JP2022098438A - Pigment composition, and use thereof - Google Patents

Abstract

To provide a pigment composition that gives a halogen-free greenish blue with good dispersibility.SOLUTION: A pigment composition contains a compound (1) represented by the following formula (1), and a divalent metal of 10-5000 ppm. The divalent metal is preferably at least one of copper and calcium. The pigment composition is preferably a coloring composition containing a dispersion medium. The coloring composition is preferably used for a composition for molding, a toner, a coating, an ink or the like.SELECTED DRAWING: None

Description

The present invention relates to pigment compositions.

In recent years, from an environmental point of view, there is a growing concern about environmental pollution caused by chemical substances, and there is an increasing demand for consideration for products during disposal and incineration. Halides may generate harmful substances such as PCBs and dioxins when incinerated, and there is a movement to refrain from using them as materials for products.

Organic pigments are used as colorants in plastic products, toners, paints, and printing inks. Known organic pigments include, for example, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, and quinacridone pigments.

Among these organic pigments, as the greenish blue pigment phthalocyanine pigment, low halogenated phthalocyanine blue (for example, CI Pigment Blue76) is used as an environmentally friendly product. Since low-halogenated phthalocyanine blue contains chlorine and bromine in its chemical structure, toxic substances such as dioxin may be generated during combustion. However, there was no environmentally friendly product to replace the low-chlorinated phthalocyanine nin blue.

Therefore, Patent Document 1 discloses a phthalocyanine pigment having no halogen.

WO2013 / 015180

However, the phthalocyanine pigment described in Patent Document 1 does not contain a halogen, but has a problem of poor dispersibility.

An object of the present invention is to provide a pigment composition capable of obtaining a halogen-free greenish blue color having good dispersibility.

The pigment composition of the present invention contains the compound (1) represented by the following formula (1) and 10 to 5000 ppm of a divalent metal.
Equation (1)

According to the above invention, it is possible to provide a pigment composition, a coloring composition, a molding composition, a toner, a paint and a printing ink which can obtain a halogen-free greenish blue color having good dispersibility.

In the present specification, the descriptions such as "(meth) acryloyl", "(meth) acrylic acid", "(meth) acrylate", and "(meth) acryloyloxy" are referred to as "acryloyl and", respectively, unless otherwise specified. / Or methacryloyl ”,“ acrylic acid and / or methacrylic acid ”,“ acrylate and / or methacrylate ”, and“ acryloyloxy and / or methacryloyloxy ”. Further, "PO" represents "propylene oxide" and "EO" represents "ethylene oxide". The ethylenically unsaturated double bond is a (meth) acryloyl group, an allyl group, a vinyl group, a vinyl ether group or the like. Further, "CI" described in the present specification means a color index (CI).

<Pigment composition>
The pigment composition of the present invention contains the compound (1) represented by the following formula (1) and 10 to 5000 ppm of a divalent metal.
Equation (1)

As described above, the pigment composition of the present invention contains the compound (1) and an appropriate amount of divalent metal to improve the dispersibility, which has been a problem of the metal-free phthalocyanine compound, and the metal-free phthalocyanine is preferable. The hue (greenish blue) can be maintained. The pigment composition of the present invention can be used in a wide range of applications that require coloring of molded products, toners, paints, printing inks, and the like.

The reason why the dispersibility is improved by containing the compound (1) and an appropriate amount of the divalent metal can be divided into the following two.
The first is the case where the divalent metal is derived from a metal-containing pigment. In this case, the reason for the excellent dispersibility is that the divalent metal pigment that is easy to disperse is adsorbed on the surface of the compound (1), and the divalent metal pigment that is easy to disperse from the surface state of the compound (1) that is difficult to disperse. It is presumed that it will be in a surface state. It is presumed that the presence of the divalent metal pigment on the surface causes the above effect even in a small amount, does not impair the hue of the compound (1), and produces a good greenish blue pigment.
The second is the case where it is derived from a metal compound other than a pigment. In this case, the reason why the dispersibility is excellent is that the compound (1) contains a salt of a divalent metal to prevent the aggregation of the compound (1), that is, the secondary aggregation of the pigment composition is reduced, so that the dispersibility is excellent. I guess it will improve. This is because the compound (1) has a strong π-π interaction, so that secondary agglomeration in which the primary particles of the pigment agglomerate easily occurs even after the pigment is formed, but it is divalent such as a calcium salt during drying. It is presumed that the presence of the metal salt plays a role in preventing the secondary aggregation of the pigment, the particles of the compound (1) are easily loosened at the time of dispersion, and the dispersibility is improved.

By combining the effect of modifying the surface condition of the compound (1) of the divalent metal phthalocyanine and the effect of the salt of the divalent metal (calcium salt, etc.) to prevent the secondary aggregation of the pigment, the dispersibility is further improved. It is presumed that a pigment composition having viscosity stability can be obtained.

The content of the divalent metal in 100% by mass of the pigment composition of the present invention is preferably 10 to 5000 ppm, more preferably 25 ppm to 3000 ppm, more preferably 50 to 1500 ppm, still more preferably 80 ppm to 1000 ppm.

<Synthesis of compound (1)>
Examples of the method for synthesizing compound (1) include the following methods.

Compound (1) can be synthesized by a demetallizing reaction by contacting a specific metallic phthalocyanine with an acid.
Examples of the metallic phthalocyanine include lithium phthalocyanine, sodium phthalocyanine, calcium phthalocyanine, magnesium phthalocyanine and the like.
Examples of the acid include sulfuric acid and hydrochloric acid.

Further, a method of directly obtaining from phthalonitrile, 1,3-diiminoisoindoline or the like can also be mentioned.

Any known method may be used for producing the metallic phthalocyanine, and for example, phthalic acids, urea, a metal or a metal salt, a catalyst and the like may be heated in the presence or absence of an organic solvent. Can be manufactured.

After synthesizing the compound (1), it is preferable to perform separation treatment from the reaction solvent such as filtration of the solvent and distillation of the solvent, and then washing with water or an organic solvent. Acids and alkalis may be used for cleaning. If further purification is required, impurities may be removed by operations such as sublimation, acid paste, acid slurry, reprecipitation, recrystallization, and extraction, which are known purification techniques.

<Divalent metal>
The divalent metal may be used as long as it can solve the problem, and is not limited thereto, and examples thereof include copper, beryllium, calcium, magnesium, strontium, barium, nickel, iron, zinc, lead, cobalt, and molybdenum. .. Among these, copper and calcium are preferable in terms of improving weather resistance and heat resistance in addition to dispersibility.
Examples of the addition of the divalent metal include (1) a method of adding a metal-containing pigment and (2) a method of adding a metal compound other than the pigment.

(Metal-containing pigment)
Metal-containing pigments include, for example, copper phthalocyanine, calcium phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, C.I. I. Pigment Yellow 150 and the like. Among these, a divalent metal phthalocyanine compound that strongly interacts with the compound (1) is preferable, and copper phthalocyanine having high weather resistance and heat resistance in addition to dispersibility is more preferable.

The reason why the divalent metal phthalocyanine is preferable is that the divalent metal phthalocyanine that is easily dispersed is adsorbed on the surface of the compound (1), and the surface state of the compound (1) that is difficult to disperse is changed to the surface of the divalent metal phthalocyanine that is easily dispersed. It is presumed that it will be in a state and the dispersibility will be improved. It is presumed that the presence of the divalent metal phthalocyanine on the surface causes the above effect even in a small amount, does not impair the hue of the compound (1), and produces a good greenish blue pigment.

Hereinafter, a method for producing a pigment composition when the divalent metal is derived from copper phthalocyanine will be described.
The production method includes, for example, a method of blending compound (1) and copper phthalocyanine, a method of co-synthesizing copper phthalocyanine during the synthesis of compound (1), a method of blending copper phthalocyanine during synthesis of compound (1), and a method of pigmenting. Examples include a method of blending copper phthalocyanine. As a method of blending the compound (1) and copper phthalocyanine at the time of pigmentation, a pigment is obtained by an acid pacing method, an acid slurry method, a dry milling method, a salt milling method, a solvent salt milling method, a solvent method, or a combination thereof. There is a method of making it.

In addition, pigmentation is a state in which a crude pigment called crude, which is a coarse crystal and has a wide particle size distribution, can be used as a pigment through processes for the purposes of purification, control of crystal shape and particle size, surface treatment, and the like. It is a process to process.

Pigmentization by acid pacing dissolves crude pigments in concentrated sulfuric acid and mixes them with a large excess of water to precipitate fine pigment particles. Then, by repeating filtration and washing with water and drying, a pigment composition having a desired crystal shape and particle size can be obtained.

As the acid pacing, for example, a method of dissolving a crude pigment in 98% sulfuric acid 5 to 30 times by mass thereof and mixing the obtained sulfuric acid solution with water 5 to 30 times by mass thereof can be mentioned. The temperature at which the pigment is dissolved in sulfuric acid should be such that reactions such as decomposition and sulfonation of raw materials do not occur. The temperature at the time of melting is preferably, for example, 3 to 40 ° C. Further, the method of mixing the sulfuric acid solution of the pigment and water, and the conditions such as the mixing temperature are not particularly limited. In many cases, the pigment particles that precipitate tend to be fine when mixed at a lower temperature than a high temperature. Therefore, the temperature at the time of mixing is preferably, for example, 0 ° C to 60 ° C. The water used at the time of mixing may be any water that can be industrially used. However, pre-cooled water is preferable from the viewpoint of reducing the temperature rise at the time of precipitation.

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

By filtering and washing the slurry obtained by the above method to remove acidic components, and then drying and pulverizing the slurry, a pigment adjusted to a desired particle size can be obtained. When filtering the slurry, the slurry in which the sulfuric acid solution and water are mixed may be filtered as it is, but if the slurry has poor filterability, the slurry may be heated and stirred and then filtered. Alternatively, the slurry may be neutralized with a base and then filtered.

For pigmentation by solvent salt milling, a clay-like mixture consisting of at least three components of a crude pigment, a water-soluble inorganic salt and a water-soluble solvent is strongly kneaded using a kneader or the like. The mixture after kneading is put into water and stirred with various stirrers to form a slurry. The water-soluble inorganic salt and the water-soluble solvent are removed by filtering the obtained slurry. By repeating the above slurrying, filtration, and washing with water, a pigment composition having a desired crystal shape and particle size can be obtained.

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

Pigmentization by solvent salt milling often generates heat with kneading. Therefore, from the viewpoint of safety, it is preferable to use a water-soluble solvent having a boiling point of about 120 to 250 ° C. Specific examples of the water-soluble solvent include 2- (methoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, and 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 Mono Examples thereof include ethyl ether and low molecular weight polypropylene glycol.

In the solvent method, phthalocyanine semi-cludes are heated in a reaction vessel using organic solvents such as aromatic, alcohol-based, ester-based, and ether-based to loosen the secondary aggregation of phthalocyanine semi-cludes and convert the crystal form. This is a method for obtaining a pigment composition having a desired crystal shape and particle size by simultaneously performing crystal growth to a required particle size.

It is preferable that the crude pigment is immersed in a large excess liquid medium containing an organic solvent and stirred at a temperature of 50 to 180 ° C. for 30 minutes to 5 hours. The amount of the liquid medium used is preferably 300 to 1500 parts by weight per 100 parts by weight of the object to be pigmented. As the liquid medium, an organic solvent and water may be used in combination. An organic solvent having no affinity for water may be used as an emulsion with a surfactant.

