions include, for example, horizontal sand mills, vertical sand mills, annular bead mills, attritors, microfluitizers, high speed mixers, homomixers, homogenizers, high pressure homogenizers, ball mills, paints. Examples thereof include a shaker, a roll mill, a stone mill type mill, an ultrasonic disperser, a high pressure disperser, a counter-collision type disperser, and an oblique collision type disperser. In addition, a disperser and a mixer usually used for preparing various dispersions in the art can be appropriately selected and used.

Further, before the dispersion, a treatment such as pre-dispersion using a kneader or a kneaded meat mixer such as a 3-roll mill or solid dispersion using a 2-roll mill or the like may be performed. In addition, after dispersing with various dispersers, post-treatment that is stored in a heated state at 30 to 80 ° C. for several hours to 1 week, and post-treatment using an ultrasonic disperser or a collision-type beadless disperser. Is effective for imparting dispersion stability to the pigment dispersion.

<Paint>
The paints herein contain coloring compositions (pigment compositions, resins, solvents).
Examples of the resin include thermosetting resins and thermoplastic resins. The thermosetting resin is preferably a resin having a glass transition temperature of 10 ° C. or higher. Examples of the type of thermosetting resin include acrylic resin, polyester, polyurethane and the like. Further, 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 isocyanate curing agents, epoxy curing agents, aziridine curing agents, amine curing agents and the like.
The thermoplastic resin is preferably a resin having a glass transition temperature of 30 ° C. or higher. Examples of the thermoplastic resin include nitrocellulose and polyester. The thermosetting resin and the thermoplastic resin can be used together.

Among the solvents, examples of the water-insoluble solvent include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.
Among the solvents, examples of the water-soluble solvent include water, monohydric alcohol, divalent alcohol and glycol. Examples of the water-soluble solvent include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Also, water-dilutable monoethers derived from polyhydric alcohols can be mentioned. Specific examples thereof include methoxypropanol or methoxybutanol. Further, for example, a water-dilutable glycol ether such as butyl glycol or butyl diglycol can also be mentioned. The paint is called a water-based paint when the solvent contains water as described above.

The paint can further contain known additives.

Applications of the paint include, for example, metal paints, plastic paints and the like.

<Printing ink>
The printing ink of the present specification contains a coloring composition (pigment composition, resin, solvent). The printing ink is an ink other than the injet ink, and examples thereof include an offset printing ink, a flexo printing ink, a gravure printing ink, and a color filter ink. As described above, when the solvent contains water, it is called a water-based printing ink.

Examples of the resin include rosin resin, rosin-modified phenol resin, polyurethane, nitrocellulose, acrylic resin, styrene-acrylic resin, petroleum resin and the like.

Examples of the water-insoluble solvent among the solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.

Among the solvents, water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Also included are water-dilutable monoethers derived from polyhydric alcohols. For example, methoxypropanol or methoxybutanol can be mentioned. Also included are water-dilutable glycol ethers such as butyl glycol or butyl diglycol.

The printing ink may further contain a brightening material. The bright material is particles having an average thickness of 0.5 to 10 μm and an average particle diameter of 5 to 50 μm, and examples thereof include metal flakes, mica, and coated glass flakes. Examples of the metal flakes include aluminum flakes and gold powder. Examples of mica include ordinary mica and coated mica. Examples of the coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide.

The content of the bright material is preferably 0.1 to 10% by mass in 100% by mass of the printing ink. In addition, other coloring pigments usually used in the art and various additives may be blended as required. The method for producing the printing ink, the method for applying the printing ink, and the method for drying the printing ink are not particularly limited, and a method well known in the art can be used.

The printing ink can further contain known additives.

<Inkjet ink>
The inkjet ink of the present invention preferably contains a pigment composition, a resin, and a solvent. Inkjet inks can be roughly classified into (solvent-based) inkjet inks, water-based inkjet inks, and ultraviolet-curable inkjet inks, depending on the presence or absence of a solvent and its type. Aqueous inkjet inks are preferred herein. Hereinafter, the water-based inkjet ink will be mainly described.

The content of the pigment composition is preferably 0.5 to 30% by mass, more preferably 1 to 15% by mass, based on 100% by mass of the water-based inkjet ink.

The resin used in the water-based inkjet ink is important for obtaining the fixability of the ink on the printed matter (base material).
Examples of the type of resin include acrylic resin, styrene-acrylic resin, polyester resin, polyamide resin, polyurethane resin and the like. Examples of the resin form include water-soluble resins and emulsion particles. Among these, emulsion particles are preferable. Emulsion particles include single composition particles, core-shell type particles, and the like, and can be arbitrarily selected and used. When emulsion particles are used, it is easy to reduce the viscosity of the water-based inkjet ink, and a recorded material having excellent water resistance can be easily obtained. The resin can be used by neutralizing the acidic functional group with a pH adjusting agent such as ammonia, various amines, and various inorganic alkalis, if necessary.

The resin content is preferably 2 to 30% by mass, more preferably 3 to 20% by mass, based on 100% by mass of the non-volatile content of the inkjet ink. When it is contained in an appropriate amount, the discharge stability is improved and the fixability is also improved.

Examples of the solvent include water-insoluble solvents, water, and water-soluble solvents. Examples of water-soluble solvents include glycol ethers and diols. These solvents penetrate very quickly into the substrate, and have low liquid absorption or non-absorption such as coated paper, art paper, vinyl chloride sheet, film, and cloth. It penetrates quickly even into liquid substrates. Therefore, it dries quickly at the time of printing, and accurate printing can be realized. In addition, since it has a high boiling point, it also acts as a wetting agent.

The water-soluble solvent is important for preventing drying and solidification at the nozzle portion of the printer head of the water-based inkjet ink and for obtaining ink ejection stability. Water-soluble solvents include, for example, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, Examples thereof include 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4 methylpentanone and the like.

The content of the water-soluble solvent containing water is preferably 15 to 50% by mass in 100% by mass of the inkjet ink.

Inkjet inks can further contain additives. Examples of the additive include a drying accelerator, a penetrant, a preservative, a chelating agent, a pH adjuster, a surfactant and the like.

The drying accelerator is used to accelerate the drying of the water-based inkjet ink after printing. Examples of the drying accelerator include alcohols such as methanol, ethanol and isopropyl alcohol. The content of the drying accelerator is preferably 1 to 50% by mass in 100% by mass of the water-based inkjet ink.

The penetrant is used when the substrate is a permeable material such as paper, to promote the penetration of the ink into the substrate and to accelerate the apparent drying property. Examples of the penetrant include surfactants such as polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, and sodium dioctyl sulfosuccinate, in addition to the water-soluble solvent. The amount of the penetrant used is preferably 0.1 to 5% by mass based on 100% by mass of the water-based inkjet ink. When an appropriate amount is used, printing bleeding and paper omission are unlikely to occur.

Preservatives include, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinthione-1-oxide, zinc pyridinethion-1-oxide, 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-3-one. Amine salt and the like can be mentioned. The amount of the preservative used is preferably 0.05 to 1.0% by mass in 100% by mass of the water-based inkjet ink.

The chelating agent is used to capture metal ions contained in the aqueous inkjet ink and prevent precipitation of insoluble matter in the nozzle portion or the ink. Examples of the chelating agent include ethylenediaminetetraacetic acid, a sodium salt of ethylenediaminetetraacetic acid, a diammonium salt of ethylenediaminetetraacetic acid, and a tetraammonium salt of ethylenediaminetetraacetic acid. The amount of the chelating agent used is preferably 0.005 to 0.5% by mass in 100% by mass of the water-based inkjet ink.

