JP2022113966A - Pigment composition and use thereof - Google Patents

Abstract

To provide a pigment composition excellent in clarity, dispersibility and crystal stability.SOLUTION: A pigment composition contains composite pigment particles containing C.I. Pigment Red 269 and C.I. Pigment Red 150. In the composite pigment particles 100 mol%, a content of C.I. Pigment Red 150 is 10-50 mol%. Preferably, a powder X-ray diffraction of the composite pigment particles using CuKα rays has no maximum peak in a range of: a diffraction angle (2θ)=13.5-14.5°.SELECTED DRAWING: Figure 1

Description

The present invention relates to pigment compositions containing composite pigment particles and uses thereof.

Organic pigments capable of reproducing hues from red to magenta include, for example, soluble azo pigments, insoluble azo pigments, and quinacridone pigments, and are used in applications such as plastic products, toners, paints, and printing inks. Of these, soluble azo pigments have vivid hues, high tinting strength, and have the advantage of being inexpensive. There is a problem that the presence of ions adversely affects printing characteristics. On the other hand, quinacridone pigments are superior to other pigments in terms of fastness and vividness, but are significantly inferior to other pigments in coloring power and dispersion stability, and are also expensive. On the other hand, naphthol-based azo pigments, which are classified as insoluble azo pigments, have a good balance of production cost, coloring strength, and fastness, and are therefore being investigated for use in various applications. However, it has drawbacks in terms of crystal stability, such as insufficient clarity and dispersibility, and growth of pigment crystals depending on the dispersion medium.
For this reason, 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 tinting strength. (Patent document 1)

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

JP-A-2002-156795 JP-A-2005-107147

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

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

The pigment composition of the present invention contains C.I. I. Pigment Red 269, and C.I. I. A pigment composition containing composite pigment particles comprising Pigment Red 150,
C.I. in 100 mol % of the composite pigment particles I. The content of Pigment Red 150 is 10-50 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 within the range of diffraction angle (2θ) = 13.5 to 14.5°. .

The present invention also relates to a coloring composition comprising the pigment composition and a dispersing 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 paint 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 present invention, it is possible to provide a pigment composition, a coloring composition, a resin composition for molding, a toner, a paint, a printing ink, and an inkjet ink which are excellent in clarity, dispersibility and crystal stability.

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

Terms used herein are defined. "(Meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, respectively " acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide”. "C.I." means a color index (C.I.). Solid solution refers to a mode in which X-ray diffraction of a composite pigment containing two pigments shows the crystal lattice of one pigment (host) and the other pigment (guest) is buried in the crystal lattice of the host component. .

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

A composite pigment particle such as a solid solution has the property of complementing the drawbacks 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. Pigment Red 269's low dispersibility was reduced by the guest component C.I. I. Pigment Red 150 complements and C.I. I. Pigment Red 150's low crystalline stability was measured by C.I. I. Pigment Red 269 complements, in addition to C.I. I. The vividness of Pigment Red 269 can be improved. Therefore, C.I. I. When the content of Pigment Red 150 is 10 mol % or more, dispersibility is improved. Also, C.I. I. When the content of Pigment Red 150 is 50 mol % or less, 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 simple mixture of multiple pigments is used as a sample, the X-ray diffraction pattern obtained is the superposition of the X-ray diffraction patterns of each pigment, and the intensity of each diffraction peak is the blending ratio of each pigment. depends on In contrast, when a plurality of pigments form a solid solution, a different X-ray diffraction pattern is obtained than when the plurality of pigments are simply mixed. Specifically, phenomena such as the fact that the intensity of each diffraction peak does not depend on the blending ratio of the pigment, the half width of the diffraction peak increases, and the like are observed.

C. I. The structure of Pigment Red 269 is shown in the following chemical formula (1). Also, 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, powder X-ray diffraction using CuKα rays of the composite pigment particles preferably does not have a maximum peak in the diffraction angle (2θ) range of 13.5 to 14.5°. C. at a diffraction angle (2θ) of 13.5-14.5° I. This is because the crystal stability is more improved than when a maximum peak derived from Pigment Red 150 appears.

Also, the pigment composition of the present invention preferably has a maximum peak in the diffraction angle (2θ) range of 12.5 to 13.5°. In the present invention, not having a maximum peak in the range of diffraction angle (2θ)=13.5 to 14.5° means C.I. I. It means that the peak derived from Pigment Red 150 is not observed as a shoulder peak of the maximum peak appearing in the diffraction angle (2θ)=12.5 to 13.5° range.

The pigment composition of the present invention contains C.I. I. Pigment Red 269, and C.I. I. Pigment Red 150 is contained in the composite pigment particles, and 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 to produce 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. Pigment Red 269 coupler component N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, and C.I. I. It can be produced by a coupling reaction with 3-hydroxy-2-naphthamide, which is a coupler component of Pigment Red 150.

Specifically, a solution containing a diazo component obtained by diazotizing a base component and a solution containing a coupler component are prepared and coupled. One solution containing both the coupler components N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide and 3-hydroxy-2-naphthamide is prepared as the solution containing the coupler component. can be used for coupling to obtain the pigment composition of the present invention. 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 stepwise. Also good. In the latter case, C.I. I. A pigment composition can be obtained by sequentially coupling 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. It may also 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 and kind of the water-soluble organic solvent added, the amount of water, and the kind and amount of the base. When the temperature does not contain a water-soluble organic solvent, the temperature is preferably 50 to 95°C.

The base is preferably, for example, a base that is soluble in water and capable of dissolving the coupler component, and that does not form an insoluble salt when neutralized with the acid in the aqueous acid solution or the solution containing the diazo component described below. More preferred bases are, for example, sodium hydroxide and potassium hydroxide. As a result, the cost, dissolving power of the coupler component, waste liquid treatment, etc. are improved.

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

As the water-soluble organic solvent that can be used for the solution containing the coupler component and the solution containing the diazo component, for example, any water-soluble organic solvent can be used as long as it can be freely mixed with water. The organic solvent includes, for example, aprotic polar solvents such as dimethyl sulfoxide and N,N-dimethylformamide; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; Examples 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 to be 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, it is 1 to 1 in 100% by mass of the entire slurry after coupling. 50% by weight is preferred.

Coupling methods include, for example, reverse coupling, forward coupling, acid precipitation forward coupling and the like. Among these, from the viewpoint of particle size control and reaction yield, reverse coupling or positive acid precipitation coupling, which will be described later, is preferable.

As the method of reverse coupling, for example, a known method can be used, and examples include a method of adding a solution containing a coupler component to a solution containing a diazo component. The temperature during coupling is desirably 0 to 50°C, and is particularly desirably 10 to 30°C from the viewpoints of suppression of deterioration and decomposition of the diazo component and reaction rate.
A buffer solution may be added in advance to the solution containing the diazo component. Any kind of buffer may be used as long as it has a buffering capacity, but an acetic acid-sodium acetate aqueous solution is preferably used. When a buffer solution is added, it is desirable to adjust the pH of the solution containing the diazo component within the range of 3.0 to 6.5. From the viewpoint of improving the reaction rate and dispersibility, it is preferable to heat the slurry after coupling as necessary.

For the method of acid precipitation positive coupling, for example, a known method can be used. After obtaining an acid precipitation coupler slurry by reacting a solution containing a coupler component with an acid aqueous solution, A method of adding a solution containing a diazo component and carrying out a coupling reaction can be mentioned. Any temperature can be selected as the temperature of the acid aqueous solution during acid precipitation, but the temperature is preferably 0 to 30°C. From the viewpoint of improving the reaction rate, the acid precipitation coupler slurry is preferably heated as necessary before adding the solution containing the diazo component. However, if the temperature is too high, the diazo component tends to deteriorate and decompose, so the temperature of the acid precipitation coupler slurry during the coupling reaction is preferably 50° C. or less.
The pH of the acid precipitation 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 addition of the solution containing the diazo component becomes extremely slow, and if the pH exceeds 6.5, the diazo component tends to deteriorate, which is undesirable. Any acid can be used as the acid for adjusting the pH 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.
As for the method of adding the acid, the acid used for acid precipitation may be added in excess of the equivalent of the base in the solution containing the coupler component, may be added in advance when the base is dissolved, or may be added to the diazo solution. A necessary amount may be added later to the coupler slurry after acid precipitation. Moreover, from the viewpoint of improving the reaction rate and dispersibility, it is preferable to heat the slurry after coupling as necessary.

Various additives can be used as necessary when producing the pigment composition of the present invention. Examples of additives include surfactants and resins. The additive may be added in advance to the solution containing the coupler component, the solution containing the diazo component, or the acid solution for acid precipitation, or may be added to the slurry after the coupling reaction. Subsequent pigment may be added to the reslurried pigment presscake that has been filtered and washed. Further, it may be added when performing a known dissolution precipitation method represented by acid pasting described later, or a solvent salt milling method. When it is added to a solution containing a coupler component, it may be added before dissolving the coupler or after acid precipitation.