The organic solvent at this time includes aromatic or aliphatic hydrocarbons such as toluene, xylene and mineral spirits; ketones such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone; propanol, butanol, isopropyl alcohol and iso. Alcohols such as butanol, methyl cellosolve, butyl cellosolve, cyclohexanol; halogenated hydrocarbons such as trichloroethane, trichloroethylene, chlorobenzene; ethers such as tetrahydrofuran, dioxane, diglime, anisole; ethyl acetate, propyl acetate, butyl acetate, cellosolve acetate , Esters such as butyl cellosolve acetate; amides such as dimethylform amide, N-methylpyrrolidone and the like. Furthermore, a mixture of two or more of these solvents can also be used. It is also possible to add water to these solvents and use them in the form of an aqueous solution or a liquid-liquid two-phase system.

After this liquid medium treatment, after removing the solvent by distillation operation, decompression operation, etc., a dry pigment can be obtained in the case of organic solvent treatment only, and in the case of organic solvent-water aqueous solution or liquid-liquid two-phase system. Can be made into a water slurry, and a dry pigment can be obtained through a filtration step and a drying step. Further, in the case of an aqueous solution of an organic solvent-water, it is directly filtered without performing operations such as distillation and depressurization, washed until the organic solvent component in the pigment is completely removed, and then a dry pigment is obtained through a drying step. You can also. Alternatively, it can be dried with a spray dryer or the like in the state of a dispersion liquid containing washing water.

(Metal compounds other than pigments)
Metal compounds other than pigments include inorganic salts such as calcium chloride, calcium sulfate, calcium hydroxide, calcium carbonate, calcium oxide, magnesium sulfate, strontium chloride, copper (II) chloride and barium sulfate, calcium acetate and calcium benzoate. , And other organic acid salts. Among these, calcium salt is preferable, calcium sulfate and calcium chloride are more preferable, and calcium sulfate is further preferable from the viewpoint of solubility in water and pH when dissolved in water.

The solubility of calcium sulfate in water (20 ° C.) is as low as 2.55 g / L, so that it is easy to precipitate when the pigment composition is dried, the secondary aggregation of the pigment composition is alleviated, and the dispersibility is improved. Is expected.

As a method for producing a pigment composition containing the compound (1) and calcium, an aqueous solution in which calcium is dissolved is used at the time of washing after synthesizing the compound (1), or washing after the compound (1) is pigmentized. A method of using an aqueous solution of calcium instead of water in the process of using water, such as using an aqueous solution of calcium dissolved in water, a method of pouring calcium water into a dried compound (1), or a calcium compound. In the process of using water as described above, a method of using an aqueous solution in which calcium is dissolved is preferable instead of water.

The reason why the method of using an aqueous solution in which calcium is dissolved instead of water in the step of using water as described above is preferable is that the compound (1) is slurryed with calcium in a state containing water before drying to form a compound (1). This is because the secondary aggregation of 1) is suppressed, so that the dispersibility can be expected to be further improved.

It is more preferable that the divalent metal contains a divalent metal phthalocyanine compound which is a metal-containing pigment and a calcium salt which is a metal compound other than the pigment.

This has even better dispersibility and viscosity stability by combining the effect of the divalent metal phthalocyanine to modify the surface condition of the compound (1) and the effect of the calcium salt to prevent the secondary aggregation of the pigment. This is because a pigment composition can be obtained.

[Dye derivative]
The pigment composition can contain a dye derivative to the extent that the problem can be solved in order to facilitate adjustment to a desired particle size and facilitate dispersion. The dye derivative is a compound having an acidic group, a basic group, a neutral group or the like in the organic dye residue. The dye derivative is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group or a phosphate group, an amine salt thereof, a sulfonamide group or a compound having a basic substituent such as a tertiary amino group at the terminal. Examples thereof include compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo, disazo, polyazo and other azo pigments. ..
Specifically, as the diketopyrrolopyrrole dye derivative, JP-A-2001-22520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine. Examples of the dye derivative are JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, and Patent No. 5735266. Japanese Patent Application Laid-Open No. 09-272812, Japanese Patent Application Laid-Open No. 10-245501, Japanese Patent Application Laid-Open No. 10-265697, Japanese Patent Application Laid-Open No. 2007-079094, WO2009 / 025325 pamphlet, as a quinacridone-based dye derivative, JP-A-48- JP-A-54128, JP-A-03-9961, JP-A-2000-273383, JP-A-2011-162662 as a dioxazine-based dye derivative, and JP-A-2007-314785 as a thiazineindigo-based dye derivative. Examples of JP-A and triazine-based dye derivatives include JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, and JP-A-2004-217842. JP-A-2007-314681, JP-A-2009-57478 for benzoisoindole-based dye derivatives, JP-A-2003-167112 for quinophthalone-based dye derivatives, JP-A-2006-291194, JP-A. 2008-31281, 2012-226110, naphthol-based dye derivatives, 2012-208329, 2014-5439, and azo-based dye derivatives, 2001-172520. Japanese Unexamined Patent Publication No. 2012-172092, JP-A-2004-307854 as acidic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005 as basic substituents. Examples thereof include known dye derivatives described in JP-A-181383, JP-A-2005-213404, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a sex group is synonymous with a dye derivative.

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

<Coloring composition>
The coloring composition of the present invention preferably contains the above pigment composition and a dispersion medium.

The content of the pigment composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass in the coloring composition.

[Dispersed medium]
Examples of the dispersion medium include resins and solvents. Examples of the resin include a resin type dispersant and a binder resin. Examples of the solvent include water and organic solvents. If necessary, a small molecule dispersant such as a surfactant can be used.

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Examples of the binder resin include polyolefin resins, polyester resins, styrene copolymers, acrylic resins, and modified resins thereof. The binder resin is, for example, a polymer such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), low-density polyethylene (LDPE), a polyolefin resin such as polypropylene; a polyester resin such as polyethylene terephthalate; styrene-. p-Chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methylmethacrylate copolymer Copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinylmethylketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer Styrene copolymers such as coalesced, styrene-acrylonitrile-inden copolymers; acrylic resins such as acrylic resins and methacrylic resins; polyvinyl chlorides, phenolic resins, naturally modified phenolic resins, natural resin modified maleic acid resins, polyvinylacetates, Silicone resin, polyurethane resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, nitrocellulose resin, polyamide resin, epoxy resin, xylene resin, polyvinyl butyral resin, polyvinyl acetal resin, cellulose ester resin, alkyd resin, rosin resin , Ketone resin, cyclized rubber, chlorinated polyolefin resin, terpene resin, Kumaron inden resin, alkyd resin, amino resin, epoxy resin, petroleum resin, and modified resins thereof.

The content of the resin is preferably 0 to 50% by mass, more preferably 0 to 30% by mass in the coloring composition.

Organic solvents can be classified into water-soluble solvents and water-insoluble solvents.
Examples of the water-soluble solvent include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin and the like. Examples of the water-insoluble solvent include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.

Each material constituting the coloring composition can be used alone or in combination of two or more.

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

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

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

The molding composition may contain wax. The wax consists of low molecular weight polyolefins. These are polymers of olefin monomers such as ethylene, propylene, butylene and may be block, random copolymers or terpolymers. Specifically, it is a polymer of α-olefins such as low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene (PP).

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

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

The melt flow rate (MFR) determined according to JIS K-7210 of the wax is preferably larger 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 composition may contain other additives. Other additives are materials generally used in the technical field of molded products, and are other than antioxidants, light stabilizers, dispersants, metal soaps, antistatic agents, flame retardants, lubricants, fillers, and pigment compositions. Examples include colorants.

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

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

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

Examples of the melt kneading include a single-screw kneading extruder, a twin-screw kneading extruder, and a tandem twin-screw kneading extruder. The melt-kneading temperature varies depending on the type of thermoplastic resin, but is usually 150 to 30.
It is about 0 ° C.

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

<Ink>
The ink of the present specification contains a coloring composition (pigment composition, dispersion medium). Examples of the ink include printing ink, inkjet ink, color filter ink and the like. Examples of the printing ink include offset printing ink, flexo printing ink, gravure printing ink, silk screen printing ink and the like. As the ink, focusing on the curing method, an active energy ray-curing type ink can be mentioned. When the ink contains water, it is called water-based ink. Hereinafter, preferred embodiments of the ink will be described.

The method for producing the ink (mixing means) is not particularly limited, but the ink can be preferably produced by mixing using, for example, a roller mill, a ball mill, a pebble mill, an attritor, or a sand mill.

The method for printing the printing ink is not particularly limited, and a known method can be used. Specific examples thereof include roll coaters, rod coaters, blades, wire bars, doctor knives, spin coaters, screen coaters, gravure coaters, offset gravure coaters, flexo coaters and the like.
Further, heating may be performed as needed at the time of printing.

The base material on which the printing ink is printed is not particularly limited, and known materials can be used. Specifically, polyolefins such as polyethylene and polypropylene, polyethylene terephthalates, polycarbonate, polyesters such as polylactic acid, polystyrene-based resins such as polystyrene, AS resin, and ABS resin, nylon, polyamide, polyvinyl chloride, polyvinylidene chloride, cellophane, Coated paper such as art paper, coated paper, cast paper, high-quality paper, medium-quality paper, non-coated paper such as newspaper, synthetic paper such as YUPO paper, aluminum, etc., or a film made of a composite material thereof. Examples include a base material. Further, a vapor-deposited base material obtained by depositing an inorganic compound such as silica, alumina, or aluminum on polyethylene terephthalate or a nylon film can also be mentioned. The base material may be further coated with polyvinyl alcohol or the like on the vapor-deposited surface of the inorganic compound or the like, or may be further subjected to surface treatment such as corona treatment.

The printing ink can further contain known binder resins, additives, glittering materials, solvents and the like according to various uses.

(Binder resin)
The printing ink may appropriately contain a known resin. The resin is not particularly limited, and is not particularly limited, for example, acrylic resin, polyester resin, styrene resin, epoxy resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin, phenol resin, naturally modified phenol resin, and natural. Resin-modified maleic acid resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, cellulose-based resin (for example, ethyl cellulose, cellulose acetate, nitrocellulose), silicone resin, furan resin, polyvinyl Butyral resin, polyvinyl acetal resin, terpene resin, kumaron inden resin, xylene resin, diallyl phthalate resin, alkyd resin, rosin-modified alkyd resin, petroleum resin, urea resin, synthetic rubber such as butadiene-acrylic nitrile copolymer, etc. Can be mentioned. The binder resin can be used alone or in combination of two or more.

(Additive)
The printing ink can contain known additives. Additives include, for example, pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, defoaming agents, antistatic agents, trapping agents, blocking inhibitors, hydrocarbon waxes, isocyanate-based curing agents, silane coupling agents, etc. Can be mentioned.

The dispersant can also be used in combination to stably disperse the pigment. As the dispersant, a surfactant such as anionic, nonionic, cationic or zwitterionic can be used. From the viewpoint of storage stability of the ink, the dispersant is preferably contained in the ink in an amount of 0.1 to 10.0% by mass with respect to 100% by mass of the total weight of the ink. Further, it is more preferably contained in the range of 0.1 to 3.0% by mass.

Silica particles can be used in combination as an anti-blocking agent. Examples of the silica particles include crystalline silica, amorphous silica, hydrophobic silica, and hydrophilic silica. Hydrophobic silica is silica obtained by knitting hydrophilic functional groups with alkylsilane or the like to make it hydrophobic, and hydrophilic silica is silica having a hydrophilic functional group on its surface. Among these, hydrophilic ones are preferable.
The average particle size of the silica particles is preferably 1 to 5 μm. The content of the silica particles is preferably 0.1 to 3.0% by mass, more preferably 0.2 to 2.5% by mass, and further preferably 0.2 to 1.5% by mass in 100% by mass of the printing ink. preferable.
Examples of commercially available products include "SS-50F", "BY-601" and "AY-6A3" manufactured by Tosoh Silica, and "P-73" manufactured by Mizusawa Industrial Chemicals.