Examples of the pH adjuster include various amines, inorganic salts, ammonia, various buffer solutions and the like.

Inkjet ink is produced by blending and mixing each material. After mixing, it is preferable to perform filtration to remove coarse particles. Examples of the mixing include a stirrer using wings, various dispersers, an emulsifier and the like. The order of addition of each material and the mixing method are arbitrary.

Inkjet ink is preferably filtered. As a result, the ejection property from the inkjet printer is improved. A known method can be used for filtration.

As the inkjet ink of the present specification, various inkjet methods can be used. Examples of the inkjet method include a charge control type, a continuous injection type such as a spray type, a piezo method, a thermal method, and an electrostatic suction method.

Preservatives are used to prevent the growth of mold and bacteria. The type of preservative is not particularly limited, but for example, sodium dehydroacetate, sodium benzoate, sodiumpyridinthione-1-oxide, zincpyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, 1- Examples thereof include an amine salt of benzisothiazolin-3-one. These are preferably used in the range of 0.1 to 2% by mass based on the total mass of the pigment dispersion.

A pH regulator is used to adjust the pH to the desired value. The type of the pH adjuster is not particularly limited, and examples thereof include basic compounds such as various organic bases and inorganic bases, acidic compounds such as hydrochloric acid, sulfuric acid, and phosphoric acid, and various buffer solutions. As the basic compound, for example, those described above can be used.

Antifoaming agents are used to prevent the generation of foam during manufacturing. The type of defoaming agent is not particularly limited, and a commercially available product can also be used. For example, Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol 104BC, Surfinol 104DPM, Surfinol 104PA, Surfinol 104PG-50, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol 485, Surfinol. PSA-336 (all manufactured by Nisshin Kagaku Kogyo Co., Ltd.), ADDITOLVXW 6211, ADDITOLVXW4973, ADDITOR VXW6235, ADDITOLXW375, ADDITOR XW376, ADDITORVXW6381, ADDITORVXW6381, ADDITOR VXW6386, ADDITORVXW63 Can be mentioned.

Wetting agents are used to improve pigment dispersion. A smooth coating film can be easily obtained by the wetting agent. The type of wetting agent is not particularly limited, and a commercially available product can also be used. For example, ADDITORVXL6237N, ADDITOR XL260N, ADDITORVXL6212, ADDITOR UVX7301 / 65, ADDITOR XW330, ADDITOR VXW6200, ADDITORVXW6205, ADDITORLVXW6324, ADDITORLVXW6394, ADDITORLVXW6208, ADDITORLVXW6208

In the production of inkjet ink, the method of mixing the raw materials can be carried out by using a high-speed disperser, an emulsifier, or the like, in addition to a normal stirrer using blades. At that time, the order of adding the raw materials, the mixing method, and the like are arbitrary.

The inkjet inks described herein can be suitably used for various inkjet printers. The applicable inkjet method is not particularly limited, and examples thereof include a charge control type, a continuous injection type such as a spray type, a piezo method, a thermal method, and an electrostatic suction method.

The inkjet ink of the present invention can be particularly suitably used as a magenta color, and other colors (cyan color, yellow color, black color, white color, red color, green color, blue color, orange color, pink color, gold color) can be used. , Silver color, bronze color, etc.) can be used as an ink set. The ink set is, for example, a four-color ink set in which cyan, yellow, and black are added to the magenta color using the inkjet ink of the present invention, and special colors such as orange, red, and green are added. It can be suitably used as an ink set of 5 or more colors. The pigment concentration, viscosity, dynamic viscoelasticity, surface tension, coating order, evaporation rate of volatile matter, etc. of each ink are design items, and can be appropriately adjusted according to the desired characteristics.

Inkjet ink is preferably filtered. As a result, the ejection property from the inkjet printer is improved. For filtration, any conventionally known method can be adopted.

The inkjet ink of the present invention can be applied to various conventionally known substrates. The base material is, for example, a highly water-absorbent base material such as plain paper, cloth, or knit, a low water-absorbent base material such as art paper, coated paper, vinyl chloride, wood, concrete, polyethylene film, polypropylene film, or polyethylene terephthalate film. Examples thereof include non-water-absorbent base materials such as metals (aluminum, stainless steel, etc.).

Hereinafter, the present invention will be described based on examples. The present invention is not limited to these. In Examples and Comparative Examples, "parts" and "%" mean "parts by mass" and "% by mass".

<Manufacturing of pigment composition>
(Example 1) Production of Pigment Composition 1 24.2 parts of 3-amino-4-methoxybenzanilide was added to 294 parts of water as a base component, and the mixture was stirred to prepare a suspension, and 137 parts of ice was further added. The temperature was adjusted to 5 ° C. or lower. 31.6 parts of 35% hydrochloric acid was added thereto, and the mixture was stirred for 30 minutes. Then, 7.1 parts of sodium nitrite was added to 14 parts of water, a prepared aqueous solution was added, and the mixture was stirred for 1 hour to diazotize. Two parts of sulfamic acid was added to the reaction mixture to eliminate nitrite. A buffer solution consisting of a mixed solution of 36.5 parts of a 25% aqueous sodium hydroxide solution, 36.5 parts of ice, and 37.7 parts of 80% acetic acid was added thereto to prepare a solution containing a diazo component.

On the other hand, N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2- as a coupler component while heating a mixture of 133.6 parts of water and 32.6 parts of a 25% aqueous sodium hydroxide solution to 85 ° C. 30.1 parts of naphthamide and 1.9 parts of 3-hydroxy-2-naphthamide were added and dissolved. To this, 66.8 parts of ice was added and cooled to prepare a coupler solution. This solution was added to a solution containing a diazo component over 20 minutes to carry out a coupling reaction.

After stirring for 1 hour, the slurry was heated to 30 ° C. and further stirred for 30 minutes. The slurry was further heated to 50 ° C., stirred for 30 minutes, filtered and washed with water to obtain a pigmented press cake. The press cake was dried under the conditions of 90 ° C. for 18 hours and then pulverized to obtain 154.4 parts of a pigment composition.

(Example 2) Production of Pigment Composition 2 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (30.1 parts) and 3-hydroxy-2-naphthamide (1.9 parts) were added to N-. -(5-Chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 26.7 parts, 3-hydroxy-2-naphthamide 3.8 parts The same procedure as in Example 1 was carried out, except that the pigment was changed to 3-hydroxy-2-naphthamide. Composition 2 53.0 parts was obtained.

(Example 3) Production of Pigment Composition 3 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (30.1 parts) and 3-hydroxy-2-naphthamide (1.9 parts) were added to N-. -(5-Chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 23.4 parts and 3-hydroxy-2-naphthamide 5.7 parts were changed in the same manner as in Example 1 to carry out the pigment. 51.7 parts of the composition was obtained.

(Example 4) Production of Pigment Composition 4 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (30.1 parts) and 3-hydroxy-2-naphthamide (1.9 parts) were added to N-. -(5-Chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 20.1 parts and 3-hydroxy-2-naphthamide 7.6 parts were changed in the same manner as in Example 1 to carry out the pigment. Composition 4 500.3 parts was obtained.

(Example 5) Production of Pigment Composition 5 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (30.1 parts) and 3-hydroxy-2-naphthamide (1.9 parts) were added to N-. -(5-Chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 16.7 parts, 3-hydroxy-2-naphthamide 9.5 parts The same procedure as in Example 1 was carried out, except that the pigment was changed to 3-hydroxy-2-naphthamide. 5 49.0 parts of the composition was obtained.

(Example 6) Production of Pigment Composition 6 Example except that 2.7 parts of Neoperex G-15 (manufactured by Kao Corporation, anionic surfactant) is added as an additive when preparing the coupler solution. In the same manner as in No. 3, 52.7 parts of the pigment composition was obtained.