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

Anionic surfactants are, for example, fatty acid salts, alkylsulphate salts, alkylarylsulphonates, alkylnaphthalenesulphonates, alkylsulphates, dialkylsulphonates, dialkylsulphosuccinates, alkyldiaryletherdisulphonates, Alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phosphate, glycerol borate Fatty acid esters, polyoxyethylene glycerol fatty acid esters and the like can be mentioned.

Examples of amphoteric surfactants include betaines, sulfobetaines, alkylbetaines, alkylamine oxides and the like.

Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethyleneoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid Examples include esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like.
Among these, a combination of an amphoteric surfactant and an anionic surfactant is preferred.

Surfactants can be used alone or in combination of two or more.

The amount of 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, polymethacrylic acid acid, vinylnaphthalene-(meth)acrylic acid copolymer, styrene-(anhydride) maleic acid copolymer, maleic acid-maleic anhydride copolymer, vinylnaphthalene-(anhydride) maleic acid copolymer, α-olefin- Examples thereof include (anhydrous) maleic acid copolymers, α-olefin-maleic acid alkyl ester copolymers, resins having acid groups such as polyester-modified acrylic acid polymers, acrylic copolymers and salts thereof.

Resin can be used alone or in combination of two or more.

The amount of 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 inorganic bases and organic bases.
Examples of inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal salts of silicic acid such as sodium orthosilicate, sodium metasilicate and sodium sesquisilicate; alkali metal salts of phosphoric acid, alkali metal salts of carbonic acid such as disodium carbonate, sodium hydrogencarbonate and dipotassium carbonate, alkali metal salts of boric acid such as sodium borate, ammonia;
Examples of organic bases include alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine, aminoethanol, methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, butylaminoethanol, diethylaminoethanol, dibutylaminoethanol, Examples include alkanolamines such as diethanolamine and triethanolamine, and amines having nonionic groups such as methoxypoly(oxyethylene/oxypropylene)-2-propylamine.

A basic compound can be used individually or in combination of 2 or more types.

For the production of the pigment composition of the present invention, a known dissolution deposition method typified by acid pasting can be used. Specifically, pigments (C.I. Pigment Red 269 and C.I. Pigment Red 150) are dissolved in a good solvent, mixed with a large excess of a poor solvent to precipitate pigment composition particles, and a solvent can be filtered or distilled off to produce a pigment composition.

Here, the good solvent is not particularly limited as long as it can dissolve the pigment, for example, inorganic acids (sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, hydrochloric acid, phosphoric acid, etc.) and their aqueous solutions, organic acids (dichloroacetic acid, methanesulfone acids, etc.), inorganic bases (sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.) and their aqueous solutions, organic bases (triethylamine, diazabicycloundecene, sodium methoxide, etc.), alcoholic solvents (methanol, n-propanol , tert-amyl alcohol, etc.), ketone solvents (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (dimethyl sulfoxide, hexamethylene 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 (acetonitrile, etc.), halogen solvents (carbon tetrachloride, dichloromethane, etc.), ionic liquids (1-ethyl-3-methyl imidazolium tetrafluoroborate, etc.), carbon disulfide solvents, and the like. 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, it is preferably 100 to 5000 parts by weight, preferably 500 to 3000 parts by weight, based on 100 parts by weight of the pigment. is more preferred.

The temperature for dissolving the pigment is preferably -10 to 200°C, more preferably -10 to 130°C, and still 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, such as an aqueous solvent (water, hydrochloric acid, sodium hydroxide aqueous solution, etc.). are preferably mentioned. The amount of the poor solvent used is preferably 50 to 5,000 parts by mass, more preferably 100 to 3,000 parts by mass, based on 100 parts by mass of the pigment-containing solution, 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 of 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, composite pigment particles can be precipitated by a method of injecting a pigment solution into previously prepared ice water, or a method of continuously injecting into running water using a device such as an aspirator.

A known solvent salt milling method can be used to produce the pigment of the present invention. Specifically, a clay-like mixture consisting of at least three components of pigments (CI Pigment Red 269 and CI Pigment Red 150), a water-soluble inorganic salt and a water-soluble solvent is kneaded using a kneader or the like. Knead vigorously. The mixture after kneading is put into water and stirred with various stirrers to form a slurry. The resulting slurry is filtered to remove the water-soluble inorganic salt and water-soluble solvent to obtain composite pigment particles.

Water-soluble inorganic salts such as sodium chloride, sodium sulfate, and potassium chloride can be used. These inorganic salts are used in an amount of 1-fold or more, preferably 20-fold or less, of the pigment. When the amount of the inorganic salt is 1-fold or more by mass, the pigment can be sufficiently finely divided. Further, when the amount of the inorganic salt is 20 times or less by weight, a great deal of effort is not required to remove the water-soluble inorganic salt and the water-soluble solvent after kneading, and at the same time, the amount of pigment that can be treated at one time is reduced. Since it does not decrease, it is preferable from the viewpoint of productivity.

Since solvent salt milling often generates heat during kneading, it is preferable to use a water-soluble solvent having a boiling point of about 120 to 250° C. from the viewpoint of safety. Water-soluble solvents include, 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 Ethers, low-molecular-weight polypropylene glycols, and the like.

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, per 100 parts by mass of the pigment. By appropriately selecting the amount of the water-soluble solvent used, the kneaded material can have a viscosity suitable for solvent salt milling.

The kneading temperature during 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 performing the dissolution precipitation method and the solvent salt milling method, commercially available C.I. I. Pigment Red 269 and C.I. I. Pigment Red 150 may be used, or a pigment composition obtained by the azo pigment synthesis method may be used.

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

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

<Dispersion medium>
Dispersion media are resins and solvents. The dispersion medium can be appropriately selected according to the application of the coloring composition. Applications of the coloring composition include, for example, molding resin compositions, moldings, toners, pigment dispersions, paints, printing inks, and inkjet inks.
The coloring composition is preferably produced by mixing a pigment composition and a dispersion medium and performing dispersion treatment according to a method known in the art.

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

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

The resin as the dispersion medium may be, for example, polyolefin resin, polyester resin, styrene copolymer, acrylic resin, and modified resins thereof. Specifically, polyethylene such as high density polyethylene (HDPE), linear low density polyethylene (L-LDPE), low density polyethylene (LDPE), polyolefin resin such as polypropylene; polyester resin such as polyethylene terephthalate; styrene-p -chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer Polymer, 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 copolymers such as styrene-acrylonitrile-indene copolymers; Acrylic resins such as acrylic resins and methacrylic resins; Polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic acid resins, polyvinyl acetate, silicone Resins, polyurethanes, polyamide resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, alkyd resins, amino resins, epoxy resins, petroleum resins, and modified resins thereof.

The solvent as the dispersion medium 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 organic solvents such as toluene and xylene; aliphatic hydrocarbon organic solvents such as acetate organic solvents, ketone organic solvents, and alcohol organic solvents; Solvents may be mentioned. More specifically, acetate organic solvents such as butyl acetate and methyl acetate; ketone 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 Alcohol-based organic solvents such as polypropylene glycol, butyl glycol, and butyl diglycol are included.

[Dye derivative]
Pigment compositions and coloring compositions can contain dye derivatives. Containing 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. Dye derivatives include, for example, compounds having an acidic substituent such as a sulfo group, a carboxy group, and a phosphoric acid group, amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group A compound having a neutral substituent such as a phenyl group or a phthalimidoalkyl group can be mentioned.
Organic dyes include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzoiso Indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo. .

A dye derivative can be used individually or in combination of 2 or more types.

The coloring composition can contain known materials such as dispersants.

Applications of the coloring composition are exemplified below.
<Molding resin composition>
The molding resin composition of the present invention contains a coloring composition (pigment composition, resin). The molding resin composition preferably contains a thermoplastic resin. The molding resin composition containing a thermoplastic resin is preferably melted, kneaded, and molded into a desired shape to produce a molded product. In addition, resin is not limited to a thermoplastic resin.

Thermoplastic resins include, for example, homopolymers or copolymers using ethylene, propylene, butylene, styrene, etc. 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 resin such as polypropylene and polybutylene can be used. 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 resins and polyester resins are preferred. In addition, the number average molecular weight of the thermoplastic resin is preferably more than 30,000 and 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. If the MFR is 0.001 or more, the molding processability of the plastic molding material is good, and weld marks or flow marks are less likely to occur in the molded product. On the other hand, when the MFR is 30 or less, the molded article can easily have excellent mechanical properties. In particular, when using high-density polyethylene (HDPE), the MFR is preferably in the range of 0.005-10. Also, when using low density polyethylene (LDPE), polypropylene, or polybutene, 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, based on 100 parts by mass of the pigment composition.

The molding resin composition can contain wax. Preferably, the wax is a low molecular weight polyolefin. Low molecular weight polyolefins are polymers of olefinic monomers such as ethylene, propylene, butylene, and may be block, random copolymers or terpolymers. Specifically, polymers of α-olefins such as low-density polyethylene (LDPE), high-density polyethylene (HDPE) and polypropylene (PP).

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

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

The melt flow rate (MFR) of the wax determined according to JIS K-7210 is preferably greater than 100 g/10 minutes.