The hydrocarbon wax is not particularly limited, and known hydrocarbon waxes can be used. Specific examples of the natural wax include paraffin wax, microcrystalline wax, montan wax, carnauba wax, candelilla wax, rice wax, wood wax and the like. Examples of the synthetic wax include polyethylene wax, polypropylene wax, Fischer-Tropsch wax, polytetrafluoroethylene wax, and amide wax.
Examples of commercially available products include "WF640", "W300", and "W310" (all trade names) manufactured by Mitsui Chemicals, Inc.

(Glowing material)
The printing ink can contain a known bright material. The bright material is particles having an average thickness of 0.5 to 10 μm and an average particle diameter of 5 to 50 μm, and examples thereof include metal flakes, mica, and coated glass flakes. Examples of the metal flakes include aluminum flakes and gold powder. Examples of the mica include ordinary mica, coated mica, and the like. Examples of the coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide. The content of the bright material is preferably 0.1 to 10% by mass in 100% by mass of the printing ink.

(solvent)
As the solvent, an organic solvent or water can be used alone or in combination depending on the intended use.
Examples of the organic solvent include aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, ester organic solvents, methanol and ethanol. , N-propanol, isopropanol, n-butanol, and the like, and examples thereof include alcohol-based organic solvents.

<Gravure ink>
The gravure ink contains a coloring composition (pigment composition, dispersion medium) and a binder resin.

The ratio of the pigment composition of the present invention to the gravure ink is preferably a sufficient amount for ensuring the concentration and coloring power, that is, 1 to 50% by mass with respect to the total mass of the ink composition. Further, 10 to 90% by mass is preferable in the non-volatile content in the ink.

In addition, the pigment composition of the present invention may be used in any combination of known colorants, if necessary, as long as the problem can be solved.

Hereinafter, each component contained in the gravure ink and, if necessary, a synthesis method thereof will be described.

The gravure ink may contain water as a liquid medium, but the content thereof is 0.1 to 10% by mass in 100% by mass of the liquid medium.

(Other resins)
The gravure ink can contain other resins as a binder resin other than the binder resin. Other resins include, for example, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, rosin resin, rosin-modified maleic acid resin, terpene resin, phenol-modified terpene resin, ketone resin, and cyclization. Examples thereof include rubber, rubber chloride, butyral, petroleum resin, and modified resins thereof. These resins can be used alone or in admixture of two or more, and the content thereof is preferably 1 to 20% by mass based on 100% by mass of the solid content of the binder resin.

(Manufacturing of gravure ink)
The gravure ink can be produced by dissolving and / or dispersing the pigment composition and the binder resin in an organic solvent. Specifically, for example, an organic pigment, a silica particle mixed with a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin, and the dispersant as needed to produce a pigment dispersion dispersed in an organic solvent is obtained. The gravure ink can be produced by further adding a polyurethane resin, or if necessary, another resin, an additive, or the like to the obtained pigment dispersion. Further, the particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the crushed media of the disperser, the filling rate of the crushed media, the dispersion treatment time, the discharge rate of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to.

If the ink contains air bubbles or unexpectedly coarse particles, it is preferable to remove them by filtration or the like in order to deteriorate the print quality. As the filter, a conventionally known one can be used.

The viscosity of the gravure ink produced by the above method is in the viscosity range of 40 to 400 cps at 25 ° C. with a B-type viscometer in order to correspond to high-speed printing (50 to 300 m / min) by the gravure printing method. Is preferable. More preferably, it is 50 to 350 cps. In this viscosity range, the viscosity in Zahn Cup # 4 corresponds to about 9 to 40 seconds. The viscosity of the gravure ink can be adjusted by appropriately selecting the type and amount of the raw material used.

(Printed matter)
The gravure ink is diluted with a diluting solvent to, for example, a viscosity and concentration suitable for gravure printing, and is supplied to each printing unit alone or mixed. After printing with gravure ink on the substrate, a printed layer can be formed by removing volatile components, and a printed matter can be obtained. Printed matter can be processed in various ways. For example, an adhesive layer and a film layer can be laminated on a printed matter layer in this order and used as a laminate.

(Laminated body)
The laminate is a printed matter in which an adhesive layer and a film layer are laminated in this order on the printed matter. For example, the usual extrusion laminating method in which a molten polyethylene resin is laminated on a printed layer via various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium, and urethane on the printed surface. It is obtained by a known laminating process such as a dry laminating method or a non-solvent laminating method in which an adhesive such as is applied and a plastic film is laminated on the adhesive, or a direct laminating method in which molten polypropylene is directly pressure-bonded and laminated on a printed surface. Be done.

<Aqueous flexo ink>
The water-based flexo ink contains at least a water-based urethane resin, a pigment composition, and water. Various types of base materials can be selected, and it is also suitable for printing on impermeable base materials other than general printing paper, such as coated paper and plastic films (including plastic sheets).

The content of the pigment composition in the aqueous flexo ink is not particularly limited, but is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.

Hereinafter, each component contained in the water-based flexo ink and, if necessary, a synthesis method thereof will be described.

(Binder resin)
The water-based flexo ink preferably contains a binder resin. Examples of the binder resin include water-based resins such as water-based urethane resin, polyester resin, acrylic resin, styrene-acrylic resin, styrene-anhydrous maleic acid resin, rosin-modified maleic acid resin, cellulose-based resin, and chlorinated polyolefin. .. The binder resin can be used alone or in combination of two or more.

(Aqueous urethane resin)
The urethane resin is generally a resin obtained by reacting a polyisocyanate having two or more isocyanate groups in one molecule with a hydroxyl group-containing compound having two or more hydroxyl groups in one molecule. The water-based urethane resin of the present embodiment has the following configurations. Such a configuration can be preferably introduced by appropriately selecting the structure, type and the like of the hydroxyl group-containing compound as described later.

The number of urethane bonds (mmol / g) of the aqueous urethane resin is not particularly limited, but is preferably 2.2 to 3.0 mmol / g from the viewpoint of adjusting the molecular weight of the resin and the hardness of the coating film. More preferably, it is .3 to 2.9 mmol / g. The number of urethane bonds can be set to a desired range by appropriately adjusting the amounts of the hydroxyl group-containing compound and the polyisocyanate and the reaction conditions.

The glass transition temperature (Tg) of the aqueous urethane resin is not particularly limited, but is preferably −70 ° C. or lower, and more preferably −70 ° C. to −90 ° C. When the Tg of the water-based urethane resin is −70 ° C. or lower, the film forming property of the ink is improved and the adhesion of the coating film is improved.

The weight average molecular weight (GPC measurement, standard polystyrene conversion) of the aqueous urethane resin is not particularly limited, but is preferably 10,000 to 100,000, more preferably 30,000 to 70,000.

The hydroxyl value (mgKOH / g) of the aqueous urethane resin is not particularly limited, but is preferably 0.0 to 3.0 mgKOH / g, preferably 0.0 to 2.0 mgKOH / g, from the viewpoint of water resistance and the like. Is more preferable.

The water-based urethane resin is preferably contained in an amount of 3% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more in the total amount of the water-based flexo ink. On the other hand, the content of the water-based urethane resin is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 17% by mass or less in the total amount of the rotary printing ink.

The content of the hydrocarbon wax in the aqueous flexo ink is preferably 0.5 to 7% by mass, more preferably 1 to 4% by mass.

The water-based flexo ink contains an water-based solvent. Examples of the aqueous solvent include water and alcohol. Examples of the alcohol include n-propanol and isopropyl alcohol.

The content of the aqueous solvent is preferably 40 to 60% by mass in the aqueous flexo ink.

(Other ingredients)
The water-based flexo ink may also contain, if necessary, known additives such as a defoaming agent, a thickener, a leveling agent, a pigment dispersant, and an ultraviolet absorber. Further, a non-aqueous solvent other than alcohol (for example, a ketone solvent and an ester solvent) can be contained as long as the problem can be solved. The content of the non-aqueous solvent is preferably 20% by mass or less, more preferably 10% by mass or less in the ink.

<Active energy ray curable ink>
The active energy ray-curable ink of the present specification contains a coloring composition (pigment composition, resin), a polymerizable compound, and a photopolymerization initiator.

In the active energy ray-curable ink, in addition to the pigment composition of the present invention, a known colorant may be arbitrarily combined and used as needed within the range not deviating from the effect of the present invention.
The pigment composition of the present invention is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on the total mass of the active energy ray-curable ink.

Hereinafter, the components contained in or may be contained in the active energy ray-curable ink of the present embodiment will be described.

(Polymerizable compound)
The polymerizable compound is a compound having one or more ethylenically unsaturated bonds in the molecule. Examples of the polymerizable compound include monomers and oligomers.

(monomer)
The monomer is more preferably a (meth) acrylate monomer of a compound having a (meth) acryloyl group.
Specifically, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-carboxyethyl (meth) acrylate, 4-tert-butylcyclohexinol (meth). Acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofuruffle acrylate, caprolactone (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isodecyl (meth) ) Acrylate, 3,3,5-trimethylcyclohexanol (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (oxyethyl) (Meta) Acrylate, 1,4-Cyclohexanedimethanol (Meta) Acrylate, Cyclic Trimethylol Propaneformal (Meta) Acrylate, benzyl (Meta) Acrylate, EO Modified (2) Nonylphenol Acrylate, (2-Methyl-2-ethyl) A monofunctional (meth) acrylate monomer having one (meth) acryloyl group in the molecule such as -1,3-dioxolan-4-yl) methyl acrylate and acryloyl morpholine, and
1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol ( 200) Di (meth) acrylate, polyethylene glycol (300) di (meth) acrylate, polyethylene glycol (400) di (meth) acrylate, polyethylene glycol (600) di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) ) Acrylate, Dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, EO-modified (2) 1,6-hexanediol di (meth) acrylate, PO-modified (2) Neopentyl glycol di (meth) Acrylate, (neopentyl glycol-modified) trimethylolpropandi (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, EO-modified (4) bisphenol A-di (meth) acrylate, PO-modified (4) bisphenol A-di (4) Bifunctional (meth) acryloyl group having two (meth) acryloyl groups in the molecule such as meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, dicyclopentanyldi (meth) acrylate. Meta) Acrylate monomer,
Trimethylolpropane tri (meth) acrylate, EO-modified (3) trimethylolpropane tri (meth) acrylate, EO-modified (6) trimethylolpropane tri (meth) acrylate, PO-modified (3) trimethylolpropane tri (meth) acrylate , Ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, ethoxylated isocyanuric acid tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. A trifunctional (meth) acrylate monomer having three (meth) acryloyl groups in the molecule of
A tetrafunctional (meth) acrylate monomer having four acryloyl groups in the molecule, such as pentaerythritol tetra (meth) acrylate, EO-modified (4) pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.
A pentafunctional (meth) acrylate monomer having five (meth) acryloyl groups in a molecule such as dipentaerythritol penta (meth) acrylate,
Examples thereof include a hexafunctional (meth) acrylate monomer having six (meth) acryloyl groups in a molecule such as dipentaerythritol hexa (meth) acrylate. In addition, a vinyl group-containing monomer having no (meth) acryloyl group can also be used.

(Oligomer)
Examples of the oligomer include urethane acrylate oligomers such as aliphatic urethane acrylate oligomers and aromatic urethane acrylate oligomers, acrylic ester oligomers, polyester acrylate oligomers, and epoxy acrylate oligomers. The oligomer preferably contains about 2 to 10 ethylenically unsaturated bonds.

The weight average molecular weight of the oligomer is preferably 400 to 10,000, more preferably 500 to 5,000. Here, the "weight average molecular weight" can be determined as a polystyrene-equivalent molecular weight by general gel permeation chromatography (hereinafter, GPC).

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

The content of the polymerizable compound is preferably 40 to 80% by mass, more preferably 45 to 70% by mass in the active energy ray-curable ink.