(Example 7) Production of Pigment Composition 7 Except for adding 2.7 parts of electro stripper F (manufactured by Kao Corporation, anionic surfactant) as an additive when preparing the coupler solution, the same as in Example 3. The same procedure was carried out to obtain 7 52.7 parts of the pigment composition.

(Example 8) Production of Pigment Composition 8 The same as in Example 3 except that 2.7 parts of Anchor 20BS (manufactured by Kao Corporation, amphoteric surfactant) is added as an additive when preparing the coupler solution. This was carried out to obtain 8 52.7 parts of a pigment composition.

Example 9 Production of Pigment Composition 9 Examples except that 11.0 parts of Joncryl HPD 96 (manufactured by BASF, styrene-acrylic acid copolymer) was added as an additive when preparing the coupler solution. The same procedure as in No. 3 was carried out to obtain 9 55.5 parts of the pigment composition.

(Example 10) Production of pigment composition 10 The pigment press cake before drying of Example 3 was added to 600 parts of water to form a slurry, and Joncryl HPD 96 (manufactured by BASF, styrene-acrylic acid copolymer) was used as an additive. 11.0 parts were added and the mixture was stirred for 1 hour. 9.6 parts of 80% acetic acid was added thereto, and the mixture was stirred for 30 minutes, filtered, and washed with water to obtain a pigmented press cake. The press cake was dried under the conditions of 90 ° C. for 18 hours and then pulverized to obtain 1055.5 parts of a pigment composition.

(Example 11) Production of pigment composition 11 24.2 parts of 3-amino-4-methoxybenzanilide was added to 224 parts of water as a base component, and the mixture was stirred to prepare a suspension, and 137 parts of ice was further added. The temperature was adjusted to 5 ° C. or lower. 31.6 parts of 35% hydrochloric acid was added thereto, and the mixture was stirred for 30 minutes. Then, 7.1 parts of sodium nitrite was added to 14 parts of water, a prepared aqueous solution was added, and the mixture was stirred for 1 hour to diazotize. Two parts of sulfamic acid was added to the reaction mixture to eliminate nitrite. A buffer solution consisting of a mixture of 36.5 parts of a 25% aqueous sodium hydroxide solution, 106.5 parts of dimethyl sulfoxide, and 37.7 parts of 80% acetic acid was added thereto to prepare a solution containing a diazo component.

On the other hand, N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 23.4 as a coupler component in a mixture of 100 parts of water, 100 parts of dimethyl sulfoxide and 32.6 parts of a 25% aqueous sodium hydroxide solution. Part, 5.7 parts of 3-hydroxy-2-naphthamide were added and dissolved to prepare a coupler solution. This solution was added to a solution containing a diazo component over 20 minutes to carry out a coupling reaction.

After stirring for 1 hour, the slurry was heated to 30 ° C. and further stirred for 30 minutes. The slurry was further heated to 50 ° C., stirred for 30 minutes, filtered and washed with water to obtain a pigmented press cake. This press cake was dried under the conditions of 90 ° C. for 18 hours and then pulverized to obtain 11 51.7 parts of a pigment composition.

(Example 12) Production of Pigment Composition 12 51.7 parts of Pigment Composition 12 was carried out in the same manner as in Example 11 except that dimethyl sulfoxide was changed to acetone when preparing the solution containing the diazo component and the coupler solution. Got

(Example 13) Production of pigment composition 13 The same procedure as in Example 11 was carried out except that dimethyl sulfoxide was changed to methanol when preparing the solution containing the diazo component and the coupler solution, and the pigment composition 13 51.7 parts. Got

(Example 14) Production of pigment composition 14 24.2 parts of 3-amino-4-methoxybenzanilide was added to 294 parts of water as a base component, and the mixture was stirred to prepare a suspension, and 137 parts of ice was further added. The temperature was adjusted to 5 ° C. or lower. 31.6 parts of 35% hydrochloric acid was added thereto, and the mixture was stirred for 30 minutes. Then, 7.1 parts of sodium nitrite was added to 14 parts of water, a prepared aqueous solution was added, and the mixture was stirred for 1 hour to diazotize. Two parts of sulfamic acid was added to the reaction mixture to eliminate nitrite to prepare a solution containing a diazo component.
Further, 33.7 parts of an 80% acetic acid aqueous solution and 550 parts of water were placed in a coupling tank and stirred to obtain an acetic acid aqueous solution.

On the other hand, N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2- as a coupler component while heating a mixture of 133.6 parts of water and 32.6 parts of a 25% aqueous sodium hydroxide solution to 85 ° C. 23.4 parts of naphthamide and 5.7 parts of 3-hydroxy-2-naphthamide were added and dissolved. 66.8 parts of water was added thereto to prepare a coupler solution. This solution was added to a coupling tank for stirring an aqueous acetic acid solution over 30 minutes and acidified to obtain an acid analysis coupler slurry. A solution containing a diazo component was added to the acid analysis coupler slurry over 20 minutes, and a coupling reaction was carried out.

After stirring for 1 hour, the slurry was heated to 30 ° C. and further stirred for 30 minutes. The slurry was further heated to 50 ° C., stirred for 30 minutes, filtered and washed with water to obtain a pigmented press cake. This press cake was dried under the conditions of 90 ° C. for 18 hours and then pulverized to obtain 14 51.7 parts of a pigment composition.

Example 15 Production of Pigment Composition 15 Example except that 2.7 parts of Neoperex G-15 (manufactured by Kao Corporation, anionic surfactant) is added as an additive when preparing the coupler solution. The same procedure as in No. 14 was carried out to obtain 52.7 parts of the pigment composition.

(Example 16) Production of Pigment Composition 16 Except for adding 2.7 parts of electro stripper F (manufactured by Kao Corporation, anionic surfactant) as an additive when preparing the coupler solution, the same as in Example 14. The same procedure was carried out to obtain 16 52.7 parts of the pigment composition.

(Example 17) Production of Pigment Composition 17 The same as in Example 14 except that 2.7 parts of Anchor 20BS (manufactured by Kao Corporation, amphoteric surfactant) is added as an additive when preparing the coupler solution. This was carried out to obtain 52.7 parts of the pigment composition.

(Example 18) Production of pigment composition 18 24.2 parts of 3-amino-4-methoxybenzanilide was added to 294 parts of water as a base component, and the mixture was stirred to prepare a suspension, and 137 parts of ice was further added. The temperature was adjusted to 5 ° C. or lower. 31.6 parts of 35% hydrochloric acid was added thereto, and the mixture was stirred for 30 minutes. Then, 7.1 parts of sodium nitrite was added to 14 parts of water, a prepared aqueous solution was added, and the mixture was stirred for 1 hour to diazotize. Two parts of sulfamic acid was added to the reaction mixture to eliminate nitrite. A buffer solution consisting of a mixed solution of 36.5 parts of a 25% aqueous sodium hydroxide solution, 36.5 parts of ice, and 37.7 parts of 80% acetic acid was added thereto to prepare a solution containing a diazo component.

On the other hand, while heating a mixture of 93.6 parts of water and 22.8 parts of a 25% aqueous sodium hydroxide solution to 85 ° C., N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2 was used as a coupler component. −30.1 parts of −naphthamide was added and melted, and 46.8 parts of ice was added thereto and cooled to obtain a coupler solution A. In a separate container, 1.9 parts of 3-hydroxy-2-naphthamide was added to a mixture of 60 parts of water and 9.8 parts of a 25% aqueous sodium hydroxide solution and dissolved to obtain a coupler solution B. The prepared coupler solution A was added over 20 minutes to the solution containing the diazo component, and then the coupler solution B was added over 10 minutes to carry out a coupling reaction.