The blending amount of the wax 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 commonly used in the technical field of moldings, including antioxidants, light stabilizers, dispersants, metallic soaps, antistatic agents, flame retardants, lubricants, fillers, and composite pigment particles other than the above. and the like.

The resin composition for molding can be produced, for example, in the composition ratio of the molding. Alternatively, it can be produced as a masterbatch containing a high concentration of composite pigment particles. In the present specification, a masterbatch is preferred because it facilitates uniform dispersion of the composite pigment particles in the molded article.
For the masterbatch, for example, it is preferable to melt-knead a thermoplastic resin and a pigment composition, and then mold it into an arbitrary shape so that it can be easily used in the next step. Next, the masterbatch and a diluent resin (for example, the thermoplastic resin used in the masterbatch) are melt-kneaded to form a molded body 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 melt-knead the pigment composition and wax in advance to produce a dispersion, and then melt-knead the mixture together with the thermoplastic resin to produce a masterbatch. Apparatus used for the dispersion is preferably a blend mixer, a three-roll mill, or the like.

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

As the diluent resin (Y), the thermoplastic resin used in the masterbatch is preferably used, but other thermoplastic resins may be used as long as there is no problem in compatibility.

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

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

Examples of molding methods include blow molding, inflation molding, extrusion molding, Engel molding, and vacuum molding.

<Toner>
The toner of this specification contains a coloring composition (pigment composition, resin). The resin in the toner is preferably a thermoplastic resin called a binder resin. The toner includes dry toner and liquid toner. Among these, dry toner is preferred. For example, a dry toner is produced by melt-kneading a pigment composition and a binder resin, cooling, pulverizing, and classifying. Then, a post-treatment step of blending and mixing additives can be performed to produce the product.

Binder resins include, for example, styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, and styrene-methacrylic acid ester copolymer. , styrene-α-methyl chloromethacrylate 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-indene copolymer, polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, petroleum-based resins, and the like.

Among these, polyester resins and styrene copolymers are preferred, and polyester resins are more preferred. Since the pigment composition of the present specification has particularly excellent compatibility with polyester resins, 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, 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 10-60 mgKOH/g, more preferably 15-55 mgKOH/g. When a polyester resin having an appropriate acid value is used, separation of the release agent is easily suppressed, and reduction in image density in a high-humidity environment is less likely to occur.

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 does not easily decrease in a high humidity environment. Incidentally, the lower limit of the hydroxyl value is 0.1 mgKOH/g.

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

The toner may further contain a charge control agent. The use of a charge control agent makes it easier to obtain a toner with a stable charge amount. A positive or negative charge control agent can be appropriately selected and used as the charge control agent.

When the toner is a positively chargeable toner, the positive charge control agent includes, for example, nigrosine-based dyes, triphenylmethane-based dyes, organic tin oxides, quaternary ammonium salt compounds, and styrene- and quaternary ammonium salt functional groups. Examples include styrene/acrylic polymers copolymerized with acrylic resins. Among these, quaternary ammonium salt compounds are preferred. Examples of quaternary ammonium salt compounds include salt-forming compounds of quaternary ammonium salts and organic sulfonic acids or molybdic acids. Organic sulfonic acid is preferably naphthalenesulfonic acid.

When the toner is a negatively charged toner, the negative charge control agent includes, for example, a metal complex of a monoazo dye, a styrene-acrylic polymer obtained by copolymerizing a styrene-acrylic resin with a sulfonic acid as a functional group, an aromatic hydroxycarboxylic acid. metal salt compounds, metal complexes of aromatic hydroxycarboxylic acids, phenolic condensates, and phosphonium compounds. Preferred aromatic hydroxycarboxylic acids are salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-hydroxy-2-naphthoic acid and 3-phenylsalicylic acid. Metals used in metal salt compounds 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 Fischer-Tropsch wax, natural ester waxes such as synthetic ester waxes, carnauba wax and rice wax.

To the toner, a lubricant, a fluidizing agent, an abrasive, a conductivity-imparting agent, an image-separation preventing agent, etc., can be added, if necessary.

Lubricants include polyvinylidene fluoride, zinc stearate, and the like. Fluidizing agents 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 hydrophobized products thereof. Among them, hydrophobized silica, silicon-aluminum co-oxide, and silicon-titanium co-oxide fine powder are preferred. Examples of the hydrophobizing treatment method for these fine powders include treatment with silicone oil or a silane coupling agent such as tetramethyldisilazane, dimethyldichlorosilane, dimethyldimethoxysilane, or the like.
Examples of abrasives include silicon nitride, cerium oxide, silicon carbide, strontium titanate, tungsten carbide, calcium carbonate, and hydrophobized products thereof. Examples of conductivity-imparting agents include tin oxide and the like.

Also, the toner herein can be used as a one-component developer or a two-component developer. A two-component developer can further contain a carrier.

Examples of the carrier include magnetic powders such as iron powder, ferrite powder, and nickel powder, and products whose surfaces are coated with resin or the like. Examples of the resin that coats the carrier surface include styrene-acrylate copolymer, styrene-methacrylate copolymer, acrylate copolymer, methacrylate copolymer, fluorine-containing resin, silicone-containing resin, Examples include polyamide resins, ionomer resins, polyphenylene sulfide resins, and the like. Among these, a silicone-containing resin is preferable because it causes little formation of spent toner. The weight average particle size of the carrier is preferably 30-100 μm.

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

<Pigment dispersion>
The coloring composition can be used as an intermediate pigment dispersion for use in paints, printing inks, inkjet inks, and the like. The pigment dispersion preferably comprises a pigment composition, as well as a dispersing medium resin, and a solvent.

When the pigment dispersion is used for each purpose, it is preferable to prepare the pigment so that the viscosity hardly increases and the dispersion stability of the pigment is excellent.
The pigment dispersion of the present invention has excellent dispersibility, low initial viscosity, crystal stability, and storage stability, which cannot be obtained with conventional pigment dispersions containing naphthol azo pigments.

Herein, it is preferred to use a cross-linking agent when the pigment dispersion is made as an aqueous pigment dispersion.

For example, when resin-coated composite pigment particles are produced by coating composite pigment particles with a resin, 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. As a result, for example, when used in inkjet ink applications, ejection stability is improved. The temperature at which the cross-linking agent is added can be arbitrarily selected according to the reactivity of the cross-linking agent. Examples include a method of adding and stirring the cross-linking agent at a temperature below the reaction temperature of the cross-linking agent and the resin and then raising the temperature to the reaction temperature or higher, and a method of adding the cross-linking agent at a temperature above the reaction temperature of the cross-linking agent and the resin. .

Examples of cross-linking agents include compounds having epoxy groups, oxetanyl groups, isocyanate groups, ammonia, amino groups, quaternary ammonium salts, thiol groups, aziridinyl groups, carbodiimide groups, oxazoline groups, and the like. Particularly when the resin has a carboxyl group, it is preferable to use a compound having a bifunctional or more epoxy group in one molecule because it reacts with the carboxyl 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, even more preferably 150 to 1,000.

The amount of the cross-linking agent added is 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. By setting the amount of the cross-linking agent to be added within the above range, a stronger three-dimensional structure can be formed, which is preferable.

Epoxy compounds among cross-linking agents include, for example, 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, microfluidizers, high-speed mixers, homomixers, homogenizers, high-pressure homogenizers, ball mills, and paints. Shakers, roll mills, stone mills, ultrasonic dispersers, high-pressure dispersers, counter-impingement dispersers, oblique impingement dispersers, and the like. In addition, dispersers and mixers that are commonly used for preparing various dispersions in the art can be appropriately selected and used.

Moreover, before dispersing, pre-dispersion using a kneader, a kneading mixer such as a three-roll mill, or solid dispersion using a two-roll mill or the like may be performed. In addition, after dispersing with various dispersers, a post-treatment of storing in a heated state of 30 to 80 ° C. for several hours to about a week, and a post-treatment process using an ultrasonic disperser or a collision type beadless disperser. is effective for imparting dispersion stability to the pigment dispersion.

<Paint>
The paint herein contains a coloring composition (pigment composition, resin, solvent).
Examples of the resin include thermosetting resins and thermoplastic resins. The thermosetting resin preferably has a glass transition temperature of 10° C. or higher. Types of thermosetting resins include, for example, acrylic resins, polyesters, and polyurethanes. Also, the thermosetting resin preferably has a functional group capable of reacting with the curing agent. Examples of the functional group include a carboxyl group and a hydroxyl group. Curing agents include, for example, isocyanate curing agents, epoxy curing agents, aziridine curing agents, amine curing agents and the like.
The thermoplastic resin preferably has a glass transition temperature of 30° C. or higher. Examples of thermoplastic resins include nitrocellulose and polyester. Thermosetting resin and thermoplastic resin can be used together.

Examples of water-insoluble solvents among the solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.
Among the above solvents, examples of water-soluble solvents include water, monohydric alcohols, dihydric alcohols, and glycols. Water-soluble solvents include, for example, 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. Specific examples thereof include methoxypropanol or methoxybutanol. Also included are water-dilutable glycol ethers such as, for example, butyl glycol or butyl diglycol. Incidentally, as already explained, when the paint contains water in the solvent, it is called a water-based paint.