(Photopolymerization initiator)
Examples of the photopolymerization initiator include benzophenone-based compounds, dialkoxyacetophenone-based compounds, α-hydroxyalkylphenone-based compounds, α-aminoalkylphenone-based compounds, acylphosphine oxide-based compounds, and thioxanthone-based compounds.
Further, the photopolymerization initiator may be used alone or in combination of two or more.

Examples of the benzophenone compound include benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis (diethylamino) benzophenone, 4,
Examples thereof include 4'-bis (dimethylamino) benzophenone, [4- (methylphenylthio) phenyl] -phenylmethanone and the like.

Examples of the dialkoxyacetophenone compound include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, and diethoxyacetophenone.

Examples of the α-hydroxyalkylphenone compound include 1-hydroxy-cyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1- [4- (2-hydroxymethoxy) -phenyl. ] -2-Hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl -Propane-1-on and the like can be mentioned.

Examples of the α-aminoalkylphenone compound include 2-methyl-1- [4- (methoxythio) -phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4). -Morphorinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like can be mentioned.

Examples of the above-mentioned acylphosphine oxide compound include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphinoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide and the like. Can be mentioned.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and the like.

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

The content of the photopolymerization initiator is preferably 1 to 20% by mass, more preferably 5 to 15% by mass in the active energy ray-curable ink.

The active energy ray-curable ink of the present invention may contain a hydrocarbon wax. From the viewpoint of the balance between abrasion resistance, gloss, and piring, the content is preferably 0.5 to 5% by mass, preferably 0.5 to 4% by mass, based on the total mass of the active energy ray-curable ink. More preferred.

The active energy ray-curable ink of the present invention may contain a binder resin. By containing the binder resin, the curing shrinkage of the coating film that occurs during curing is alleviated, curling of the base material is suppressed, and the adhesion to the base material is improved.

The weight average molecular weight of the binder resin is preferably 10,000 to 100,000. More preferably, it is 10,000 to 70,000.

The binder resin may be used alone or in combination of two or more. The content of the binder resin is preferably 5 to 15% by mass with respect to the total mass of the ink composition.

(Sensitizer)
The active energy ray-curable ink may contain a sensitizer. By including a sensitizer, the curability can be further improved. Examples of the sensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, aliphatic amines, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, dibutylethanolamine and the like. Can be mentioned.

(Polymerization inhibitor)
The active energy ray-curable ink of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, and aluminum salts of N-nitrosophenylhydroxylamine. Can be mentioned.

The content of the polymerization inhibitor is preferably 0.01 to 2% by mass in the active energy ray-curable ink from the viewpoint of improving the storage stability of the active energy ray-curable ink while maintaining the curability.

It is preferable that the active energy ray-curable ink does not substantially contain water. The term "substantially free" means that the amount is 3% by mass or less with respect to the total mass of the active energy ray-curable ink.

(Constitution pigment)
The active energy ray-curable ink may contain an extender pigment. Examples of the extender pigment include clay, talc, barium sulfate, calcium carbonate, heavy calcium carbonate, barium carbonate, magnesium carbonate, silica, bentonite and the like.

<Printed matter of active energy ray-curable ink>
The printed matter of the present invention is obtained by printing an active energy ray-curable ink on a substrate and curing it with an active energy ray.

The method for curing the active energy ray-curable ink can be, for example, by irradiating with α-rays, γ-rays, electron beams, X-rays, ultraviolet rays, visible light, infrared light, or the like. Of these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable. The peak wavelength of ultraviolet rays is preferably 200 to 600 nm, more preferably 350 to 420 nm.

Examples of the active energy radiation source include mercury lamps, xenon lamps, metal hydride lamps, ultraviolet light emitting diodes (UV-LEDs), LEDs (light emitting diodes) such as ultraviolet laser diodes (UV-LD), gas / solid lasers, and the like. Will be.

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

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

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

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

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

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

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

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

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

The toner can contain a hydrocarbon wax. As the hydrocarbon wax, the same wax used for the printing ink can be used.

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

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

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

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

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

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

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

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

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

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

The water-soluble solvent is important for preventing drying and solidification at the nozzle portion of the printer head of the water-based inkjet ink and for obtaining ink ejection stability. Examples of the water-soluble solvent include 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, and ethylene glycol monoethyl ether. Examples thereof include 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetraflufuryl alcohol, 4-methoxy-4 methylpentanone and the like.

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

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

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

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

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

The chelating agent is used to capture the metal ions contained in the aqueous inkjet ink and prevent the precipitation of insoluble matter in the nozzle portion or the ink. Examples of the chelating agent include 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 in 100% by mass of the water-based inkjet ink.

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

Inkjet ink is produced by blending and mixing each material. Examples of the mixing include a stirrer using wings, various dispersers, an emulsifier and the like. The order of addition of each material and the mixing method are arbitrary.

It is preferable that the inkjet ink is mixed and then filtered or centrifuged to remove coarse particles. This improves the ejection property from the inkjet printer. Known methods can be used for filtration and centrifugation.

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

<Paint>
The paint of the present specification contains a coloring composition (pigment composition, resin, solvent).
The resin is preferably the binder resin already described. Examples of the binder resin include thermosetting resins and thermoplastic resins. The thermosetting resin is preferably a resin having a glass transition temperature of 10 ° C. or higher. Examples of the type of thermosetting resin include acrylic resin, polyester, polyurethane and the like. Further, the thermosetting resin preferably has a functional group capable of reacting with the curing agent. Examples of the functional group include a carboxyl group and a hydroxyl group. Examples of the curing agent include isocyanate curing agents, epoxy curing agents, aziridine curing agents, amine curing agents and the like.
The thermoplastic resin is preferably a resin having a glass transition temperature of 30 ° C. or higher. Examples of the thermoplastic resin include nitrocellulose and polyester. The thermosetting resin and the thermoplastic resin can be used together.

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

The paint can further contain known additives.

Examples of the use of the paint include paints for metals and paints for plastics.

<Ink set>
The ink set of the present invention is at least an ink set containing yellow ink, cyan ink, and magenta ink, and it is preferable that the cyan ink contains an ink containing the coloring composition.

The ink set of the present invention can further contain other inks such as black ink (black ink), white ink (white ink), and special color ink.

The ink set of the present invention can be used for printing ink sets such as offset printing inks, flexo printing inks, gravure printing inks, screen printing inks, and ink sets for inkjet inks. Among these, the gravure printing ink set and the inkjet ink set used for the packaging material are preferable, and the gravure printing ink set is more preferable.

<Cyan ink>
The cyan ink in the present invention contains the above pigment composition and a binder resin. Since the cyan ink contains a divalent metal as described above, the dispersibility and storage stability, which have been the weak points of the compound (1), are improved.

<Binder resin>
The binder resin is, for example, polyurethane resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, nitrocellulose resin, polyamide resin, polyvinyl acetal resin, cellulose ester resin, polystyrene resin, acrylic resin, polyester resin, alkyd resin, rosin. Examples thereof include based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, butyral, petroleum resins, and chlorinated polyolefin resins.

The content of the binder resin is preferably 4 to 25% by mass, more preferably 6 to 20% by mass in the cyan ink.

The cyan ink can further contain other pigments, resins, organic solvents, and other additives such as pigment dispersants, leveling agents, defoaming agents, waxes, plasticizers, infrared absorbers, and ultraviolet absorbers, if necessary.

<Yellow ink>
The yellow ink in the present invention is an ink that can obtain a yellow color, and includes a pigment and a binder resin. As the binder resin, the resin already described can be used.

<Magenta ink>
The magenta ink in the present invention is an ink that can obtain a magenta color, and includes a pigment and a binder resin. As the binder resin, the resin already described can be used.

<Pigment>
Examples of the pigment include organic pigments and inorganic pigments. In the present specification, for example, the following pigments can be used.

[Organic pigment]
The pigment is preferably an organic pigment. Organic pigments include, for example, soluble azo-based, insoluble azo-based, azo-based, phthalocyanine-based, halogenated phthalocyanine-based, anthraquinone-based, ansanthrone-based, dianthracinonyl-based, anthrapyrimidine-based, perylene-based, perinone-based, and quinacridone-based. , Thioindigo, dioxazine, isoindolinone, quinophthalone, azomethinazo, flavanthron, diketopyrrolopyrrole, isoindoline, indanslon and the like.

Examples of pigments include C.I. I. Shown by pigment number.

The indigo pigment is, for example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60 and the like.
When used in the cyan ink constituting the ink set of the present invention, the indigo pigment may be contained as long as the effect of the present invention is not impaired.

The red pigment is, for example, C.I. I. Pigment Red 2, C.I. I. Pigment Red 32, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 63: 1, C.I. I. Pigment Red 81, C.I. I. Pigment Red 122, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 149, C.I. I. Pigment Red 150, C.I. I. Pigment Red 166, C.I. I. Pigment Red 170, C.I. I. Pigment Red 174, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 188, C.I. I. Pigment Red 190, C.I. I. Pigment Red 202, C.I. I. Pigment Red 207, C.I. I. Pigment Red 208, C.I. I. Pigment Red 209, C.I. I. Pigment Red 214, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221 and C.I. I. Pigment Red 224, C.I. I. Pigment Red 238, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 260, C.I. I. Pigment Red 264, C.I. I. Pigment Red 269, C.I. I. Pigment Red 272, C.I. I. Pigment Violet 19 and the like.
The magenta ink preferably contains the above red pigment. Among these, it is more preferable to contain a red pigment that does not contain a halogen atom due to its chemical structure. In addition, among these, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 146, C.I. I. Pigment Red 185, and C.I. I. Pigment Violet 19 is even more preferred.

The yellow pigment is, for example, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 87, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181 and C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 194, C.I. I. Pigment Yellow 198, C.I. I. Pigment Yellow 213, C.I. I. Pigment Yellow 234, C.I. I. Pigment Yellow 235, C.I. I. Pigment Yellow 236 and the like.
The yellow ink preferably contains the above yellow pigment. Among these, it is more preferable to contain a yellow pigment that does not contain a halogen atom due to its chemical structure. In addition, among these, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, and C.I. I. Pigment Yellow 234 is even more preferred.

Purple pigments are, for example, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 37 and the like.

The green pigment is, for example, C.I. I. Pigment Green 7 and the like.

The orange pigment is, for example, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64 and the like.

Examples of the spot color ink include inks such as purple, grass, and vermilion other than cyan, magenta, and yellow, and it is preferable to include the above-mentioned purple pigment, green pigment, orange pigment, and the like.

[Inorganic pigment]
The inorganic pigments include, for example, white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithobon, antimony white, and gypsum, carbon black, iron black, and copper / chromium composite oxides. Black inorganic pigments such as, aluminum particles, mica (mica), bronze powder, chrome vermillion, yellow lead, cadmium yellow, cadmium red, ultramarine, dark blue, red iron oxide, yellow iron oxide, zircon and the like.

For the black ink, it is preferable to use carbon black from the viewpoint of excellent coloring power, hiding power, chemical resistance, and weather resistance. For example, C.I. I. Pigment Black 7 and the like. Further, it is preferable to use titanium oxide as the white ink (white ink) from the viewpoint of excellent coloring power, hiding power, chemical resistance and weather resistance. From the viewpoint of printing performance, titanium oxide is preferably surface-treated with silica and / or alumina.

Each ink can be used alone or in combination of two or more kinds of pigments in order to obtain a desired color tone.

The average primary particle size of the pigment is preferably in the range of 10 to 200 nm, more preferably in the range of 50 to 150 nm.
The content of the pigment in the ink is preferably in the range of 1 to 60% by mass based on the mass of the ink and preferably based on the non-volatile content mass of the ink in order to secure the concentration and coloring power of the ink. Is in the range of 10 to 90% by mass.