After stirring for 1 hour, the slurry was heated to 30 ° C. and further stirred for 30 minutes. The slurry was further heated to 50 ° C., stirred for 30 minutes, filtered and washed with water to obtain a pigmented press cake. This press cake was dried under the conditions of 90 ° C. for 18 hours and then pulverized to obtain 18 51.7 parts of a pigment composition.

(Example 19) Production of pigment composition 19 24.2 parts of 3-amino-4-methoxybenzanilide was added to 224 parts of water as a base component, and the mixture was stirred to prepare a suspension, and 137 parts of ice was further added. The temperature was adjusted to 5 ° C. or lower. 31.6 parts of 35% hydrochloric acid was added thereto, and the mixture was stirred for 30 minutes. Then, 7.1 parts of sodium nitrite was added to 14 parts of water, a prepared aqueous solution was added, and the mixture was stirred for 1 hour to diazotize. Two parts of sulfamic acid was added to the reaction mixture to eliminate nitrite. A buffer solution consisting of a mixture of 36.5 parts of a 25% aqueous sodium hydroxide solution, 106.5 parts of dimethyl sulfoxide, and 37.7 parts of 80% acetic acid was added thereto to prepare a solution containing a diazo component.

On the other hand, in a mixture of 70 parts of water, 70 parts of dimethyl sulfoxide and 22.8 parts of a 25% aqueous sodium hydroxide solution, N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 23. Four parts were added and dissolved to prepare a coupler solution A. In a separate container, 5.7 parts of 3-hydroxy-2-naphthamide was added to a mixture of 30 parts of water, 30 parts of dimethyl sulfoxide, and 9.8 parts of a 25% sodium hydroxide aqueous solution to dissolve it, and the coupler solution B was dissolved. And said. The prepared coupler solution A was added over 20 minutes to the solution containing the diazo component, and then the coupler solution B was added over 10 minutes to carry out a coupling reaction.

After stirring for 1 hour, the slurry was heated to 30 ° C. and further stirred for 30 minutes. The slurry was further heated to 50 ° C., stirred for 30 minutes, filtered and washed with water to obtain a pigmented press cake. This press cake was dried under the conditions of 90 ° C. for 18 hours and then pulverized to obtain 19 51.7 parts of a pigment composition.

(Example 20) Production of Pigment Composition 20 51.7 parts of Pigment Composition 20 was carried out in the same manner as in Example 19 except that dimethyl sulfoxide was changed to acetone when preparing the solution containing the diazo component and the coupler solution. Got

(Example 21) Production of Pigment Composition 21 51.7 parts of Pigment Composition 21 was carried out in the same manner as in Example 19 except that dimethyl sulfoxide was changed to methanol when preparing the solution containing the diazo component and the coupler solution. Got

(Comparative Example 1) Production of Pigment Composition 22 (CI Pigment Red 269) N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 30.1 parts, 3-hydroxy-2 The same procedure as in Example 1 was carried out except that 1.9 parts of −naphthamide was changed to 33.4 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide, and the pigment composition 22 (CI Pigment Red 269) 55.5 copies were obtained.

(Comparative Example 2) Production of Pigment Composition 23 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (30.1 parts) and 3-hydroxy-2-naphthamide (1.9 parts) were added to N-. -(5-Chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 31.8 parts, 3-hydroxy-2-naphthamide 1.0 part, the same as in Example 1 except that the pigment was changed. Composition 23 55.0 parts was obtained.

(Comparative Example 3) Production of Pigment Composition 24 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (30.1 parts) and 3-hydroxy-2-naphthamide (1.9 parts) were added to N-. -(5-Chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 13.4 parts and 3-hydroxy-2-naphthamide 11.5 parts were changed in the same manner as in Example 1 to carry out the pigment. 24 47.6 parts of the composition was obtained.

(Comparative Example 4) Production of Pigment Composition 25 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (30.1 parts) and 3-hydroxy-2-naphthamide (1.9 parts) were added to N-. Except for changing to 23.4 parts of-(5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide and 9.4 parts of N- (3-nitrophenyl) -3-hydroxy-2-naphthamide. The same procedure as in Example 1 was carried out to obtain 25 55.1 parts of the pigment composition.

(Comparative Example 5) Production of Pigment Composition 26 30.1 parts of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide and 1.9 parts of 3-hydroxy-2-naphthamide were added to 3 parts. The same procedure as in Example 1 was carried out except that the changes were made to 9.5 parts of −hydroxy-2-naphthamide and 15.7 parts of N- (3-nitrophenyl) -3-hydroxy-2-naphthamide, and the pigment composition 26 48 was carried out. I got 0.0 copies.

(Comparative Example 6) Production of Pigment Composition 27 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (30.1 parts) and 3-hydroxy-2-naphthamide (1.9 parts) were added to N-. -(5-Chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 23.4 parts, N- (4-chloro-2,5-dimethoxyphenyl) -3-hydroxy-2-naphthamide 10.9 parts The procedure was carried out in the same manner as in Example 1 except that the pigment composition was changed to 27 56.6 parts.

(Comparative Example 7) Production of Pigment Composition 28 N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide (30.1 parts) and 3-hydroxy-2-naphthamide (1.9 parts) were added to N-. -(5-Chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide 23.4 parts, N- (2-methyl-5-chlorophenyl) -3-hydroxy-2-naphthamide 9.5 parts Except for the above, the same procedure as in Example 1 was carried out to obtain 55.2 parts of the pigment composition.

(Example 22) Production of pigment composition 29 35 parts of the pigment composition 22 obtained in Comparative Example 1 was added to 1000 parts of 98% sulfuric acid, C.I. I. Pigment Red 150 (Toshiki Red 150TR, manufactured by Tokyo Color Materials Industry Co., Ltd.) was gradually added with stirring, and stirred for 4 hours to dissolve. Then, the solution was gradually added dropwise to 8000 parts of water at 10 ° C. over 30 minutes while stirring, and the cake was filtered and washed to obtain a pigmented press cake. The press cake was dried under the conditions of 90 ° C. for 18 hours and then pulverized to obtain 29 47.5 parts of the pigment composition.

(Example 23) Production of Pigment Composition 30 70 parts of the pigment composition 22 obtained in Comparative Example 1, C.I. I. 30 parts of Pigment Red 150 (manufactured by Tokyo Color Materials Industry Co., Ltd., Toshiki Red 150TR), 1000 parts of sodium chloride, and 150 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) for 8 hours at 60 ° C. h) Kneaded. Next, the kneaded mixture was put into warm water at about 70 ° C., stirred for 1 hour to form a slurry, filtered and washed to obtain a pigmented press cake. The press cake was dried under the conditions of 90 ° C. for 18 hours and then pulverized to obtain 30 97.5 parts of a pigment composition.

(Comparative Example 8) Production of Pigment Composition 31 75 parts of the pigment composition 22 obtained in Comparative Example 1, C.I. I. Pigment Red 150 (Toshiki Red 150TR, manufactured by Tokyo Color Materials Industry Co., Ltd.) was mixed with a high-speed stirring disper to obtain 31 99.9 parts of a pigment composition.

The X-ray diffraction of the obtained pigment composition was measured to evaluate the crystalline state.

(Powder X-ray diffraction measurement method)
The powder X-ray diffraction measurement was carried out in accordance with the Japanese Industrial Standards JIS K0131 (general rule of X-ray diffraction analysis), and the diffraction angle (2θ) was measured in the range of 3 ° to 35 ° using CuKα rays.