The paint can further contain known additives.

Uses of paints include, for example, paints for metals and paints for plastics.

<Printing ink>
The printing inks herein contain a coloring composition (pigment composition, resin, solvent). Printing inks are inks other than inkjet inks, and examples thereof include offset printing inks, flexographic printing inks, gravure printing inks, and color filter inks. As described above, when the solvent contains water, it is called water-based printing ink.

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

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

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. Examples include methoxypropanol or methoxybutanol. Also included are water-dilutable glycol ethers such as butyl glycol or butyl diglycol.

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

The content of the luster material is preferably 0.1 to 10% by mass in 100% by mass of the printing ink. In addition, other color pigments and various additives commonly used in the technical field may be blended as needed. The printing ink manufacturing method, coating method, and drying method are not particularly limited, and methods well known in the art can be used.

The printing inks can also contain known additives.

<Inkjet ink>
The inkjet ink of the invention preferably contains a pigment composition, a resin, and a solvent. Inkjet inks can be broadly classified into (solvent-based) inkjet inks, water-based inkjet inks, and UV-curable inkjet inks, depending on the presence or absence of a solvent and the type thereof. Water-based inkjet inks are preferred herein. The following description will focus on water-based inkjet inks.

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 to the material to be printed (substrate).
Examples of resin types include acrylic resins, styrene-acrylic resins, polyester resins, polyamide resins, and polyurethane resins. Moreover, the form of the resin includes a water-soluble resin, emulsion particles, and the like. Among these, emulsion particles are preferred. Emulsion particles include single-composition particles, core-shell type particles, and the like, and can be used by arbitrarily selecting them. When emulsion particles are used, the viscosity of the water-based inkjet ink can be easily reduced, and recorded matter with excellent water resistance can be easily obtained. The resin can be used after neutralizing the acidic functional groups with a pH adjusting agent such as ammonia, various amines, various inorganic alkalis, etc., 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 matter of the inkjet ink. When contained in an appropriate amount, the ejection stability is improved, and the fixability is also improved.

Solvents include water-insoluble solvents, water, and water-soluble solvents. Glycol ethers and diols are examples of water-soluble solvents. Penetrates quickly even into liquid substrates. Therefore, it dries quickly during printing, and accurate printing can be achieved. It also acts as a wetting agent due to its high boiling point.

The water-soluble solvent is important for preventing drying and solidification of the water-based inkjet ink at the nozzle portion of the printer head 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, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4methylpentanone 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.

Ink jet inks can further contain additives. Additives include, for example, drying accelerators, penetrants, preservatives, chelating agents, pH adjusters, surfactants, and the like.

Drying accelerators are used to accelerate the drying of water-based inkjet inks after printing. Examples of drying accelerators 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 to accelerate the penetration of the ink into the substrate and quicken the apparent drying property when the substrate is a permeable material such as paper. Examples of penetrants include water-soluble solvents, surfactants such as polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, and sodium dioctylsulfosuccinate. The amount of the penetrant to be used is preferably 0.1 to 5% by mass based on 100% by mass of the water-based inkjet ink. When used in an appropriate amount, it is difficult for printing to bleed and paper to come off.

Preservatives are, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-3-one and amine salts of. The amount of the antiseptic used is preferably 0.05 to 1.0% by mass based on 100% by mass of the water-based inkjet ink.

A chelating agent is used to capture metal ions contained in the water-based inkjet ink and prevent precipitation of insoluble matter in the nozzle or in the ink. Chelating agents include, for example, ethylenediaminetetraacetic acid, sodium salt of ethylenediaminetetraacetic acid, diammonium salt of ethylenediaminetetraacetic acid, tetraammonium salt of ethylenediaminetetraacetic acid, and the like. The amount of the chelating agent used is preferably 0.005 to 0.5% by mass based on 100% by mass of the water-based inkjet ink.

Examples of pH adjusters include various amines, inorganic salts, ammonia, and various buffer solutions.

The inkjet ink is prepared by blending and mixing each material. After mixing, it is preferable to perform filtration to remove coarse particles. For mixing, a stirrer using blades, various dispersers, emulsifiers and the like can be used. The addition order and mixing method of each material are arbitrary.

The inkjet ink is preferably filtered. This improves the ejection property from an inkjet printer. Filtration can use a well-known method.

The inkjet inks herein can use a variety of inkjet systems. 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, an electrostatic attraction method, and the like.

Preservatives are used to prevent the growth of mold and bacteria. The type of antiseptic is not particularly limited, but for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, 1- and amine salts of benzisothiazolin-3-one. These are preferably used in the range of 0.1 to 2% by weight based on the total weight of the pigment dispersion.

A pH adjuster is used to adjust the pH to a desired value. The type of pH adjuster is not particularly limited, but 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.

Defoamers are used to prevent foaming during manufacture. The type of antifoaming agent is not particularly limited, and commercially available products can also be used. For example, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol ＰＳＡ－３３６（いずれも日信化学工業社製）、ＡＤＤＩＴＯＬＶＸＷ ６２１１、ＡＤＤＩＴＯＬＶＸＷ４９７３、ＡＤＤＩＴＯＬ ＶＸＷ６２３５、ＡＤＤＩＴＯＬＸＷ３７５、ＡＤＤＩＴＯＬ ＸＷ３７６、ＡＤＤＩＴＯＬＶＸＷ６３８１、ＡＤＤＩＴＯＬ ＶＸＷ６３８６、ＡＤＤＩＴＯＬＶＸＷ６３９２、ＡＤＤＩＴＯＬ ＶＸＷ６３９３、ＡＤＤＩＴＯＬＶＸＷ６３９９、ＡＤＤＩＴＯＬ ＸＷ６５４４等（いずれもＡｌｌｎｅｘ社製）がmentioned.

Wetting agents are used to improve pigment dispersion. A smooth coating can be easily obtained with a wetting agent. The type of wetting agent is not particularly limited, and commercially available products can also be used.例えば、ＡＤＤＩＴＯＬＶＸＬ６２３７Ｎ、ＡＤＤＩＴＯＬ ＸＬ２６０Ｎ、ＡＤＤＩＴＯＬＶＸＬ６２１２、ＡＤＤＩＴＯＬ ＵＶＸ７３０１/６５、ＡＤＤＩＴＯＬ ＸＷ３３０、ＡＤＤＩＴＯＬ ＶＸＷ６２００、ＡＤＤＩＴＯＬＶＸＷ６２０５、ＡＤＤＩＴＯＬＶＸＷ６３９４、ＡＤＤＩＴＯＬＶＸＷ６２０８、ＡＤＤＩＴＯＬ ＶＸＷ６２０８/６０、ＡＤＤＩＴＯＬ ＶＸＷ６３７４（いずれもＡｌｌｎｅｘ社製）が挙げられる。

In the preparation of inkjet ink, raw materials can be mixed by using a conventional stirrer using blades, a high-speed disperser, an emulsifier, or the like. At that time, the order of adding the raw materials, the mixing method, and the like are arbitrary.

The inkjet ink of the specification can be suitably used for various inkjet printers. The applicable inkjet method is not particularly limited, but examples thereof include a charge control type, a continuous injection type such as a spray type, a piezo method, a thermal method, an electrostatic attraction method, and the like.

The inkjet ink of the present invention can be used particularly preferably as a magenta color, and other colors (cyan, yellow, black, white, red, green, blue, orange, pink, gold). , silver, bronze, etc.). The ink set is, for example, a 4-color ink set in which cyan, yellow, and black are added to the magenta color using the inkjet ink of the present invention, and further, orange, red, green, and other special colors 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 desired properties.

The inkjet ink is preferably filtered. This improves the ejection property from an inkjet printer. Any conventionally known method can be employed for filtration.

The inkjet ink of the present invention can be applied to various conventionally known substrates. Substrates include, for example, highly absorbent substrates such as plain paper, fabric, and knit; low absorbent substrates such as art paper, coated paper, vinyl chloride, wood, concrete, polyethylene film, polypropylene film, and polyethylene terephthalate film; Non-water-absorbent substrates such as metals (aluminum, stainless steel, etc.) can be used.

EXAMPLES The present invention will be described below based on examples. In addition, this invention is not limited to these. In Examples and Comparative Examples, "parts" and "%" mean "mass parts" and "mass%".

<Production of pigment composition>
(Example 1) Preparation of Pigment Composition 1 24.2 parts of 3-amino-4-methoxybenzanilide as a base component was added to 294 parts of water, stirred to prepare a suspension, and 137 parts of ice was added. The temperature was adjusted to below 5°C with 31.6 parts of 35% hydrochloric acid was added thereto and stirred for 30 minutes. Thereafter, diazotization was performed by adding an aqueous solution prepared by adding 7.1 parts of sodium nitrite to 14 parts of water and stirring for 1 hour. Two parts of sulfamic acid were added to the reaction mixture to quench the nitrous acid. A buffer consisting of a mixed solution of 36.5 parts of 25% sodium hydroxide aqueous solution, 36.5 parts of ice and 37.7 parts of 80% acetic acid was added to this to obtain a solution containing a diazo component.