<Gravure printing ink set>
The gravure printing ink set of the present invention preferably includes the above ink set.

[Polyurethane resin]
The binder resin used in the gravure printing ink set of the present invention is preferably a polyurethane resin. The polyurethane resin includes a polyurethane urea resin.
The polyurethane resin is synthesized, for example, by (1) reacting a polyol with a diisocyanate compound at a ratio of an excess of isocyanate groups to synthesize a urethane prepolymer having an isocyanate group at the terminal. Next, a two-step method for synthesizing a urethane prepolymer having an isocyanate group in a solvent by reacting it with the chain extender having an amino group and / or a terminal blocking agent, (2) polypropylene glycol, polyol, diisocyanate compound, and amino group. Examples thereof include a one-step method in which a chain extender and / or a terminal sealant having the above is reacted at once in an appropriate solvent.

The weight average molecular weight of the polyurethane resin is preferably in the range of 15,000 to 100,000. When the weight average molecular weight of the polyurethane resin is 15,000 or more, the blocking resistance of the ink, the strength of the printing film, and the oil resistance are excellent, and when it is 100,000 or less, the viscosity of the obtained ink is in an appropriate range. , Excellent gloss of printing film.

Further, the polyurethane resin preferably has an amine value from the viewpoint of printability and laminate strength. The amine value is preferably 0.5 to 20 mgKOH / g, more preferably 1 to 15 mgKOH / g.

The content of the binder resin in each color ink is preferably 4 to 25% by mass, more preferably 6 to 20% by mass in each ink.

[Organic solvent]
The organic solvent used in the gravure printing ink set of the present invention is, for example, an aromatic organic solvent such as toluene or xylene; a ketone organic solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; ethyl acetate, n-propyl acetate or butyl acetate. , Ester-based organic solvents such as propylene glycol monomethyl ether acetate; alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol and n-butanol; glycol ether-based solvents such as ethylene glycol monopropyl ether and propylene glycol monomethyl ether; Can be mentioned. It is preferable to use a mixture of two or more of these organic solvents.
In the gravure printing ink set, it is preferable to use a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent. The mass ratio of the ester-based organic solvent to the alcohol-based organic solvent (mass of the ester-based organic solvent: mass of the alcohol-based organic solvent) is preferably 95: 5 to 40:60, more preferably 90:10 to 50. : 50.
The content of the organic solvent in each color ink is preferably in the range of 60 to 90% by mass, more preferably 70 to 85% by mass, based on the mass of the ink.

The viscosity of each color ink is preferably 10 mPa · s or more from the viewpoint of preventing the pigment from settling and appropriately dispersing, and preferably 1,000 mPa · s or less from the viewpoint of workability efficiency during ink production or printing. The viscosity is a value measured at 25 ° C. with a B-type viscometer manufactured by Tokimec.

[water]
The gravure printing ink set of the present invention can further contain water. By containing a predetermined amount of water, the dispersibility of the pigment due to the polyurethane resin is improved, and the printability such as highlight transfer property, plate fog property, and trapping property is improved.
The water content is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, still more preferably 0.5 to 5% by mass, based on the mass of the gravure printing ink. It is particularly preferably 0.5 to 4% by mass.

[Silica particles]
The gravure printing ink set of the present invention can further contain silica particles in each ink. By including silica particles, wetting and spreading of the ink during overprinting are promoted, trapping property is improved, and highlight transfer property is maintained.
Examples of the silica particles include natural products, synthetic products, and crystalline, amorphous, hydrophobic, and hydrophilic particles. As a method for synthesizing silica particles, there are a dry method and a wet method. The dry method is known as a combustion method and an arc method, and the wet method is known as a sedimentation method and a gel method. Any method may be used for synthesizing silica particles. Further, the silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or hydrophobic silica obtained by modifying the hydrophilic functional group with alkylsilane or the like to make it hydrophobic. It is preferably hydrophilic silica.
Examples of such silica particles include a nip gel series and a nip sill series manufactured by Tosoh Silica Co., Ltd. and a Mizuka sill series manufactured by Mizusawa Industrial Chemicals Co., Ltd.

Since the silica particles form irregularities on the surface of the ink layer, the average particle size is preferably 1 to 10 μm. It is more preferably 1 to 8 μm, still more preferably 1 to 6 μm. The average particle size of the silica particles means the particle size at an integrated value of 50% (D50) in the particle size distribution, and can be obtained by the Coulter counter method.
The specific surface area of the silica particles is preferably 50 to 600 m ² / g by the BET method. More preferably, it is 100 to 450 m ² / g. As the silica particles used in the gravure printing ink of the present invention, two or more kinds of silica particles having different average particle diameters or BET method specific surface areas can be used in combination.

The content of the silica particles is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, and further preferably 0.2 to 2% based on the mass of each ink. It is by mass, particularly preferably 0.2 to 1.5% by mass.

[Other additives]
The gravure printing ink set of the present invention contains extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, and flame retardants as required in each ink. Other additives such as, etc. can be included.

<Clear ink>
The gravure printing ink set of the present invention can further contain clear ink. The desorbed layer formed from the clear ink has a function of being neutralized with an alkaline aqueous solution and being dissolved or swollen to be peeled off from the substrate. This promotes the desorption of the printed layer from the base material and promotes the recycling of printed matter and packaging materials.
The basic compounds used in the alkaline aqueous solution are, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) ₂ ), ammonia, barium hydroxide (Ba (OH) ₂ ). , Sodium carbonate (Na ₂ CO ₃ ). More preferably, it is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
In the present specification, the step of neutralizing with an alkaline aqueous solution to dissolve or swell may be referred to as "alkaline treatment". Further, a layer having desorption property by alkaline treatment may be referred to as a "desorption layer". That is, the print layer formed by the clear ink corresponds to a layer having desorption property (detachable layer).

[Carboxy group-containing resin]
The clear ink preferably contains a carboxy group-containing resin. For example, it functions as a primer composition to be printed on a substrate before the color ink.
Examples of the carboxy group-containing resin include acrylic resin, polyurethane resin, polyester resin, amino resin, phenol resin, epoxy resin, and cellulose. Among these, polyurethane resin is preferable because it has good laminating suitability.

The hydroxyl value of the carboxy group-containing polyurethane resin is preferably 1 to 35 mgKOH / g, more preferably 10 to 30 mgKOH / g. When it is 1 mgKOH / g or more, it is preferable because the desorption property by an alkaline aqueous solution is good, and when it is 35 mgKOH / g or less, it is preferable because the substrate adhesion is good.
The acid value of the carboxy group-containing polyurethane resin is preferably 15 mgKOH / g or more, more preferably 15 to 70 mgKOH / g, and even more preferably 20 to 50 mgKOH / g. When it is 15 mgKOH / g or more, it is preferable because the desorption property by an alkaline aqueous solution is good, and when it is 70 mgKOH / g or less, the adhesion to the substrate is improved and the retort resistance when used as a packaging material is good. .. Both the hydroxyl value and the acid value are values measured according to JIS K0070.

The weight average molecular weight of the carboxy group-containing polyurethane resin is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, still more preferably 15,000 to 50,000.

The molecular weight distribution (Mw / Mn) of the carboxy group-containing polyurethane resin is preferably 6 or less. When the molecular weight distribution is 6 or less, the influence caused by the excessive high molecular weight component, the unreacted component, the side reaction component and other low molecular weight components can be avoided, and the desorption property and the drying property of the primer composition can be avoided. Good retort resistance.
Further, the smaller the molecular weight distribution, that is, the sharper the molecular weight distribution, the more uniformly the dissolution / exfoliation action by the alkaline aqueous solution occurs and the desorption property is improved, which is preferable. The molecular weight distribution is more preferably 5 or less, still more preferably 4 or less. The molecular weight distribution is preferably 1.5 or more, more preferably 1.2 or more.

The carboxy group-containing polyurethane resin may have an amine value. When the carboxy group-containing polyurethane resin has an amine value, the amine value is preferably 0.1 to 20 mgKOH / g, more preferably 1 to 10 mgKOH / g.

The carboxy group-containing polyurethane resin can be synthesized, for example, by reacting a polyol, a hydroxy acid and a polyisocyanate. By using a hydroxy acid, an acid value can be imparted to the polyurethane resin. It is preferable that the polyurethane resin is further modified into a polyurethane urea resin by reacting with a polyamine.

The clear ink may further contain polyisocyanate as a curing component. The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates, and examples thereof include aliphatic polyisocyanates and aromatic aliphatic polyisocyanates.
In addition, the clear ink may contain other components other than the carboxy group-containing resin and polyisocyanate, and like the above-mentioned cyan, yellow, and magenta color inks, it contains additives such as an organic solvent and an anti-blocking agent. can do.

<Inkjet ink set>
The inkjet ink set of the present invention preferably includes the above ink set. The inkjet inks constituting the inkjet ink set of the present invention are as described above.

<Printed matter>
The printed matter of the present invention includes a substrate and a printed layer formed from a gravure printing ink set. The printing layer is formed by printing cyan ink, yellow ink, and magenta ink on a substrate.
The gravure printing method is not particularly limited and can be appropriately selected from known methods. The gravure printing method is roughly divided into front printing and back printing. For example, when the base material is white paper or white film in front printing, yellow ink, magenta ink, cyan ink, etc. are applied on the base material. A printed matter can be obtained by printing in the order of black ink.
Further, for example, when the base material is a transparent film in back printing, it is preferable to print on the base material in the order of black ink, cyan ink, magenta ink, yellow ink, and white ink to produce a printed matter.
When the ink set of the present invention contains a clear ink, it is preferable that the clear ink is printed on a substrate before the color ink.
The thickness of the print layer can be appropriately selected depending on the intended use, the type and number of inks used, and the number of times of overprinting, but is usually in the range of 0.5 to 10 μm.

[Base material]
The base material is, for example, a polyolefin base material such as polyethylene or polypropylene; a polycarbonate base material; a polyester base material such as polyethylene terephthalate or polylactic acid; a polystyrene base material; a polystyrene resin such as AS or ABS; a polyamide base material such as nylon; Polyvinyl chloride base material; polyvinyl chloride base material; cellophane base material; paper base material; aluminum foil base material; composite base material composed of these composite materials; The base material may be in the form of a film or a sheet. Of these, polyester base materials and polyamide base materials having a high glass transition point are preferably used.

The surface of the base material may be vapor-filmed with a metal oxide or the like, or may be coated with polyvinyl alcohol or the like. Examples of such a surface-treated substrate include GL-AE manufactured by Toppan Printing Co., Ltd. and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd., in which aluminum oxide is vapor-deposited on the surface. The base material may be treated with an additive such as an antistatic agent or an ultraviolet protection agent, if necessary, or may be corona-treated or low-temperature plasma-treated.

The thickness of the base material is not particularly limited and is usually in the range of 5 to 100 μm.

[Desorption layer]
The printed matter of the present invention may contain a desorption layer. Here, the "desorption layer" refers to a person having the property of being neutralized with an alkaline aqueous solution and having the property of peeling from the substrate by dissolving or swelling. The layer having desorption property is preferably a layer formed from the above-mentioned clear ink, but other layers may be desorption layers.

The thickness of the desorbed layer is not particularly limited and is usually in the range of 0.5 to 5 μm.

<Packaging material>
The packaging material of the present invention contains printed matter at least in part thereof. Examples of the packaging material include a structure in which a printed matter, an adhesive layer, and a sealant base material are sequentially laminated. Packaging materials are four-sided seal packaging, three-way seal packaging, pillow packaging, stick bag, gusset bag, square bottom bag, standing pouch, deep squeezed container, vacuum packaging, skin pack, chuck bag, spout pouch, twist packaging. It can be suitably used for packages having various shapes such as wrapping, shrink wrapping, labels, liquid paper packs, and paper trays.