The measurement conditions were as follows.
X-ray diffractometer: RINT2100 manufactured by Rigaku
Sampling width: 0.02 °
Scan speed: 2.0 ° / min
Divergence slit: 1 °
Divergence vertical restriction slit: 10 mm
Scattering slit: 2 °
Light receiving slit: 0.3 mm
Tube: Cu
Tube voltage: 40kV
Tube current: 40mA

The following example of powder X-ray diffraction measurement is shown in the figure. Example 3 is shown in FIG. 1, Comparative Example 1 is shown in FIG. 2, C.I. I. Pigment Red 150 (manufactured by Tokyo Color Materials Industry Co., Ltd., Toshiki Red 150TR) is shown in FIG. 3, and Comparative Example 8 is shown in FIG.

The contents of the produced pigment composition are shown in Table 1. The content in the table is a numerical value calculated from the amount of raw materials used.

The pigment compositions of Examples 1 to 23 were solid solutions, and composite pigment particles were formed. In the table, PR is C.I. I. Abbreviation for Pigment Red.

<Coloring composition and its characteristic evaluation>
Using the obtained pigment composition, coloring compositions for various purposes were prepared and their characteristics were evaluated.

-Forming resin composition 1. Preparation of Molding Resin Composition and Preparation of Molded Body (Example A-1) Preparation of Molded Body a-1
Two parts of the obtained pigment composition 1 and 1000 parts of polypropylene resin (product name: Prime Polypro J105, manufactured by Prime Polymer Co., Ltd.) were melt-kneaded at 220 ° C. using a twin-screw extruder, and then cut with a pelletizer. A pellet-shaped molding resin composition was obtained. Next, the molding resin composition is injection-molded using an injection molding machine in which the injection conditions are set to a molding temperature of 220 ° C. and a mold temperature of 40 ° C., and a molded body a-1 (plate) having a thickness of 1 mm is obtained. Got

(Examples A-2 to A-23, Comparative Examples A-1 to A-8) Preparation of Molds a-2 to a-31 The pigment composition 1 of Example A-1 was changed as shown in Table 2. Except for the above, the same procedure as in Example A-1 was carried out to obtain molded products a-2 to a-31.

(Example A-24) Preparation of molded product a-32 Two parts of the obtained pigment composition 1 and 1000 parts of a polyethylene terephthalate resin (product name: Vylope EMChaihun 307, manufactured by Toyo Spinning Co., Ltd.) were 275 by a twin-screw extruder. It was melt-kneaded at ° C. and then cut with a pelletizer to obtain a pellet-shaped resin composition for molding. Next, the molding resin composition was injection-molded using an injection molding machine in which the injection conditions were set to a molding temperature of 275 ° C. and a mold temperature of 85 ° C. to obtain a molded product (plate) having a thickness of 3 mm.

(Examples A-25 to A-46, Comparative Examples A-9 to A-16) Preparation of Molds a-33 to a-62 The pigment composition 1 of Example A-24 was changed as shown in Table 3. Except for the above, the same procedure as in Example A-24 was carried out to obtain molded products a-33 to a-62.

2. Evaluation of molded product (dispersibility)
Each molded product produced was visually observed to confirm the presence or absence of coarse particles. The results are shown in Tables 2 and 3.

(Clarity)
Each molded product produced was visually observed and evaluated according to the following criteria. The results are shown in Tables 2 and 3.
〇: A brighter red color than the molded products (a-22 and a-53) produced in Comparative Examples A-22 and A-53 Δ: The molded products produced in Comparative Examples A-22 and A-53 (a-22) And a-53) equivalent red x: a dull red color than the molded articles (a-22 and a-53) produced in Comparative Examples A-22 and A-53.

From the results of Tables 2 and 3, the molded articles of Examples A-1 to A-44 had no coarse particles and had good dispersibility. The sharpness is also good.

-Toner (Example B-1)
2500 parts of the obtained pigment composition 3 and 2500 parts of a polyester resin (product name: M-325, manufactured by Sanyo Chemical Industries, Ltd.) were mixed and kneaded in a pressure kneader. Mixing and kneading were carried out at a set temperature of 120 ° C. for 15 minutes. Next, the obtained kneaded product was taken out from the pressure kneader, and further kneaded using three rolls having a roll temperature of 95 ° C. The obtained kneaded product was cooled and then roughly pulverized to 10 mm or less to obtain a colored composition.
500 parts of the obtained coloring composition, 4375 parts of the above polyester resin, 50 parts of a calcium salt compound (charge control agent) of 3,5-di-tert-butylsalicylic acid, and an ethylene homopolymer (release agent, molecular weight 850, Mw). / Mn = 1.08, melting point 107 ° C.) 75 parts are mixed (3000 rpm, 3 minutes) using a Henschel mixer having a volume of 20 L, and further at a discharge temperature of 120 ° C. using a twin-screw kneading extruder. Melt kneading was performed. Then, the kneaded product was cooled and solidified, and then coarsely pulverized with a hammer mill. Next, the obtained coarsely pulverized product was finely pulverized using a type I jet mill (IDS-2 type) and then classified to obtain toner matrix particles.
Next, 2500 parts of the toner mother particles obtained above and 12.5 parts of hydrophobic titanium oxide (STT-30A manufactured by Titan Kogyo Co., Ltd.) were mixed with a 10 L Henschel mixer to obtain a negatively charged toner 1.

On the other hand, as a comparison target, a negatively charged toner 2 was obtained in the same manner as in Example A-35, except that the pigment composition 3 was changed to the pigment composition 22.
The obtained negatively charged toner 1 and negatively charged toner 2 were each sliced to a thickness of 0.9 μm using a microtome to form a sample. Next, the dispersed state of the pigment was observed for each sample using a transmission electron microscope. As a result, it was found that the pigment was uniformly distributed in the negatively charged toner 1 using the pigment composition 3 and the dispersibility was higher than that in the negatively charged toner 2 using the pigment composition 22.

<3> Coloring composition 1. Adjustment of Coloring Composition (Example C-1) Adjustment of Coloring Composition 1 First, the following raw materials and 230 parts of steel beads were placed in a 225 ml glass bottle, and a paint shaker manufactured by Red Devil Co., Ltd. was used for 60 minutes. It was dispersed to give a mixture.
-Pigment composition 1:19 parts-Acrylic resin (DIC, Acrydic 47-712): 7.7 parts-Dispersion solvent (toluene: xylene: butyl acetate: ENEOS T-SOL150 FLUID) has a mass ratio of 3 : 3: 2: 2 mixed solvent): 40.7 parts Next, 75.4 parts of acrylic 47-712 and 17.2 parts of melamine resin (Amidia L-117-60 manufactured by DIC) were added to the above mixture. In addition, the mixture was further dispersed for 10 minutes to obtain a dispersion liquid.
Then, the steel beads were removed from the dispersion to obtain a coloring composition 1.

(Examples C-2 to C-23, Comparative Examples C-1 to C-8) Adjustment of Coloring Compositions c-2 to c-31 The pigment composition 1 of Example C-1 is as shown in Table 4. The same procedure as in Example C-1 was carried out except for the modification, to obtain coloring compositions c-2 to c-31.

2. Evaluation of coloring composition (crystal stability)
In order to evaluate the crystal stability (effect of suppressing crystal growth), first, the average primary particle size of the pigment particles in each coloring composition was measured. In the measurement method, the coloring composition was dropped onto a mesh covered with a support film, and the dried product was used as a sample. Next, the particles of the sample were photographed with a transmission electron microscope (H-7650 type transmission electron microscope manufactured by Hitachi High-Technologies Corporation), and the longer one of the 50 primary particles of the pigment constituting the secondary aggregate was photographed. The diameter (major axis) of each was measured. A value obtained by averaging them was calculated, and the value was taken as the average primary particle size. The prepared coloring composition was sealed in a screw cap bottle, stored at 50 ° C. for 1 week, and then the same measurement was performed, and the crystal stability was evaluated by the change in the average primary particle size before and after storage. The results are shown in Table 4.