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

After stirring for 1 hour, the slurry was heated to 30° C. and stirred for an additional 30 minutes. This slurry was further heated to 50° C., stirred for 30 minutes, filtered and washed with water to obtain a pigment presscake. The press cake was dried at 90° C. for 18 hours and then pulverized to obtain 54.4 parts of a pigment composition 1.

Example 2 Preparation of Pigment Composition 2 30.1 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, 1.9 parts of 3-hydroxy-2-naphthamide, N -(5-Chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide 26.7 parts, except for changing 3-hydroxy-2-naphthamide 3.8 parts in the same manner as in Example 1, pigment 53.0 parts of composition 2 were obtained.

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

Example 4 Preparation of Pigment Composition 4 30.1 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, 1.9 parts of 3-hydroxy-2-naphthamide, N -(5-Chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide 20.1 parts, except for changing 3-hydroxy-2-naphthamide 7.6 parts, carried out in the same manner as in Example 1, pigment 50.3 parts of composition 4 were obtained.

Example 5 Preparation of Pigment Composition 5 30.1 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, 1.9 parts of 3-hydroxy-2-naphthamide, N -(5-Chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide 16.7 parts, except for changing 3-hydroxy-2-naphthamide 9.5 parts in the same manner as in Example 1, pigment 49.0 parts of composition 5 were obtained.

(Example 6) Production of Pigment Composition 6 Except for adding 2.7 parts of Neoperex G-15 (manufactured by Kao Corporation, an anionic surfactant) as an additive when preparing the coupler solution, 3 to obtain 52.7 parts of Pigment Composition 6.

(Example 7) Production of Pigment Composition 7 Same as Example 3, except that 2.7 parts of Electrostripper F (manufactured by Kao Corporation, an anionic surfactant) was added as an additive when preparing the coupler solution. A pigment composition 7 (52.7 parts) was obtained in the same manner.

(Example 8) Production of Pigment Composition 8 In the same manner as in Example 3, except that 2.7 parts of Amphithol 20BS (manufactured by Kao Corporation, an amphoteric surfactant) was added as an additive when preparing the coupler solution. to obtain Pigment Composition 8 (52.7 parts).

(Example 9) Preparation of Pigment Composition 9 Except for adding 11.0 parts of Joncryl HPD 96 (manufactured by BASF, styrene-acrylic acid copolymer) as an additive when preparing the coupler solution, 3 to obtain Pigment Composition 9 (55.5 parts).

(Example 10) Production of Pigment Composition 10 The undried pigment press cake 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 added as an additive. 11.0 parts were added and stirred for 1 hour. After 9.6 parts of 80% acetic acid was added to the mixture and stirred for 30 minutes, the mixture was filtered and washed with water to obtain a pigment presscake. The press cake was dried at 90° C. for 18 hours and then pulverized to obtain 10 55.5 parts of a pigment composition.

(Example 11) Preparation of Pigment Composition 11 24.2 parts of 3-amino-4-methoxybenzanilide as a base component was added to 224 parts of water, stirred to prepare a suspension, and 137 parts of ice was added. The temperature was adjusted to below 5°C with 31.6 parts of 35% hydrochloric acid was added thereto and stirred for 30 minutes. Thereafter, diazotization was performed by adding an aqueous solution prepared by adding 7.1 parts of sodium nitrite to 14 parts of water and stirring for 1 hour. Two parts of sulfamic acid were added to the reaction mixture to quench the nitrous acid. A buffer 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 to the mixture to prepare a solution containing a diazo component.

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

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

(Example 12) Production of Pigment Composition 12 The procedure of Example 11 was repeated except that acetone was used instead of dimethyl sulfoxide in preparing the solution containing the diazo component and the coupler solution. got

(Example 13) Production of Pigment Composition 13 The procedure of Example 11 was repeated except that methanol was used instead of dimethyl sulfoxide in preparing the solution containing the diazo component and the coupler solution. got

(Example 14) Preparation of pigment composition 14 24.2 parts of 3-amino-4-methoxybenzanilide as a base component was added to 294 parts of water, stirred to prepare a suspension, and 137 parts of ice was added. The temperature was adjusted to below 5°C with 31.6 parts of 35% hydrochloric acid was added thereto and stirred for 30 minutes. Thereafter, diazotization was performed by adding an aqueous solution prepared by adding 7.1 parts of sodium nitrite to 14 parts of water and stirring for 1 hour. 2 parts of sulfamic acid was added to the reaction mixture to eliminate nitrous acid to obtain a solution containing a diazo component.
Further, 33.7 parts of an 80% aqueous acetic acid solution and 550 parts of water were put into a coupling tank and stirred to obtain an aqueous acetic acid solution.

On the other hand, a mixture of 133.6 parts of water and 32.6 parts of a 25% aqueous sodium hydroxide solution was heated to 85° C. to give N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2- as a coupler component. 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 to this to prepare a coupler solution. This solution was added over 30 minutes to a coupling tank in which an aqueous acetic acid solution was stirred to acidify out, thereby obtaining an acidifying coupler slurry. A solution containing a diazo component was added to the acid precipitation coupler slurry over 20 minutes to carry out a coupling reaction.

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

(Example 15) Production of Pigment Composition 15 Except for adding 2.7 parts of Neoperex G-15 (manufactured by Kao Corporation, an anionic surfactant) as an additive when preparing the coupler solution, In the same manner as in 14, 52.7 parts of pigment composition 15 was obtained.

(Example 16) Preparation of Pigment Composition 16 Same as Example 14 except that 2.7 parts of Electrostripper F (manufactured by Kao Corporation, an anionic surfactant) was added as an additive when preparing the coupler solution. A pigment composition 16 (52.7 parts) was obtained in the same manner.

(Example 17) Production of Pigment Composition 17 The procedure of Example 14 was repeated except that 2.7 parts of Amphithol 20BS (manufactured by Kao Corporation, an amphoteric surfactant) was added as an additive when preparing the coupler solution. to obtain 52.7 parts of Pigment Composition 17.

(Example 18) Preparation of Pigment Composition 18 24.2 parts of 3-amino-4-methoxybenzanilide as a base component was added to 294 parts of water, stirred to prepare a suspension, and 137 parts of ice was added. The temperature was adjusted to below 5°C with 31.6 parts of 35% hydrochloric acid was added thereto and stirred for 30 minutes. Thereafter, diazotization was performed by adding an aqueous solution prepared by adding 7.1 parts of sodium nitrite to 14 parts of water and stirring for 1 hour. Two parts of sulfamic acid were added to the reaction mixture to quench the nitrous acid. A buffer consisting of a mixed solution of 36.5 parts of 25% sodium hydroxide aqueous solution, 36.5 parts of ice and 37.7 parts of 80% acetic acid was added to this to obtain 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 added as a coupler component. - 30.1 parts of naphthamide was added and dissolved, and 46.8 parts of ice was added and cooled to obtain a coupler solution A. A coupler solution B was prepared by adding and dissolving 1.9 parts of 3-hydroxy-2-naphthamide in a mixture of 60 parts of water and 9.8 parts of a 25% aqueous sodium hydroxide solution in a separate vessel. The prepared coupler solution A was added to the solution containing the diazo component over 20 minutes, 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 stirred for an additional 30 minutes. This slurry was further heated to 50° C., stirred for 30 minutes, filtered and washed with water to obtain a pigment presscake. The press cake was dried at 90° C. for 18 hours and then pulverized to obtain 51.7 parts of Pigment Composition 18.

(Example 19) Preparation of Pigment Composition 19 24.2 parts of 3-amino-4-methoxybenzanilide as a base component was added to 224 parts of water, stirred to prepare a suspension, and 137 parts of ice was added. The temperature was adjusted to below 5°C with 31.6 parts of 35% hydrochloric acid was added thereto and stirred for 30 minutes. Thereafter, diazotization was performed by adding an aqueous solution prepared by adding 7.1 parts of sodium nitrite to 14 parts of water and stirring for 1 hour. Two parts of sulfamic acid were added to the reaction mixture to quench the nitrous acid. A buffer 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 to the mixture to prepare a solution containing a diazo component.

On the other hand, 23 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide as a coupler component was added to a mixture of 70 parts of water, 70 parts of dimethyl sulfoxide and 22.8 parts of a 25% aqueous sodium hydroxide solution. 4 parts were added and dissolved to obtain a coupler solution A. In a separate container, add 5.7 parts of 3-hydroxy-2-naphthamide to a mixture of 30 parts of water, 30 parts of dimethyl sulfoxide, and 9.8 parts of a 25% aqueous sodium hydroxide solution and dissolve. and The prepared coupler solution A was added to the solution containing the diazo component over 20 minutes, 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 stirred for an additional 30 minutes. This slurry was further heated to 50° C., stirred for 30 minutes, filtered and washed with water to obtain a pigment presscake. The press cake was dried at 90° C. for 18 hours and then pulverized to obtain 51.7 parts of Pigment Composition 19.