The packaged material of the packaging material includes, for example, foodstuffs (for example, rice grains, confectionery, seasonings, edible oils and fats, cooked foods, etc.), beverages (for example, alcoholic beverages, soft drinks, mineral water, etc.), and daily / cultural supplies (for example). For example, pharmaceuticals, cosmetics, stationery, etc.), electronic parts, etc. may be mentioned.

[Adhesive layer]
Examples of the adhesive component that can be used to form the adhesive layer include a thermoplastic resin in addition to a laminate adhesive and a hot melt adhesive. Among the adhesive components, the laminate adhesive and the hot melt adhesive are, for example, a polyether adhesive; a polyurethane adhesive; an epoxy adhesive; a polyvinyl acetate adhesive; a cellulose adhesive; a (meth) acrylic adhesive. Agent; Among these adhesive components, a polyurethane adhesive is preferably used.

The adhesive component can be used alone or in combination of two or more.
The thickness of the adhesive layer is usually in the range of 1 to 6 μm.

[Sealant base material]
The sealant base material is a base material constituting the innermost layer of the laminated film, and a resin material that can be fused to each other by heat (having heat-sealing property) is used. Examples of the sealant base material include unstretched polypropylene (CPP), vapor-deposited unstretched polypropylene film (VMCPP), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene vinyl acetate copolymer (EVA) and the like. Be done.
The thickness of the sealant base material is not particularly limited, but is preferably in the range of 10 to 200 μm, more preferably in the range of 15 to 150 μm, in consideration of processability to the packaging material, heat sealability, and the like. Further, by providing the sealant base material with irregularities having a height difference of 5 to 20 μm, it is possible to impart slipperiness and tearability of the packaging material to the sealant base material.
Further, the method of laminating the sealant base material is not particularly limited. For example, a method of laminating the adhesive layer and the sealant base film by heat (heat laminating, dry laminating), or a method of melting the sealant base resin, extruding it onto the adhesive layer, cooling and solidifying it, and laminating it (extrusion). Lamination method) and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the Examples. In addition, "part" means "part by mass", and "%" means "mass%". The total of the copper content and the calcium content in the table is the content of the divalent metal.

(Method for identifying pigment composition)
The MALDI TOF-MS spectrum was used to identify the pigment composition used in the present invention. For the MALDI TOF-MS spectrum, the obtained compound was identified by matching the molecular ion peak of the obtained mass spectrum with the mass number obtained by calculation using the MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics. rice field.

(Measuring method of free copper)
Free copper was determined by the following method. First, 5 g of the pigment was precisely weighed, dissolved in 50 g of concentrated sulfuric acid while paying attention to heat generation, and stirred for 4 hours to prepare a sulfuric acid solution. After stirring, the sulfuric acid solution was added to 500 g of water to precipitate the pigment. After sufficiently stirring, the pigment was washed with water by filtration, the filtrate and the washing liquid were combined, and the volume was adjusted to 1000 ml. Atomic absorption analysis (polarized Zeeman atomic absorption spectrophotometer Z8100 type, manufactured by Hitachi, Ltd.) was used to determine the copper concentration by comparing it with a calibration curve with a copper standard solution. From the obtained copper concentration, the content of free copper per 1 kg of pigment was determined.

<Manufacturing of pigment composition>
[Example 1]
(Manufacturing of Pigment Composition [1-1])
1-pentanol 40,000 parts, o-phthalodinitrile 10,000 parts, copper chloride (I)
) 0.19 copies, 1,8-diazabicyclo [5.4.0] Undec-7-en 11,882
The parts were mixed, heated and stirred, and refluxed for 6 hours. After completion of the reaction, the obtained blue precipitate was filtered off and washed with methanol to obtain a blue cake.
Then, the obtained cake was put into 100,000 parts of ion-exchanged water and stirred, 98% sulfuric acid 3,158 was added, and the cake was heated and stirred at 80 ° C. for 3 hours. After completion of stirring, the blue precipitate was filtered off, washed with ion-exchanged water until the specific electric conductivity of the filtrate became 2 μS / cm or less, dried at 80 ° C., and pulverized to obtain a blue powder.
Then, blue powder was added to 100,000 parts of tetrahydrofuran, and the mixture was stirred and refluxed for 3 hours. After the stirring is completed, the blue precipitate is filtered off, washed with methanol, dried under reduced pressure, and the pigment composition containing the compound (1) and copper phthalocyanine [1-1] is 9,661.3 parts (yield 9).
6%) was obtained.

When the pigment composition [1-1] was analyzed by high frequency inductively coupled plasma emission spectroscopy (ICP emission spectroscopy), the copper content was 12 ppm and the calcium content was below the detection limit (1 ppm or less). there were. When the TOF-MS spectrum of the pigment composition was measured, a peak of 514.17 and a peak of 575.08 were detected, which matched the MS of the metal-free phthalocyanine and the copper phthalocyanine. It was confirmed that the composition contained the compound (1) and copper phthalocyanine. Moreover, when the free copper of the pigment composition was measured, the content of free copper was below the detection limit (0.2 ppm or less). From this result, all the copper contained in the pigment composition is derived from copper phthalocyanine.

[Examples 2 to 5, Production Example 1]
(Production of Pigment Compositions [1-2] to [1-5], [2-1])
The same operation as in Example 1 was performed except that 0.19 parts of copper (I) chloride used in Example 1 was replaced with 0.19 parts of copper (I) chloride by mass shown in Table 1, and the compound (1) was used. ) And copper phthalocyanine-containing pigment compositions [1-2] to [1-5] and [2-1] were obtained. In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 1 were obtained.

[Manufacturing Example 2]
(Manufacturing of Pigment Composition [2-2])
10000 parts of 1-pentanol was mixed with 10,000 parts of o-phthalodinitrile and 11,8-diazabicyclo [5.4.0] undec-7-ene (11,882 parts), and the mixture was heated and stirred.
It was refluxed for 6 hours. After completion of the reaction, the obtained blue precipitate was filtered off and washed with methanol to obtain a blue cake.
Then, the obtained cake was put into 100,000 parts of ion-exchanged water and stirred, 98% sulfuric acid 3,158 was added, and the cake was heated and stirred at 80 ° C. for 3 hours. After completion of stirring, the blue precipitate was filtered off, washed with ion-exchanged water until the specific electric conductivity of the filtrate became 2 μS / cm or less, dried at 80 ° C., and pulverized to obtain a blue powder.
Then, blue powder was added to 100,000 parts of tetrahydrofuran, and the mixture was heated and stirred at 80 ° C. for 2 hours. After the stirring is completed, the blue precipitate is filtered off, washed with methanol, and dried under reduced pressure to provide 9,461.3 parts (yield 94%) of the pigment composition [2-2] containing the compound (1). Obtained.

In the obtained pigment composition [2-2], the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 1 were obtained.

[Manufacturing Example 3]
(Manufacturing of Pigment Composition [2-3])
1-pentanol 40,000 parts, o-phthalodinitrile 10,000 parts, copper chloride (I)
) 1,931.43 parts and 1,8-diazabicyclo [5.4.0] undec-7-ene 11,882 parts were mixed, heated and stirred, and refluxed for 6 hours. After completion of the reaction, the obtained blue precipitate was filtered off and washed with methanol to obtain a blue cake.
Then, the obtained cake was put into 100,000 parts of ion-exchanged water and stirred, 98% sulfuric acid 3,158 was added, and the cake was heated and stirred at 80 ° C. for 3 hours. After completion of stirring, the blue precipitate was filtered off, washed with ion-exchanged water until the specific electric conductivity of the filtrate became 2 μS / cm or less, dried at 80 ° C., and pulverized to obtain a blue powder.
Then, blue powder was added to 80,000 parts of 98% sulfuric acid, and the mixture was heated and stirred at 60 ° C. for 3 hours. After the stirring was completed, the sulfuric acid solution was added dropwise to 400,000 parts of ion-exchanged water with stirring to obtain a blue precipitate. The obtained blue precipitate was filtered off, washed with ion-exchanged water until the specific conductivity of the filtrate became 2 μS / cm or less, dried at 80 ° C., and pulverized to obtain a blue powder.
Then, blue powder was added to 100,000 parts of tetrahydrofuran, and the mixture was stirred and refluxed for 2 hours. After the stirring was completed, the blue precipitate was filtered off, washed with methanol, and dried under reduced pressure to obtain 11,016.3 parts (yield 98%) of a pigment composition containing copper phthalocyanine. ..

When the calcium content of the obtained pigment composition [2-3] was analyzed in the same manner as in Example 1, it was below the detection limit (1 ppm or less).

[Example 6]
(Manufacturing of Pigment Composition [1-6])
Instead of 0.19 parts of copper (I) chloride used in Example 1, the pigment composition [2-3] 9.1
The same operation as in Example 1 was carried out except that 1 part was used to obtain a pigment composition [1-6] containing compound (1) and copper phthalocyanine. In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 1 were obtained.

[Example 7]
(Manufacturing of Pigment Composition [1-7])
300.00 parts of the pigment composition [2-2], 0.03 part of the pigment composition [2-3], 1000 parts of sodium chloride, and 200 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). It was charged and kneaded at 80 ° C. for 8 hours. Next, the kneaded mixture was put into 30,000 parts of ion-exchanged water at about 70 ° C., stirred for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then at 80 ° C. for a whole day and night. The pigment composition [1-7] containing the compound (1) and copper phthalocyanine, which was refined by drying and pulverizing, was obtained.
In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[Examples 8 to 9]
(Production of Pigment Compositions [1-8] to [1-9])
The same operation as in Example 7 was carried out except that the pigment composition [2-2] and the pigment composition [2-3] were changed to the amounts shown in Table 2, and the compound (1) and copper phthalocyanine were contained. Pigment compositions [1-8] to [1-9] were obtained.
In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[Example 10]
(Manufacturing of Pigment Composition [1-10])
Add 300.00 parts of the pigment composition [2-2] and 0.03 part of the pigment composition [2-3] to 2,400 parts of cooled 98% sulfuric acid while maintaining 10 ° C. or lower, and add 10 ° C. or less. Was stirred for 3 hours. After the stirring was completed, the sulfuric acid solution was added dropwise to 12,000 parts of ion-exchanged water with stirring to obtain a blue precipitate. The obtained blue precipitate was filtered off, washed with ion-exchanged water until the specific electric conductivity of the filtrate became 2 μS / cm or less, dried at 80 ° C., and pulverized to contain the compound (1) and copper phthalocyanine. 291.1 parts (yield 97%) of the pigment composition [1-10] was obtained.
In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[Example 11]
(Manufacturing of Pigment Composition [3-1])
1-pentanol 40,000 parts, o-phthalodinitrile 10,000 parts, copper chloride (I)
) 1.56 copies, 1,8-diazabicyclo [5.4.0] Undec-7-en 11,882
The parts were mixed, heated and stirred, and refluxed for 6 hours. After completion of the reaction, the obtained blue precipitate was filtered off and washed with methanol to obtain a blue cake.
Then, the obtained cake was put into 100,000 parts of ion-exchanged water and stirred, 98% sulfuric acid 3,158 was added, and the cake was heated and stirred at 80 ° C. for 3 hours. After the stirring is completed, the blue precipitate is filtered off, washed with ion-exchanged water until the specific electric conductivity of the filtrate becomes 2 μS / cm or less to form a blue cake, and then 2,500 parts of a 0.2% calcium sulfate aqueous solution. Was passed through the cake in 3 portions. The cake was taken out, dried at 80 ° C., and then pulverized to obtain a blue powder.
Then, blue powder was added to 100,000 parts of tetrahydrofuran, and the mixture was stirred and refluxed for 3 hours. After the stirring is completed, the blue precipitate is filtered off, washed with methanol, dried under reduced pressure, and the pigment composition containing the compound (1) and copper phthalocyanine [3-1] 9,716.4 parts (yield 9).
7%) was obtained.