-Water-based coloring composition 1. Preparation of water-based coloring composition (Example D-1) Preparation of water-based coloring composition d-1 The following raw materials and 70 parts of 1.25 mm diameter zirconia beads were placed in a 70 ml glass bottle, and a paint shaker manufactured by Red Devil Co., Ltd. was used. The mixture was dispersed over 60 minutes using a dispersion to obtain a dispersion.
-Pigment composition 1: 3.15 parts-Polyester-modified acrylic acid polymer (made by Allnex, ADDITOR XW 6528): 5.25 parts-Wetting agent (manufactured by Allnex, ADDITOR XW 6374): 0.95 parts-Disappearing Foaming agent (ADDITOR XW 6211 manufactured by Allnex): 0.63 parts, ion-exchanged water: 21.52 parts Next, zirconia beads were removed from the above dispersion liquid to obtain an aqueous coloring composition d-1.

(Examples D-2 to D-23, Comparative Examples D-1 to D-8) Adjustment of water-based coloring compositions d-2 to d-31 The pigment composition 1 of Example D-1 is as shown in Table 5. The same procedure as in Example D-1 was carried out except that the composition was changed to D-2 to obtain aqueous coloring compositions d-2 to d-31.

2. Evaluation of water-based coloring composition (initial viscosity and viscosity stability)
The initial viscosity of the obtained water-based coloring composition at 25 ° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosities after aging at 25 ° C. for 1 week and after accelerating at 50 ° C. for 1 week were measured. Based on the obtained measured values, the rate of increase in viscosity with respect to the initial viscosity was calculated, used as an index of viscosity stability, and evaluated according to the following evaluation criteria. The results are shown in Table 5. The lower the initial viscosity, the better the dispersibility. Further, the smaller the viscosity increase rate, the better the dispersion stability. If it is "4", "3" and "2" in the following evaluation criteria, it is a practical level.

(Evaluation criteria for initial viscosity)
4. The initial viscosity is less than 5.0 mPa · s. Very good 3. The initial viscosity is 5.0 mPa · s or more and less than 7.5 mPa · s. Good 2. The initial viscosity is 7.5 mPa · s or more and less than 10.0 mPa · s. Practical use 1. The initial viscosity is 10.0 mPa · s or more. Impractical

(Evaluation criteria for viscosity stability)
4. The viscosity increase rate is less than 20%. Very good 3. The viscosity increase rate is 20% or more and less than 30%. Good 2. The viscosity increase rate is 30% or more and less than 40%. Practical use 1. The viscosity increase rate is 40% or more. Impractical

・ Water-based paint 1. Adjustment of water-based paint (Example E-1)
The following raw materials were stirred using a high-speed stirrer to obtain water-based paint 1 (stored at 25 ° C. for 1 week).
-Water-based coloring composition d-1 (stored at 25 ° C. for 1 week): 1.4 parts-Acrylic resin (manufactured by DIC, Burnock WD-304): 13.6 parts-Melamine resin (manufactured by Allnex, Cymel 325): 3.4 copies

The following raw materials were stirred using a high-speed stirrer to obtain water-based paint 2 (stored at 50 ° C. for 1 week).
-Water-based coloring composition d-1 (stored at 50 ° C. for 1 week): 1.4 parts-Acrylic resin (manufactured by DIC, Burnock WD-304): 13.6 parts-Melamine resin (manufactured by Allnex, Cymel 325): 3.4 copies

The obtained water-based paint 1 and water-based paint 2 were coated on a commercially available polyethylene terephthalate (PET) film having a thickness of 100 μm using a 7 mil applicator. After the coating, the PET film was dried at room temperature for 18 hours. Then, it was dried at 60 ° C. for 5 minutes and at 140 ° C. for 20 minutes to obtain a coating film e-1.

(Examples E-2 to E-23, Comparative Examples E-1 to E-8) Preparation of water-based paint and preparation of coating films e-2 to e-31 Water-based coloring composition d-1 of Example E-1 Was changed as shown in Table 6, and the same procedure as in Example E-1 was carried out to obtain coating films e-2 to e-31.

2. Evaluation of coating film (stable hue)
Using a colorimeter (manufactured by Konica Minolta, CM-700d), measure the color of the coating film stored at 25 ° C for 1 week and the coating film stored at 50 ° C for 1 week, and obtain the color difference (ΔE *) as follows. Judging by the standard. The results are shown in Table 6. The smaller the color difference, the better the dispersion stability of the paint. If it is "4", "3" and "2" in the following evaluation criteria, it is a practical level.
(Hue stability evaluation criteria)
4. ΔE * is less than 1.0.
3. 3. ΔE * is 1.0 or more and less than 2.0.
2. ΔE * is 2.0 or more and less than 3.0.
1. 1. ΔE * is 3.0 or more.

(Coloring power)
The coating film stored at 25 ° C. for 1 week was visually observed and evaluated according to the following criteria. The results are shown in Table 6.
(Evaluation criteria for coloring power)
〇: The reflection density is higher than that of the coated material (e-22) produced in Comparative Example E-1 Δ: Equivalent to the coated material (e-22) produced in Comparative Example E-1 ×: In Comparative Example E-1 The reflection density is lower than that of the produced painted product (e-22).

(Clarity)
The coating film stored at 25 ° C. for 1 week was visually observed and evaluated according to the following criteria. The results are shown in Table 6.
(Evaluation criteria for sharpness)
〇: Brighter red than the coated product (e-22) produced in Comparative Example E-1 Δ: Red equivalent to the coated product (e-22) produced in Comparative Example E-1 ×: Comparative Example E-1 Dull red color than the painted product (e-22) made in

・ Gravure ink 1. Preparation of gravure ink First, the resin measurement method will be described below.
(Hydroxy group value)
Obtained according to JIS K0070.
(Acid value)
Obtained according to JIS K0070.
(Amine value)
The amine value was determined according to the following method according to JIS K0070 with the same amount of potassium hydroxide as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of the resin. The sample was precisely weighed in an amount of 0.5 to 2 g (sample non-volatile content: Sg). To the precisely weighed sample, 50 mL of a mixed solution of methanol / methyl ethyl ketone = 60/40 (mass ratio) was added and dissolved. Bromophenol blue was added to the obtained solution as an indicator, and the obtained solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). With the point where the color of the solution changed from green to yellow as the end point, the amine titer was determined by the following formula using the titration amount (AmL) at this time.
Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

(Weight average molecular weight)
The weight average molecular weight was determined by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (HLC-8220 manufactured by Tosoh Corporation) and using polystyrene as a standard substance as a converted molecular weight. The measurement conditions are shown below.
Column: The following columns were connected in series and used.
Tosoh Guard Column HXL-H
Tosoh TSKgel G5000HXL
Tosoh TSKgel G4000HXL
Tosoh TSKgel G3000HXL
Tosoh TSKgelG2000HXL
Detector: RI (Differential Refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min

(Glass-transition temperature)
The glass transition temperature (Tg) was determined by DSC (Differential Scanning Calorimetry). The measuring machine uses DSC8231 manufactured by Rigaku Co., Ltd., and the measurement temperature range is -70 to 250 ° C., the temperature rise rate is 10 ° C./min, and the midpoint between the endothermic start temperature and the end temperature based on the glass transition in the DSC curve is glass. The transition temperature was used.