(Example 20) Production of Pigment Composition 20 The procedure of Example 19 was repeated except that acetone was used instead of dimethyl sulfoxide in preparing the solution containing the diazo component and the coupler solution. got

(Example 21) Production of Pigment Composition 21 The procedure of Example 19 was repeated except that methanol was used instead of dimethyl sulfoxide in 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 Pigment Composition 22 (CI Pigment Red 269) 55.5 parts were obtained.

(Comparative Example 2) Preparation of Pigment Composition 23 30.1 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, 1.9 parts of 3-hydroxy-2-naphthamide, N -(5-Chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide 31.8 parts, except for changing 3-hydroxy-2-naphthamide 1.0 parts, carried out in the same manner as in Example 1, pigment 55.0 parts of composition 23 were obtained.

(Comparative Example 3) Preparation of Pigment Composition 24 30.1 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, 1.9 parts of 3-hydroxy-2-naphthamide, N -(5-Chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide 13.4 parts, except for changing to 3-hydroxy-2-naphthamide 11.5 parts, carried out in the same manner as in Example 1, pigment 47.6 parts of composition 24 were obtained.

(Comparative Example 4) Preparation of Pigment Composition 25 30.1 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, 1.9 parts of 3-hydroxy-2-naphthamide, N -(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide 23.4 parts, except for changing to N-(3-nitrophenyl)-3-hydroxy-2-naphthamide 9.4 parts, The procedure was carried out in the same manner as in Example 1 to obtain 55.1 parts of Pigment Composition 25.

(Comparative Example 5) Preparation of Pigment Composition 26 30.1 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, 1.9 parts of 3-hydroxy-2-naphthamide, -Hydroxy-2-naphthamide 9.5 parts, N-(3-nitrophenyl)-3-hydroxy-2-naphthamide 15.7 parts was changed in the same manner as in Example 1, pigment composition 26 48 .0 copies were obtained.

(Comparative Example 6) Preparation of Pigment Composition 27 30.1 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, 1.9 parts of 3-hydroxy-2-naphthamide, 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 56.6 parts of Pigment Composition 27 was obtained in the same manner as in Example 1 except that

(Comparative Example 7) Preparation of Pigment Composition 28 30.1 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide, 1.9 parts of 3-hydroxy-2-naphthamide, N -(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide 23.4 parts, N-(2-methyl-5-chlorophenyl)-3-hydroxy-2-naphthamide 9.5 parts Other than that, the procedure was carried out in the same manner as in Example 1 to obtain 55.2 parts of Pigment Composition 28.

(Example 22) Production of Pigment Composition 29 To 1000 parts of 98% sulfuric acid was added 35 parts of Pigment Composition 22 obtained in Comparative Example 1, C.I. I. 15 parts of Pigment Red 150 (Toshiki Red 150TR manufactured by Tokyo Shikizai Kogyo Co., Ltd.) was gradually added with stirring and dissolved by stirring for 4 hours. Then, the solution was gradually added dropwise to 8000 parts of water at 10° C. over 30 minutes with stirring, followed by filtration and washing to obtain a pigment presscake. This press cake was dried at 90° C. for 18 hours and then pulverized to obtain 47.5 parts of Pigment Composition 29.

(Example 23) Production of Pigment Composition 30 70 parts of Pigment Composition 22 obtained in Comparative Example 1, C.I. I. Pigment Red 150 (manufactured by Tokyo Shikizai Kogyo Co., Ltd., Toshiki Red 150TR) 30 parts, sodium chloride 1000 parts, and diethylene glycol 150 parts were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 60 ° C. for 8 hours ( h) Kneaded. Next, the kneaded mixture was put into hot water of about 70° C., stirred for 1 hour to form a slurry, filtered and washed to obtain a pigment press cake. This press cake was dried at 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 Pigment Composition 22 obtained in Comparative Example 1, C.I. I. Pigment Red 150 (manufactured by Tokyo Shikizai Kogyo Co., Ltd., Toshiki Red 150TR) was mixed with 25 parts using a high-speed stirring disper to obtain 99.9 parts of Pigment Composition 31.

The X-ray diffraction of the resulting 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 Japanese Industrial Standards JIS K0131 (general rules for X-ray diffraction analysis), using CuKα rays, with diffraction angles (2θ) ranging from 3° to 35°.

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 longitudinal limiting slit: 10mm
Scattering slit: 2°
Light receiving slit: 0.3 mm
Tube: Cu
Tube voltage: 40kV
Tube current: 40mA

The following examples of powder X-ray diffraction measurements are shown in the figures. Example 3 is shown in FIG. 1, Comparative Example 1 is shown in FIG. I. Pigment Red 150 (Toshiki Red 150TR manufactured by Tokyo Shikizai Kogyo Co., Ltd.) is shown in FIG. 3, and Comparative Example 8 is shown in FIG.

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

The pigment compositions of Examples 1-23 were solid solutions and composite pigment particles were formed. In the table, PR stands for C.I. I. It is an abbreviation for Pigment Red.

<Coloring composition and its property evaluation>
Coloring compositions for various applications were prepared using the obtained pigment composition, and their properties were evaluated.

- Resin composition for molding1. Preparation of molding resin composition and production of molded product (Example A-1) Production of molded product a-1
2 parts of the obtained pigment composition 1 and 1000 parts of a polypropylene resin (product name: Prime Polypro J105, manufactured by Prime Polymer Co., Ltd.) are melt-kneaded at 220° C. in a twin-screw extruder, and then cut with a pelletizer. A resin composition for molding in the form of pellets 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. got

(Examples A-2 to A-23, Comparative Examples A-1 to A-8) Preparation of molded bodies a-2 to a-31 Pigment composition 1 of Example A-1 was changed as shown in Table 2. Molded bodies a-2 to a-31 were obtained in the same manner as in Example A-1 except that

(Example A-24) Preparation of molded article a-32 2 parts of the obtained pigment composition 1 and 1000 parts of polyethylene terephthalate resin (product name: Vylopet EMChaihun 307, manufactured by Toyobo Co., Ltd.) were extruded at 275 parts by twin-screw extruder. C. and then cut with a pelletizer to obtain a resin composition for molding in the form of pellets. Next, the resin composition for molding 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 body (plate) having a thickness of 3 mm.

(Examples A-25 to A-46, Comparative Examples A-9 to A-16) Preparation of molded bodies a-33 to a-62 Change pigment composition 1 of Example A-24 as shown in Table 3 Moldings a-33 to a-62 were obtained in the same manner as in Example A-24 except that

2. Evaluation of compact (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.

(Vividness)
Each molded article produced was visually observed and evaluated according to the following criteria. The results are shown in Tables 2 and 3.
○: Brighter red than the molded bodies (a-22 and a-53) produced in Comparative Examples A-22 and A-53 △: Molded bodies produced in Comparative Examples A-22 and A-53 (a-22 And red equivalent to a-53) ×: darker red than the compacts (a-22 and a-53) produced in Comparative Examples A-22 and A-53

From the results in Tables 2 and 3, the molded bodies of Examples A-1 to A-44 had no coarse particles and had good dispersibility. In addition, clearness is also good.

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

On the other hand, for comparison, 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 dispersion state of the pigment was observed for each sample using a transmission electron microscope. As a result, it was found that the negatively charged toner 1 using the pigment composition 3 had a higher dispersibility than the negatively charged toner 2 using the pigment composition 22 because the pigment was uniformly distributed.

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

(Examples C-2 to C-23, Comparative Examples C-1 to C-8) Preparation of coloring compositions c-2 to c-31 Pigment composition 1 of Example C-1 as shown in Table 4 Colored compositions c-2 to c-31 were obtained in the same manner as in Example C-1 except for the change.

2. Evaluation of coloring composition (crystal stability)
In order to evaluate the crystal stability (crystal growth inhibitory effect), 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 are photographed with a transmission electron microscope (manufactured by Hitachi High-Technologies Corporation, model H-7650 transmission electron microscope). The diameter (major axis) of each was measured. A value obtained by averaging them was calculated, and the value was defined as the average primary particle size. The prepared colored composition was sealed in a screw cap bottle and stored at 50° C. for 1 week, 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. Table 4 shows the results.

- Aqueous coloring composition1. 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 zirconia beads with a diameter of 1.25 mm were charged in a 70 ml glass bottle, and a paint shaker manufactured by Red Devil Co., Ltd. was charged. and dispersed for 60 minutes to obtain a dispersion.
・Pigment composition 1: 3.15 parts ・Polyester-modified acrylic acid polymer (ADDITOL XW 6528, manufactured by Allnex): 5.25 parts ・Wetting agent (ADDITOL XW 6374, manufactured by Allnex): 0.95 parts Foaming agent (ADDITOL XW 6211, manufactured by Allnex): 0.63 parts Ion-exchanged water: 21.52 parts Next, the zirconia beads were removed from the dispersion to obtain a water-based coloring composition d-1.