In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 3 were obtained.

[Examples 12 to 18]
(Production of Pigment Compositions [3-2] to [3-8])
1.56 parts of copper (I) chloride and 0.2% calcium sulfate aqueous solution used in Example 11 2
The same operation as in Example 11 was carried out except that the mass parts of copper (I) chloride and 0.2% calcium sulfate aqueous solution shown in Table 3 were used instead of 500 parts, and the compound (1) and copper phthalocyanine were added. Pigment compositions containing [3-2] to [3-8] were obtained. In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 3 were obtained.

[Examples 19 to 20]
(Manufacturing of Pigment Compositions [3-9] to [3-10])
Instead of 1.56 parts of copper (I) chloride and 2500 parts of 0.2% calcium sulfate aqueous solution used in Example 11, parts of copper (I) chloride by mass shown in Table 3 and types shown in Table 3. The same operation as in Example 11 was carried out except that a calcium salt aqueous solution having a concentration and a part by mass was used to obtain pigment compositions [3-9] to [3-10] containing the compound (1) and copper phthalocyanine. .. In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 3 were obtained.

[Example 21]
(Manufacturing of Pigment Composition [3-11])
Instead of 1.56 parts of copper (I) chloride used in Example 12, the pigment composition [2-3] 9.
The same operation as in Example 12 was carried out except that 11 parts were used and the 0.2% aqueous calcium sulfate solution was changed to the parts by mass shown in Table 3, and the pigment composition containing the compound (1) and copper phthalocyanine [3]. -11] was obtained. In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 3 were obtained.

[Example 22]
(Manufacturing of Pigment Composition [3-12])
10000 parts of 1-pentanol was mixed with 10,000 parts of o-phthalodinitrile and 11,8-diazabicyclo [5.4.0] undec-7-ene (11,882 parts), and the mixture was heated and stirred.
It was refluxed for 6 hours. After completion of the reaction, the obtained blue precipitate was filtered off and washed with methanol to obtain a blue cake.
Then, the obtained cake was put into 100,000 parts of ion-exchanged water and stirred, 98% sulfuric acid 3,158 was added, and the cake was heated and stirred at 80 ° C. for 3 hours. After the stirring is completed, the blue precipitate is filtered off, washed with ion-exchanged water until the specific electric conductivity of the filtrate becomes 2 μS / cm or less to form a blue cake, and then 2,435 parts of a 0.2% calcium sulfate aqueous solution. Was passed through the cake in 3 portions. The cake was taken out, dried at 80 ° C., and then pulverized to obtain a blue powder.
Then, blue powder was added to 100,000 parts of tetrahydrofuran, and the mixture was stirred and refluxed for 3 hours. After the stirring is completed, the blue precipitate is filtered off, washed with methanol, and dried under reduced pressure to provide 9,464.5 parts (yield 94%) of the pigment composition [3-12] containing the compound (1). Obtained.

In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 4 were obtained.

[Examples 23 to 25, Production Example 4]
(Production of Pigment Compositions [3-13] to [3-15], [4-1])
The same operation as in Example 22 was performed except that the 0.2% calcium sulfate aqueous solution shown in Table 4 was used instead of 2,435 parts of the 0.2% calcium sulfate aqueous solution used in Example 22. , [3-13] to [3-15], [4-1] of the pigment composition containing the compound (1) were obtained. In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 4 were obtained.

[Examples 26 to 27]
(Manufacturing of Pigment Compositions [3-16] to [3-17])
The same operation as in Example 22 was performed except that the calcium salt aqueous solution of the type, concentration and mass shown in Table 4 was used instead of 2,435 parts of the 0.2% calcium sulfate aqueous solution used in Example 22. , Pigment compositions [3-16] to [3-17] containing the compound (1) were obtained. In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 4 were obtained.

[Example 28]
(Manufacturing of Pigment Composition [3-18])
Pigment composition [2-2] 300.00 parts, pigment composition [2-3] 0.03 parts, sodium chloride 1,000 parts, and diethylene glycol 200 parts, 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho). It was charged inside and kneaded at 80 ° C. for 8 hours. Next, the kneaded mixture was put into 30,000 parts of ion-exchanged water at about 70 ° C., stirred for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then made into a blue cake. 380 parts of a 0.2% calcium sulfate aqueous solution was passed through the cake in 3 portions. The cake was taken out, dried at 80 ° C. for 24 hours and night, and pulverized to obtain a pigment composition [3-18] containing the finely divided compound (1) and copper phthalocyanine.
In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 5 were obtained.

[Examples 29 to 30]
(Manufacturing of Pigment Compositions [3-19] to [3-20])
The same operation as in Example 28 was carried out except that the pigment composition [2-2] and the pigment composition [2-3] were changed to the amounts shown in Table 5, and the compound (1) and copper phthalocyanine were contained. Pigment compositions [3-19] to [3-20] were obtained.
In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 5 were obtained.

[Example 31]
(Manufacturing of Pigment Composition [3-21])
Add 300.00 parts of the pigment composition [2-2] and 0.03 part of the pigment composition [2-3] to 2400 parts of cooled 98% sulfuric acid while maintaining 10 ° C. or lower, and add 3 at 10 ° C. or lower. Stir for hours. After the stirring was completed, the sulfuric acid solution was added dropwise to 12,000 parts of ion-exchanged water with stirring to obtain a blue precipitate. The obtained blue precipitate was filtered off, washed with ion-exchanged water until the specific conductivity of the filtrate became 2 μS / cm or less to form a blue cake, and then 380 parts of a 0.2% calcium sulfate aqueous solution was applied 3 times. I divided it into pieces and passed it through the cake. The cake was taken out, dried at 80 ° C., and then pulverized to obtain 291.6 parts (yield 97%) of a pigment composition [3-21] containing compound (1) and copper phthalocyanine.
In the obtained pigment composition, the contents of copper and calcium and the amount of free copper were measured in the same manner as in Example 1, and the results shown in Table 5 were obtained.

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

<1> Evaluation of molding composition <1-1 Heat resistance evaluation>

[Example A-1]
Pigment composition [1-1] 1.5 parts, polypropylene resin (product name: Prime Polypro J-105G OS, manufactured by Prime Polymer Co., Ltd.) 1500 parts, titanium oxide (CR-80 Ishihara Sangyo Co., Ltd.) 15 parts, calcium stearate After 5.0 parts were put into a bag and mixed, they were put into a twin-screw extruder and melt-kneaded to prepare resin pellets. Using the prepared resin pellets, injection molding was performed under the condition that the temperature inside the barrel was 200 ° C., and 11 colored plates having a thickness of 3 mm were prepared. Next, the molding conditions were adjusted in advance so that the residence time in the barrel was 5 minutes, and the temperature in the barrel was further raised by 20 ° C. to perform the same operation. This was repeated up to 300 ° C. For the coloring plate, in order to detect the average color difference, a colorimeter (CM-700d manufactured by Konica Minolta Co., Ltd.) capable of measuring the total light emission of the 6th to 11th coloring plates is used. I measured the color. The hue was evaluated with a colored plate injected at 200 ° C., and the color was used as a reference color. When the ΔE * was 2 or less with respect to the reference color, the colored plate whose temperature was raised by 20 ° C. was evaluated to have heat resistance at that temperature. The maximum heat resistant temperature was 260 ° C.

[Examples A-2 to A-31, Comparative Examples A-1 to A-3]
Colored plates were obtained and evaluated in the same manner as in Example A-1, except that the pigment compositions of Example A-1 were changed to the pigment compositions shown in Table 6.

[Example A-32]
1.0 part of the pigment composition [1-1] used in Example A-1 was changed to 0.999 parts of the pigment composition [2-2] and 0.001 part of the pigment composition [2-3]. Except for the above, heat resistance test evaluation was performed in the same manner as in Example A-1.

[Example A-33]
1.0 part of the pigment composition [1-1] used in Example A-1 was changed to 0.999 parts of the pigment composition [3-13] and 0.001 part of the pigment composition [2-3]. Except for the above, heat resistance test evaluation was performed in the same manner as in Example A-1.

<1-2 Hue evaluation>
In Examples A-1 to A-33 and Comparative Examples A-1 to A-3, the 6th to 11th sheets 6 in order to detect the average color difference of the colored plates injected at 200 ° C. The colors of the colored plates were measured using a colorimeter (CM-700d, manufactured by Konica Minolta) capable of measuring the total luminous flux.
The color measurement values were compared with the colored plates of Comparative Example A-2 (pigment composition [2-2]), and the color difference (ΔE *) was obtained and evaluated according to the following criteria.

(Evaluation criteria)
5. ΔE * is less than 1.5. Very good 4. ΔE * is 1.5 or more and less than 3.0. Very good 3. ΔE * is 3.0 or more and less than 4.5. Good 2. ΔE * is 4.5 or more and less than 6.0. Practical use 1. ΔE * is 6.0 or more. Impractical

<Evaluation result>
Compared with Comparative Example A-2, which contains only compound (1), the pigment compositions of Examples A-1 to A-21 and A-28 to A-33 containing copper phthalocyanine have an increased heat resistance. It was seen.
However, Comparative Example A-1 containing 10021 ppm of copper had a large hue shift as compared with Comparative Example A-2 containing only metal-free phthalocyanine, and was not practical as a greenish blue pigment.
It is presumed that the reason why the pigment composition containing copper phthalocyanine is excellent in heat resistance is that the properties are exhibited by adsorbing copper phthalocyanine having excellent heat resistance on the surface of the compound (1) or the like. It is presumed that the presence of copper phthalocyanine on the surface causes the above effect even in a small amount, does not impair the hue of compound (1), and produces a good greenish blue pigment.

<1-3 Variance evaluation>
(Preparation of 10% colored resin composition)
[Example B-1]
A twin-screw extruder (Toshiba Machine Co., Ltd.) was mixed with 1078.8 parts of Prime Polypro J-105G powder resin manufactured by Prime Polymer Co., Ltd., 120 parts of pigment composition [1-1], and 1.2 parts of calcium stearate until uniform. 1150 parts of a colored resin composition (1) having a pigment content of 10% was obtained by heating, melting and kneading at a set temperature of 200 ° C. with TEM-18SS manufactured by the same company without causing strand breakage or pulsation while degassing.

[Examples B-2 to B-31, Comparative Examples B-1 to B-3]
Colored resin compositions (2) to (34) were obtained in the same manner as in Example B-1, except that the pigment composition of Example B-1 was changed to the pigment composition shown in Table 7. ..

[Example B-32]
All except that 120 parts of the pigment composition [1-1] of Example B-1 was changed to 119.88 parts of the pigment composition [2-2] and 0.12 parts of the pigment composition [2-3]. The colored resin composition (35) was obtained in the same manner as in Example B-1.

[Example B-33]
All except that 120 parts of the pigment composition [1-1] of Example B-1 was changed to 119.88 parts of the pigment composition [3-13] and 0.12 parts of the pigment composition [2-3]. The colored resin composition (36) was obtained in the same manner as in Example B-1.

(Measurement of pressure rise at the tip of the extruder)
When a large number of undispersed pigments are present in the colored resin composition, the mesh is clogged with extrusion. Therefore, the obtained colored resin composition was subjected to a colored resin composition 1000 having a pigment content of 10% by using a single-screw extruder (Laboplast Mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a metal mesh having a 25 micron cut at the tip. Parts (100 parts as pigment) were extruded. The difference (bar) between the pressure applied at the initial stage of extrusion and the pressure applied to the mesh when 1000 parts of the colored resin composition having a pigment content of 10% is extruded is obtained, divided by the amount of extruded pigment (g), and is an index of dispersibility. (Bar / g) and the following scores were given.