(Synthesis Example 1) [Polyurethane Resin PU1]
200 parts of polypropylene glycol (hereinafter “PPG700”) having a number average molecular weight of 700, 127 parts of isophorone diisocyanate (hereinafter “IPDI”), and 81.8 parts of ethyl acetate are reacted at 80 ° C. for 4 hours under a nitrogen stream to terminal isocyanate. A resin solution of urethane prepolymer was obtained. Next, a mixed solvent of 49.5 parts of isophorone diamine (hereinafter “IPDA”), 3 parts of 2-ethanolamine, and ethyl acetate / isopropanol (hereinafter “IPA”) = 50/50 (mass ratio) 803. A resin solution of the obtained terminal isocyanate urethane prepolymer was gradually added to the mixture of 9 parts at 40 ° C., and then reacted at 80 ° C. for 1 hour to have a non-volatile content of 30% and an amine value of 3.5 mgKOH / g. , A polyurethane resin solution PU1 having a hydroxyl value of 7.3 mgKOH / g and a weight average molecular weight of 40,000 was obtained. The glass transition temperature was −32 ° C.

(Example F-1) 30 parts of polyurethane resin solution PU1 (nonvolatile content 30%) is used as an adjusting binder resin for gravure ink f-1, and polyethylene wax (A-C400A manufactured by Honeywell Co., Ltd.) is used as a hydrocarbon wax. 0.8 parts in terms of non-volatile content, 0.5 parts in terms of non-volatile content of chlorinated polypropylene resin (370M chlorine content 30%, non-volatile content 50% manufactured by Nippon Paper Co., Ltd.), 10 parts of pigment composition 1, methyl ethyl ketone (hereinafter "MEK") 58.7 parts of a solution of / n-propyl acetate (hereinafter “NPAC”) / IPA = 40/40/20 (mass ratio) was mixed and dispersed with an Eiger mill for 15 minutes to obtain gravure ink f-1. ..

(Examples F-2 to F-23, Comparative Examples F-1 to F-8) Adjustment of Gravure Inks f-2 to f-31 The pigment composition 1 of Example F-1 was changed as shown in Table 7. The same procedure as in Example F-1 was carried out except that the gravure inks f-2 to f-31 were obtained.

(Example F-24) Printing of Gravure Ink f-1 Using the gravure ink f-1 obtained above, a mixed solvent consisting of MEK / NPAC / IPA = 40/40/20 (mass ratio) was used. Dilute to a viscosity of 16 seconds (25 ° C, Zahn cup No. 3), and use a gravure printing machine equipped with a Helio 175-line gradation plate (plate type compressed gradation 100% to 3%) to obtain the following base material ( In the case of OPP, printing was performed on the corona discharge-treated surface) at a printing speed of 80 m / min to obtain OPP printed matter and CPP printed matter.
(Base material)
-OPP: Biaxially stretched polypropylene (OPP) film with single-sided corona discharge treatment (FOR thickness 25 μm manufactured by Futamura Chemical Co., Ltd.)
-CPP: Unstretched polypropylene (CPP) film without corona treatment (CP-S thickness 30 μm manufactured by Mitsui Chemicals Tohcello Co., Ltd.)

(Examples F-25 to F-46, Comparative Examples F-9 to F-16) Printing of Gravure Inks f-2 to f-31 The gravure inks f-1 of Example F-24 are as shown in Table 8. Except for the changes, the same procedure as in Example F-24 was carried out to obtain OPP printed matter and CPP printed matter, respectively.

2. Evaluation of gravure ink and printed matter (stability of ink over time)
Each of the prepared gravure inks was placed in a closed container and stored at 40 ° C. for 10 days. Then, the viscosity was measured to evaluate the change in viscosity from that before storage. The viscosity was measured at 25 ° C. The number of outflow seconds was 4. The results are shown in Table 7. The viscosity of each ink in the B-type viscometer before storage was in the range of 40 to 500 cps (25 ° C.).
(Evaluation criteria for stability over time)
5. Viscosity change less than 2 seconds (good)
4. Viscosity change is 2 seconds or more and less than 5 seconds (practical)
3. 3. Viscosity change is 5 seconds or more and less than 10 seconds (slightly defective)
2. Viscosity change is 10 seconds or more and less than 15 seconds (defective)
1. 1. Viscosity change is 15 seconds or more (extremely defective)
Note that 5 and 4 are ranges in which there is no practical problem.

(Clarity)
Each of the obtained OPP printed matter and CPP printed matter was visually observed and evaluated according to the following criteria. The results are shown in Table 8.
(Evaluation criteria for sharpness)
〇: Brighter red than the printed matter (f-22) produced in Comparative Example F-9 Δ: Red equivalent to the printed matter (f-22) produced in Comparative Example F-9 ×: Prepared in Comparative Example F-9 Dull red than the printed matter (f-22)

・ Flexo ink 1. Adjustment of flexo ink (synthesis example 2) [Polyurethane resin PU2]
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, stirrer, recirculator, and nitrogen gas introduction tube, PTG-3000SN (polytetramethylene glycol manufactured by Hodoya Chemical Co., Ltd., functional group number 2, hydroxyl value 37, number average molecular weight 3000 ) 121.8 parts, PEG2000 (polyethylene glycol made by Nichiyu Co., Ltd., number of functional groups 2, hydroxyl value, number 56, average molecular weight 2000), 24.4 parts, 2,2-dimethylol propionic acid, 32.7 parts, and isophorone diisocyanate, 66.9 parts. , 90 ° C. for 3 hours. After cooling, a mixed solution of 16.6 parts of 25% ammonia water and 73.0 parts of ion-exchanged water was gradually added dropwise to the obtained water-soluble resin to neutralize it to make it water-soluble, and an aqueous solution of polyurethane resin PU2 was obtained. rice field. The acid value of the obtained polyurethane resin PU2 was 55 mgKOH / g, and the weight average molecular weight (Mw) was 36000.

(Measurement of acid value)
The number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin. The dried polyurethane resin PU2 was calculated by potentiometric titration with a potassium hydroxide / ethanol solution according to the method described in JIS K2501.

(Measurement of weight average molecular weight (Mw))
Polystyrene-equivalent value measured by GPC (Gel Permeation Chromatography). The dried polyurethane resin PU2 is dissolved in tetrahydrofuran to prepare a 0.1% solution, and the weight average molecular weight is measured by HLC-8320-GPC (column number M-0053 molecular weight measurement range of about 20 to about 4 million) manufactured by Toso. Was measured.

(Example G-1) 15 parts of adjusting pigment composition of flexo ink g-1, 35.0 parts of polyurethane resin PU2, 0.1 part of nonionic surfactant (Surfinol 104PA, manufactured by Air Products Co., Ltd.), n- 2.0 parts of propanol, 2.0 parts of polyethylene wax (Aqua Petro DP2502B, manufactured by Toyo Adre), 0.2 parts of defoamer (Tegoformex 1488, manufactured by Ebonic), 45.7 parts of ion-exchanged water are high. After stirring and mixing with a speed mixer, the mixture was dispersed in a sand mill filled with 1.25 mm diameter zirconia beads for 60 minutes to obtain flexo ink g-1.

(Examples G-2 to G-23, Comparative Examples G-1 to G-8) Adjustment of flexo inks g-2 to g-31 The pigment composition 1 of Example G-1 was changed as shown in Table 9. Except for the above, the same procedure as in Example G-1 was carried out to obtain flexo inks g-2 to g-31.