(Examples D-2 to D-23, Comparative Examples D-1 to D-8) Preparation of aqueous coloring compositions d-2 to d-31 Pigment composition 1 of Example D-1 as shown in Table 5 Except for changing to, in the same manner as in Example D-1, water-based coloring compositions d-2 to d-31 were obtained.

2. Evaluation of water-based coloring composition (initial viscosity and viscosity stability)
The initial viscosity at 25° C. of the resulting water-based colored composition was measured using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosity was measured after aging at 25° C. for 1 week and after aging at 50° C. for 1 week. Based on the obtained measured values, the rate of increase in viscosity relative to the initial viscosity was calculated and used as an index of viscosity stability, and evaluated according to the following evaluation criteria. Table 5 shows the results. The lower the initial viscosity, the better the dispersibility. Moreover, 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 1. The initial viscosity is 10.0 mPa·s or more. impractical

(Evaluation criteria for viscosity stability)
4. Viscosity increase rate is less than 20%. Very good3. The viscosity increase rate is 20% or more and less than 30%. good2. The viscosity increase rate is 30% or more and less than 40%. Practical 1. The viscosity increase rate is 40% or more. impractical

・Water-based paint 1. Preparation of water-based paint (Example E-1)
Using a high-speed stirrer, the following raw materials were stirred 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, Barnock WD-304): 13.6 parts ・ Melamine resin (manufactured by Allnex, Cymel 325): 3.4 copies

Using a high-speed stirrer, the following raw materials were stirred 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, Barnock WD-304): 13.6 parts Melamine resin (manufactured by Allnex, Cymel 325): 3.4 copies

Using a 7 mil applicator, the aqueous paint 1 and the aqueous paint 2 thus obtained were applied to a commercially available polyethylene terephthalate (PET) film having a thickness of 100 μm. 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 140° C. for 20 minutes to obtain a coated 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 in the same manner as in Example E-1 to obtain coated films e-2 to e-31.

2. Evaluation of paint film (hue stability)
Using a colorimeter (manufactured by Konica Minolta, CM-700d), the color of the coated film stored at 25 ° C. for 1 week and the coated film stored at 50 ° C. for 1 week was measured, and the color difference (ΔE*) was obtained. Judged by standards. Table 6 shows the results. The smaller the color difference, the more excellent 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. ΔE* is 1.0 or more and less than 2.0.
2. ΔE* is 2.0 or more and less than 3.0.
1. ΔE* is 3.0 or more.

(color strength)
The coated film stored at 25°C for 1 week was visually observed and evaluated according to the following criteria. Table 6 shows the results.
(Evaluation criteria for coloring strength)
○: higher reflection density than the painted article (e-22) prepared in Comparative Example E-1 △: equivalent to the painted article (e-22) prepared in Comparative Example E-1 ×: in Comparative Example E-1 Reflection density is lower than the prepared painted object (e-22)

(Vividness)
The coated film stored at 25°C for 1 week was visually observed and evaluated according to the following criteria. Table 6 shows the results.
(Evaluation criteria for sharpness)
○: Brighter red than the painted object (e-22) produced in Comparative Example E-1 △: Red equivalent to the painted object (e-22) produced in Comparative Example E-1 ×: Comparative Example E-1 Darker red than the painted object (e-22) prepared in

・ Gravure ink 1. Preparation of gravure ink First, the method for measuring the resin will be described below.
(hydroxyl value)
It was obtained according to JIS K0070.
(acid number)
It was obtained according to JIS K0070.
(amine value)
The amine value was obtained by the following method according to JIS K0070 in terms of mg of potassium hydroxide equivalent to the equivalent of hydrochloric acid required to neutralize the amino groups contained in 1 g of the resin. 0.5 to 2 g of the sample was accurately weighed (sample non-volatile content: Sg). 50 mL of a mixed solution of methanol/methyl ethyl ketone=60/40 (mass ratio) was added to the accurately weighed sample to dissolve the sample. Bromophenol blue was added to the resulting solution as an indicator, and the resulting solution was titrated with a 0.2 mol/L ethanolic hydrochloric acid solution (potency: f). The point at which the color of the solution changed from green to yellow was defined as the end point, and the titration amount (Am L) at this time was used to determine the amine value by the following formula.
Amine value = (A x f x 0.2 x 56.108) / S [mgKOH/g]

(Weight average molecular weight)
The weight-average molecular weight was obtained by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation) and obtaining the converted molecular weight using polystyrene as a standard substance. Measurement conditions are shown below.
Column: The following columns were connected in series and used.
Tosoh guard column HXL-H
Tosoh TSKgelG5000HXL
Tosoh TSKgelG4000HXL
Tosoh TSKgelG3000HXL
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 measurement). A DSC8231 manufactured by Rigaku Co., Ltd. was used as the measuring instrument, the measurement temperature range was −70 to 250° C., the temperature increase rate was 10° C./min, and the midpoint between the endothermic start temperature and the end temperature based on the glass transition in the DSC curve was set to a glass temperature. was taken as the transition temperature.

(Synthesis Example 1) [Polyurethane resin PU1]
200 parts of polypropylene glycol having a number average molecular weight of 700 (hereinafter “PPG700”), 127 parts of isophorone diisocyanate (hereinafter “IPDI”), and 81.8 parts of ethyl acetate are reacted at 80° C. for 4 hours under a stream of nitrogen to form a terminal isocyanate. A resin solution of urethane prepolymer was obtained. Next, 49.5 parts of isophoronediamine (hereinafter "IPDA"), 3 parts of 2-ethanolamine, and a mixed solvent of ethyl acetate/isopropanol (hereinafter "IPA") = 50/50 (mass ratio) of 803.5 parts. To a mixture of 9 parts, the obtained resin solution of the terminal isocyanate urethane prepolymer was gradually added at 40°C, followed by reaction at 80°C for 1 hour to obtain a nonvolatile content of 30% and an amine value of 3.5 mgKOH/g. , a hydroxyl value of 7.3 mgKOH/g and a weight average molecular weight of 40,000. The glass transition temperature was -32°C.

(Example F-1) Preparation of Gravure Ink f-1 30 parts of polyurethane resin solution PU1 (30% non-volatile content) was used as the binder resin, and polyethylene wax (A-C400A manufactured by Honeywell) was used as the hydrocarbon wax. 0.8 parts in terms of conversion, 0.5 parts of chlorinated polypropylene resin (manufactured by Nippon Paper Industries Co., Ltd. 370M chlorine content 30% non-volatile content 50%) in terms of non-volatile content, 10 parts of pigment composition 1, methyl ethyl ketone (hereinafter “MEK )/n-propyl acetate (hereinafter “NPAC”)/IPA = 40/40/20 (mass ratio) 58.7 parts were mixed and dispersed for 15 minutes with an Eiger mill 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 Pigment composition 1 of Example F-1 was changed as shown in Table 7. Gravure inks f-2 to f-31 were obtained in the same manner as in Example F-1 except that

(Example F-24) Printing of gravure ink f-1. The following base material ( In the case of OPP, the corona discharge treated surface) was printed at a printing speed of 80 m/min to obtain OPP prints and CPP prints.
(Base material)
・ OPP: Biaxially stretched polypropylene (OPP) film with corona discharge treatment on one side (Futamura Chemical Co., Ltd. FOR thickness 25 μm)
・ CPP: Unstretched polypropylene (CPP) film without corona treatment (CP-S thickness 30 μm manufactured by Mitsui Chemicals Tohcello)

(Examples F-25 to F-46, Comparative Examples F-9 to F-16) Printing of gravure inks f-2 to f-31 An OPP printed matter and a CPP printed matter were obtained in the same manner as in Example F-24 except for the change.

2. Gravure ink and printed matter evaluation (ink stability over time)
Each prepared gravure ink was placed in a sealed container and stored at 40° C. for 10 days. After that, the viscosity was measured to evaluate the viscosity change from before storage. The viscosity was measured at 25°C with a Zahn cup No. A run time of 4 seconds was performed. Table 7 shows the results. All inks had a viscosity within the range of 40 to 500 cps (25° C.) measured by a Brookfield viscometer before storage.
(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. Viscosity change from 5 seconds to less than 10 seconds (slightly poor)
2. Viscosity change is 10 seconds or more and less than 15 seconds (bad)
1. Viscosity change for 15 seconds or more (extremely poor)
Note that 5 and 4 are within a practically acceptable range.

(Vividness)
The obtained OPP printed matter and CPP printed matter were visually observed and evaluated according to the following criteria. Table 8 shows the results.
(Evaluation criteria for sharpness)
○: Brighter red than the printed matter (f-22) produced in Comparative Example F-9 △: Red equivalent to the printed matter (f-22) produced in Comparative Example F-9 ×: Produced in Comparative Example F-9 Darker red than printed matter (f-22)

・ Flexo ink 1. Preparation of Flexographic Ink (Synthesis Example 2) [Polyurethane Resin PU2]
While introducing nitrogen gas into a reaction vessel equipped with a thermometer, a stirrer, a reflux device, and a nitrogen gas introduction tube, PTG-3000SN (polytetramethylene glycol manufactured by Hodogaya Chemical Co., Ltd.; ) 121.8 parts, 24.4 parts of PEG2000 (NOF polyethylene glycol, functional group number 2, hydroxyl value 56, number average molecular weight 2000), 2,2-dimethylolpropionic acid 32.7 parts and isophorone diisocyanate 66.9 parts were charged. , 90° C. for 3 hours. After cooling, a mixed solution of 16.6 parts of 25% aqueous ammonia and 73.0 parts of ion-exchanged water was gradually added dropwise to the resulting water-soluble resin to neutralize it, thereby obtaining an aqueous solution of polyurethane resin PU2. rice field. The obtained polyurethane resin PU2 had an acid value of 55 mgKOH/g and a weight average molecular weight (Mw) of 36,000.

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

(Measurement of weight average molecular weight (Mw))
A value converted to polystyrene by GPC (gel permeation chromatography) measurement. The dried polyurethane resin PU2 is dissolved in tetrahydrofuran to prepare a 0.1% solution, and the weight-average molecular weight is determined by Tosoh HLC-8320-GPC (column number M-0053, molecular weight measurement range of about 2,000 to about 4,000,000). was measured.

(Example G-1) Flexographic ink g-1 adjustment pigment composition 15 parts, polyurethane resin PU2 35.0 parts, nonionic surfactant (Surfinol 104PA, manufactured by Air Products) 0.1 part, n- 2.0 parts of propanol, 2.0 parts of polyethylene wax (Aquapetro DP2502B, Toyo Adolé Co., Ltd.), 0.2 parts of antifoaming agent (Tegoformex 1488, Evonik Co., Ltd.), and 45.7 parts of ion-exchanged water were added. After stirring and mixing with a speed mixer, the mixture was dispersed with a sand mill filled with zirconia beads with a diameter of 1.25 mm for 60 minutes to obtain flexographic ink g-1.

(Examples G-2 to G-23, Comparative Examples G-1 to G-8) Preparation of flexographic inks g-2 to g-31 Pigment composition 1 of Example G-1 was changed as shown in Table 9. Flexo inks g-2 to g-31 were obtained in the same manner as in Example G-1 except that

2. Evaluation of flexo ink (coarse grain)
Using a grind gauge (according to JIS K5600-2-5), the presence or absence of coarse particles in the flexographic ink was confirmed and evaluated according to the following evaluation criteria. Table 9 shows the results.
(Evaluation criteria for coarse particles)
○: The size of coarse particles is less than 60 μm (good)
△: The size of coarse particles is 60 or more and less than 90 μm (no practical problem)
×: The size of coarse particles is 90 μm or more (defective)

(viscosity stability)
Viscosity at 25° C. was measured using a Zahn cup (No. 4). Further, the composition was stored in a constant temperature machine at 40° C. for 1 week, accelerated over time, and then the rate of change in viscosity before and after the lapse of time 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)
△: Viscosity change rate before and after storage at 40 ° C. for 1 week is ± 10% or more and less than ± 15% (practically no problem)
×: Viscosity change rate before and after storage at 40 ° C. for 1 week is ± 15% or more (defective)

- Aqueous inkjet inks1. Preparation of water-based inkjet ink (water-based IJ ink) (Example H-1) Preparation of water-based IJ ink h-1 Pigment composition 1: 19.0 parts Styrene-acrylic acid copolymer (manufactured by BASF Japan, John Krill 61J): 16.4 parts Surfactant (manufactured by Kao Corporation, Emulgen 420): 5.0 parts Ion-exchanged water: 59.6 parts and 200 parts of zirconia beads with a diameter of 1.25 mm are placed in a 200 ml glass bottle. It was prepared and dispersed for 6 hours using a paint shaker manufactured by Red Devil. Next, the zirconia beads were removed from the above dispersion to obtain an aqueous colored composition.

Next, the above 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 (manufactured by BASF Japan, Joncryl 60): 3.3 parts - Surfactant (manufactured by Kao Corporation, Emulgen 420): 2 0 part of deionized water: 64.9 parts Then, diethylene glycol monobutyl ether was added to the above mixture as appropriate 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 membrane filter and further filtered using a 0.45 μm membrane filter to obtain aqueous IJ ink g-1.

(Examples H-2 to H-23, Comparative Examples H-1 to H-8) Preparation of water-based IJ inks h-2 to h-31 Aqueous IJ Inks h-2 to h-31 were obtained in the same manner as in Example H-1 except for the changes.

2. Evaluation of water-based IJ ink (tinting strength)
The prepared water-based IJ ink was filled in a cartridge of a Seiko Epson printer PX-105 (piezo type inkjet printer), and printed on A4 size plain paper. The printed matter was visually observed and evaluated according to the following criteria. Table 10 shows the results.
(Evaluation criteria for coloring strength)
○: Higher reflection density than printed matter using the water-based IJ ink (h-22) prepared in Comparative Example H-1 △: Water-based IJ ink (h-22) prepared in Comparative Example H-1 was used Equivalent to printed matter ×: Reflection density is lower than printed matter using water-based IJ ink (h-22) prepared in Comparative Example H-1

(Vividness)
The prepared water-based IJ ink was filled in a cartridge of a Seiko Epson printer HG-5130, and printing was performed. The printed matter was visually observed and evaluated according to the following criteria. Table 10 shows the results.
(Evaluation criteria for sharpness)
○: Brighter than prints using the water-based IJ ink (h-22) prepared in Comparative Example H-1 △: Prints using the water-based IJ ink (h-22) prepared in Comparative Example H-1 Equivalent ×: More dull than the print using the water-based IJ ink (h-22) prepared in Comparative Example H-1

Also, when the base material was changed from A4 size plain paper to coated paper, polypropylene film (OPP film), polyethylene terephthalate film, and aluminum foil, the same results were obtained when the coloring strength was evaluated. When the base material was not paper, the base material was attached to A4 plain paper.
In addition, using MAXIFYMB5430 (thermal inkjet printer) manufactured by Canon Inc., a tank filled with the prepared water-based IJ ink was mounted as a magenta ink, and the same results were obtained when coloring power was evaluated.

(viscosity stability)
For each water-based IJ ink, the initial viscosity at 25° C. was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosity was measured after being aged at 50° C. for 4 weeks. Using each measured value, the rate of increase in viscosity relative to the initial viscosity was calculated and used as an index of viscosity stability, and evaluated according to the following criteria. Table 10 shows the results. It is considered that the smaller the viscosity increase rate, the better the viscosity stability.
(Evaluation criteria for viscosity stability)
O: The viscosity increase rate is less than 20%.
Δ: The viscosity increase rate is 20% or more and less than 40%.
x: Viscosity increase rate is 40% or more.

(Crystal stability)
As an index of crystal stability (crystal growth inhibitory effect), the average primary particle size of the pigment in each water-based IJ ink was measured. Water-based IJ ink is dropped on a mesh with a support film, and the dried product is used as a sample, and the particles are photographed with a transmission electron microscope (manufactured by Hitachi High-Technologies Co., Ltd., H-7650 transmission electron microscope). The longer diameter (major diameter) of each of 50 primary particles of the pigment constituting the was measured. A value obtained by averaging them was calculated, and the value was defined as the average primary particle size. The prepared water-based IJ ink was sealed in a screw-capped bottle, stored at 50° C. for 4 weeks, then subjected to the same measurement, and the crystal stability was evaluated from the change in average primary particle size before and after storage. Table 10 shows the results.

From the results in the table, when the pigment composition of the present invention is used, a coloring composition that is excellent in dispersibility, coloring strength and vividness, has good crystal stability and storage stability, and can be applied to various uses can be obtained. be done. For example, a resin composition for molding can provide a molded article having excellent dispersibility and sharpness. Further, in the toner, it is possible to provide a toner excellent in pigment dispersibility. In addition, in the form of the colored composition, it can be seen that the crystal stability is improved. Moreover, the water-based coloring composition is excellent in storage stability. In addition, water-based paints are excellent in storage stability, tinting strength and vividness. It is also found that the printing ink is excellent in storage stability, dispersibility, and clarity. Furthermore, it can be seen that the water-based inkjet ink is excellent in dispersibility, coloring strength and vividness, and also has good crystal stability and storage stability.

Claims (9)

C. I. Pigment Red 269, and C.I. I. A pigment composition containing composite pigment particles comprising Pigment Red 150,
C.I. in 100 mol % of the composite pigment particles I. A pigment composition containing 10 to 50 mol % of Pigment Red 150. 2. The pigment composition according to claim 1, wherein powder X-ray diffraction using CuKα rays of said composite pigment particles does not have a maximum peak within the range of diffraction angle (2θ)=13.5 to 14.5°. A coloring composition comprising the pigment composition of claim 1 or 2 and a dispersing medium. 4. The coloring composition of claim 3, wherein said dispersion medium comprises a resin. A molding resin composition comprising the coloring composition according to claim 4 . A toner comprising the coloring composition according to claim 3 or 4. A paint comprising the coloring composition according to claim 3 or 4. A printing ink comprising the coloring composition according to claim 3 or 4. An inkjet ink comprising the coloring composition according to claim 3 or 4.

Images