2. Evaluation of flexo ink (coarse grain)
The presence or absence of coarse particles in the flexo ink was confirmed using a grind gauge (according to JIS K5600-2-5), and evaluation was performed according to the following evaluation criteria. The results are shown in Table 9.
(Evaluation criteria for coarse grains)
◯: The size of coarse particles is less than 60 μm (good)
Δ: The size of the coarse particles is 60 or more and less than 90 μm (no problem in practical use)
X: The size of coarse particles is 90 μm or more (defective)

(Viscosity stability)
The viscosity at 25 ° C. was measured using a Zahn cup (No. 4). Further, after storing in a constant temperature machine at 40 ° C. for 1 week and accelerating with time, the rate of change in viscosity before and after aging was determined. The evaluation criteria are as follows, and the results are shown in Table 9.
(Evaluation criteria for viscosity stability)
◯: Viscosity change rate before and after storage at 40 ° C for 1 week is less than ± 10% (good)
Δ: Viscosity change rate before and after storage at 40 ° C. for 1 week is ± 10% or more and less than ± 15% (no problem in practical use)
X: Viscosity change rate before and after storage at 40 ° C for 1 week is ± 15% or more (defective)

・ Water-based inkjet ink 1. Adjustment of water-based inkjet ink (water-based IJ ink) (Example H-1) Adjustment of water-based IJ ink h-1 ・ Pigment composition 1: 19.0 parts ・ Styrene-acrylic acid copolymer (manufactured by BASF Japan Ltd., John) Krill 61J): 16.4 parts, surfactant (manufactured by Kao, Emargen 420): 5.0 parts, ion-exchanged water: 59.6 parts, and 200 parts of 1.25 mm diameter zirconia beads in a 200 ml glass bottle. The ink was prepared and dispersed in a paint shaker manufactured by Red Devil for 6 hours. Then, the zirconia beads were removed from the dispersion to obtain an aqueous coloring composition.

Next, the aqueous coloring composition and the following raw materials were stirred and mixed for 30 minutes using a high-speed mixer to obtain a mixture.
-Obtained aqueous coloring composition: 12.5 parts-Styrene-acrylic acid copolymer (BASF Japan, John Krill 60): 3.3 parts-Surfactant (Kao, Emargen 420): 2 .0 parts · Ion-exchanged water: 64.9 parts Next, diethylene glycol monobutyl ether was appropriately 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. Then, it was filtered using a 1.0 μm copolymer filter, and further filtered using a 0.45 μm copolymer filter to obtain an aqueous IJ ink g-1.

(Examples H-2 to H-23, Comparative Examples H-1 to H-8) Adjustment of Aqueous IJ Inks h-2 to h-31 The pigment composition 1 of Example H-1 is as shown in Table 10. Aqueous IJ inks h-2 to h-31 were obtained in the same manner as in Example H-1 except that they were changed.

2. Evaluation of water-based IJ ink (coloring power)
The adjusted water-based IJ ink was filled in a cartridge of a printer PX-105 (piezo type inkjet printer) manufactured by Seiko Epson Corporation, and printing was performed on A4 size plain paper. The printed matter was visually observed and evaluated according to the following criteria. The results are shown in Table 10.
(Evaluation criteria for coloring power)
〇: The reflection density is higher than that of the printed matter using the water-based IJ ink (h-22) adjusted in Comparative Example H-1. Δ: The water-based IJ ink (h-22) adjusted in Comparative Example H-1 was used. Equivalent to printed matter ×: Reflection density is lower than that of printed matter using water-based IJ ink (h-22) adjusted in Comparative Example H-1.

(Clarity)
The adjusted water-based IJ ink was filled in a cartridge of a printer HG-5130 manufactured by Seiko Epson Corporation, and printing was performed. The printed matter was visually observed and evaluated according to the following criteria. The results are shown in Table 10.
(Evaluation criteria for sharpness)
〇: Vivider than the printed matter using the water-based IJ ink (h-22) adjusted in Comparative Example H-1 Δ: With the printed matter using the water-based IJ ink (h-22) adjusted in Comparative Example H-1 Equivalent ×: Duller than the printed matter using the water-based IJ ink (h-22) adjusted in Comparative Example H-1.

Further, when the base material was changed from A4 size plain paper to coated paper, polypropylene film (OPP film), polyethylene terephthalate film, and aluminum foil, and the coloring power was evaluated, the same result was obtained. When the base material was not paper, the base material was attached to A4 plain paper and used.
Further, when a tank filled with the produced water-based IJ ink was mounted as magenta ink using a MAXIFY MB5430 (thermal inkjet printer) manufactured by Canon Inc. and the coloring power was evaluated, the same result was obtained.

(Viscosity stability)
The initial viscosity of each water-based IJ ink at 25 ° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosity after aging at 50 ° C. for 4 weeks was measured. Using each measured value, the rate of increase in viscosity with respect to the initial viscosity was calculated, used as an index of viscosity stability, and evaluated according to the following criteria. The results are shown in Table 10. It is considered that the smaller the viscosity increase rate is, the better the viscosity stability is, and if it is "○" and "Δ" in the following evaluation criteria, it is a practical level.
(Evaluation criteria for viscosity stability)
〇: The viscosity increase rate is less than 20%.
Δ: The viscosity increase rate is 20% or more and less than 40%.
X: The viscosity increase rate is 40% or more.

(Crystal stability)
As an index of crystal stability (crystal growth suppressing effect), the average primary particle size of the pigment in each aqueous IJ ink was measured. Aqueous IJ ink was dropped on a mesh covered with a support film, and the dried particles were used as a sample, and the particles were photographed with a transmission electron microscope (H-7650 type transmission electron microscope manufactured by Hitachi High-Technologies Corporation). The longer diameter (major axis) of each of the 50 primary particles of the pigment constituting the above was measured. A value obtained by averaging them was calculated, and the value was taken as the average primary particle size. The prepared water-based IJ ink was sealed in a screw cap bottle, stored at 50 ° C. for 4 weeks, and then the same measurement was performed, and the crystal stability was evaluated by the change in the average primary particle size before and after storage. The results are shown in Table 10.

From the results in the table, when the pigment composition of the present invention is used, a coloring composition having excellent dispersibility, coloring power and sharpness, good crystal stability and storage stability, and applicable to various uses can be obtained. Be done. For example, a molding resin composition can provide a molded product having excellent dispersibility and sharpness. Further, as the toner, it is possible to provide a toner having excellent dispersibility of the pigment. Moreover, in the form of the coloring composition, it can be seen that the crystal stability is improved. Further, the water-based coloring composition is excellent in storage stability. Further, the water-based paint is excellent in storage stability, coloring power and sharpness. Further, it can be seen that the printing ink is excellent in storage stability, dispersibility, and sharpness. Further, it can be seen that the water-based inkjet ink is excellent in dispersibility, coloring power and sharpness, and also has good crystal stability and storage stability.

Claims (8)

C. I. Pigment Red 269, and C.I. I. A pigment composition containing composite pigment particles containing Pigment Red 150.
C.I. in 100 mol% of the composite pigment particles. I. Pigment content of Red 0.99 is Ri 10-50 mol% der,
A pigment composition in which powder X-ray diffraction using CuKα rays of the composite pigment particles does not have a maximum peak in the range of diffraction angle (2θ) = 13.5 to 14.5 °. A coloring composition comprising the pigment composition according to claim 1 and a dispersion medium. The coloring composition according to claim 2 , wherein the dispersion medium contains a resin. A resin composition for molding, which comprises the coloring composition according to claim 3. A toner containing the coloring composition according to claim 2 or 3. A paint comprising the coloring composition according to claim 2 or 3. A printing ink containing the coloring composition according to claim 2 or 3. An inkjet ink containing the coloring composition according to claim 2 or 3.

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