(Evaluation criteria)
5: Less than 0.2 bar / g Very good 4: Less than 0.3 bar / g Good 3: Less than 0.6 bar / g Practical use 2: 0.6 bar / g or more Practical use impossible 1: Resin pressure rises too much and pigment content I couldn't extrude 100g as a practical use

(Evaluation of coarse particles in film molded products)
The obtained colored resin composition having a pigment content of 10% and Prime Polypro F227D manufactured by PP Resin Prime Polymer Co., Ltd., which is a resin to be colored, are mixed so that the pigment concentration becomes 1.5%, and a T-die film molding machine is used. Using (manufactured by Toyo Seiki Co., Ltd.), a film having a molding temperature of 250 ° C. and a screw rotation speed of 50 rpm was melt-extruded to obtain a film having a film thickness of 30 μm. For the obtained films, the number of pigment particles of 1 μm or more and 50 μm or less in each film was measured with an image processing machine “Luzex 450” (manufactured by Nireco Corporation), and the following scores were given. If the score is 4 or more, it can be judged to be good.
(Evaluation criteria)
5: 1.0 x 10 ³ pieces / cm less than ² 4: 1.0 x 10 ³ to 7.0 x 10 ³ pieces / cm less than ² 3: 7.0 x 10 ³ to 2.7 x 10 ⁴ pieces / Less than cm ² 2: 2.7 × 10 ⁴ to 7.0 × 10 ⁴ pieces / cm Less than ² 1: 7.0 × 10 ⁴ pieces / cm ² or more

<Evaluation result>
Table 7 shows the results of measuring the pressure rise value at the tip of the extruder and evaluating the number of coarse particles in the film-molded product.
Examples B-1 to B-33, which are pigment compositions containing copper phthalocyanine and calcium, have excellent dispersibility as compared with Comparative Example B-2 containing no copper phthalocyanine or calcium. Further, Comparative Example B-3 containing 10546 ppm of calcium had low dispersibility.
The reason why the dispersibility is excellent by containing copper phthalocyanine in the compound (1) is that the easily dispersible copper phthalocyanine is adsorbed on the surface of the compound (1) and dispersed from the surface state of the compound (1) which is difficult to disperse. It is presumed that the surface condition of copper phthalocyanine is easy to handle. Further, it is presumed that the presence of copper phthalocyanine on the surface allows the above effect to be exhibited even in a small amount, and the hue of compound (1) is not impaired, resulting in a good greenish blue pigment.
Further, the reason why the dispersibility is excellent by containing the calcium salt in the compound (1) is that the dispersibility is improved by preventing the aggregation of the compound (1) and reducing the secondary aggregation of the pigment composition. Infer. This is because the compound (1) has a strong π-π interaction, so that secondary agglomeration in which the primary particles of the pigment agglomerate easily occurs even after the pigment is formed, but it is divalent such as a calcium salt during drying. It is presumed that the presence of the metal salt plays a role in preventing the secondary aggregation of the pigment, the particles of the compound (1) are easily loosened at the time of dispersion, and the dispersibility is improved.
Comparing Examples B-12, B-19, and B-20 having different calcium salts, the dispersibility was most improved when calcium sulfate was used. It is presumed that this is because calcium sulfate is difficult to dissolve in water and easily precipitates when the pigment composition is dried, so that calcium sulfate precipitates well between the layers before the dry aggregation of the pigment occurs, and the aggregation of the pigment is suppressed. do. It is presumed that Examples B-23, B-26, and B-27 also have the highest dispersibility when calcium sulfate is used for the same reason.
Further, Examples B-1 to B-10 and B-32 containing only copper phthalocyanine in compound (1) and Examples B-11 to B-21 and B- in which compound (1) contains copper phthalocyanine and a calcium salt. Comparing 33 in the case of containing the same amount of copper phthalocyanine, Examples B-11 to B-21 and B-33 containing copper phthalocyanine and a calcium salt had higher dispersibility. By combining the effect of modifying the surface condition of the copper phthalocyanine compound (1) and the effect of preventing the secondary aggregation of the calcium salt pigment, a pigment composition having even better dispersibility can be obtained. I presume that it was done.

<2> Evaluation of gravure ink First, the resin measurement method will be described below.

(Hydroxy group value)
The hydroxyl value is a value obtained by converting the amount of hydroxyl groups in 1 g of the resin, which is calculated by esterifying or acetylating the hydroxyl groups in the resin with an excess anhydrous acid and back-titling the remaining acid with an alkali, into the number of mg of potassium hydroxide. So, it is a value performed according to JISK0070.

(Amine value)
The amine value is the mg number of potassium hydroxide in the same amount as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of the resin. The acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of the resin, and the measuring method may be a known method, generally according to JISK0070 (1996). Will be done. The method for measuring the amine value was, for example, the following method.

-Measuring method of amine value Weigh 0.5 to 2 g of the sample. (Sample amount: Sg) Add 30 mL of neutral ethanol (BDG neutral) to the finely weighed sample and dissolve. The obtained solution is titrated with a 0.2 mol / l ethanolic hydrochloric acid solution (titer: f). With the point where the color of the solution changed from green to yellow as the end point, the amine titer was determined by the following (Equation 2) using the titration amount (AmL) at this time.
(Equation 2) Amine value = (A × f × 0.2 × 56.108) / S

(Average molecular weight)
The weight average molecular weight and the number average molecular weight were determined as polystyrene-equivalent molecular weights by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (“ShodexGPCSystem-21” manufactured by Showa Denko KK).

(Synthesis Example 1) [Polyurethane Resin PU1]
160 parts of polyester polyol (hereinafter referred to as "PMPA") obtained from adipic acid having a number average molecular weight of 2,000 and 3-methyl-1,5-pentanediol, and a number average molecular weight of 2,000.
20 parts of polypropylene glycol (hereinafter "PPG"), 20 parts of polypropylene glycol having an average molecular weight of 1,000, 53.8 parts of isophorone diisocyanate (hereinafter "IPDI"), and 63.4 parts of ethyl acetate under a nitrogen stream. The reaction was carried out at ° C. for 4 hours to obtain a solvent solution of the terminal isocyanate prepolymer. Next, 23.1 parts of isophoronediamine (hereinafter "IPDA"), 2.0 parts of iminobispropylamine (hereinafter "IBPA"), 1.0 part of 2-ethanolamine (hereinafter "2EtAm"), ethyl acetate / isopropanol (hereinafter "Isopropanol"). "IPA") = 589.7 parts of a mixed solvent of 50/50 was gradually added with the obtained terminal isocyanate prepolymer solution at 40 ° C., and then reacted at 80 ° C. for 1 hour to obtain a solid content. A polyurethane resin solution PU1 having a amine value of 11.1 mgKOH / g, a hydroxyl value of 3.3 mgKOH / g, and a weight average molecular weight of 35,000 was obtained.

[Example C-1]
(Manufacturing of gravure ink 1)
As the binder resin, 40 parts of polyurethane resin solution PU1 (nonvolatile content 30%), 5.0 parts of salt and vinegar biresin (solvine TAO: manufactured by Nisshin Kagaku Co., Ltd.), and silica particles (P-73 manufactured by Mizusawa Kagaku Co., Ltd.) 0. .6 parts, 10 parts of the pigment composition [1-1], 45.0 parts of the solution of Npropyl acetate / IPA = 50/50 (mass ratio) are mixed, and the Eiger mill until the particle size becomes 10 μm or less with a grind gauge. The mixture was dispersed in 1 to obtain gravure ink 1.

[Examples C-2 to C-31, Comparative Examples C-1 to C-3]
(Manufacturing of gravure inks 2-34)
In the method for preparing the gravure ink 1 described in Example C-1, the pigment composition [1-1] was changed as shown in Table 8, but the gravure inks 2 to 2 were similar to those in Example C-1. I got 34.

[Example C-32]
(Manufacturing of gravure ink 35)
All except that 10 parts of the pigment composition [1-1] of Example C-1 was changed to 9.99 parts of the pigment composition [2-2] and 0.01 part of the pigment composition [2-3]. Gravure ink 35 was obtained in the same manner as in Example C-1.

[Example C-33]
(Manufacturing of gravure ink 36)
All except that 10 parts of the pigment composition [1-1] of Example C-1 was changed to 9.99 parts of the pigment composition [3-13] and 0.01 part of the pigment composition [2-3]. The gravure ink 36 was obtained in the same manner as in Example C-1.

<Printing of gravure ink>
[Example D-1]
<Printing of gravure ink for laminating>
The gravure ink 1 obtained above is subjected to a viscosity of 16 seconds (25 ° C., Zahn cup No.) by a mixed solvent (methyl ethyl ketone "MEK": Npropyl acetate "NPAC": isopropanol "IPA" = 40: 40: 20). .3) Dilute to a thickness of 12 μm with a 12 μm-thick corona discharge-treated polyester (PET) film (Toyobo Co., Ltd.) using a Helio 175-line gradation plate (plate type Erongate, 75% solid pattern and 100% to 3% gradation pattern). Printing was performed on the corona discharge-treated surface of E-5100) at a printing speed of 100 m / min to obtain a printed matter 1. The printing conditions were a temperature of 25 ° C. and a humidity of 60%, and the printing distance was 4000 m.

For the obtained printed matter 1, 1.5 g / m 2 and 1.0 g / g / m ² and 1.0 g / of a polyether urethane-based laminated adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd.) as an ethyl acetate solution having a solid content of 25% by mass and 10% by mass. It was coated and dried to m ² , and then laminated with aluminum-deposited unstretched polypropylene (VMCP2203, film thickness 25 μm, manufactured by Toray Film Processing Co., Ltd.) to perform a dry laminating process.

[Examples D-2-33, Comparative Examples D-1 to 3]
The gravure inks 2 to 36 shown in Table 8 were printed in the same manner as in Example D-1 except that the gravure inks shown in Table 9 were used to obtain printed matter D-2 to D-36.

<Evaluation>
The following evaluations were made using the gravure inks 1 to 36 and the printed matter D-1 to D-36.

<Evaluation of dispersibility>
The shorter the production time of the gravure ink, the higher the dispersibility. When the dispersion time of Comparative Example C-2 was 100%, the dispersibility of each pigment composition was evaluated according to the following criteria.

(Evaluation criteria)
5. Dispersion time less than 25% (very good)
4. Dispersion time 25% or more and less than 50% (good)
3. 3. Dispersion time is 50% or more and less than 75% (slightly good)
2. 2. Dispersion time is 75% or more and less than 100% (practical, but slightly defective)
1. 1. Dispersion time is 100% or more (defective)

<Ink stability over time>
Each of the gravure inks 1 to 36 was placed in a closed container and stored at 40 ° C. for 10 days. After that, the viscosity was measured and the change in viscosity from before storage was evaluated. The viscosity was measured at 25 ° C. It was performed in 4 outflow seconds.

(Evaluation criteria)
5. Viscosity change less than 2 seconds (good)
4. Viscosity change is 2 seconds or more and less than 5 seconds (practical)
3. 3. Viscosity change is 5 seconds or more and less than 10 seconds (slightly defective)
2. 2. Viscosity change is 10 seconds or more and less than 15 seconds (defective)
1. 1. Viscosity change is 15 seconds or more (extremely poor)
Note that 5 and 4 are ranges in which there is no practical problem.

<Hue evaluation>
Regarding hue, the printed matter is overlaid on white bleached paper (BYK Bico-chart uncoated N2C), and the color is measured with a colorimeter (Konica Minolta, CM-700d) capable of measuring the total luminous flux, and compared. The color difference (ΔE *) was obtained based on Example D-2 and evaluated according to the following criteria.

(Evaluation criteria)
5. ΔE * is less than 1.5. Very good 4. ΔE * is 1.5 or more and less than 3.0. Very good 3. ΔE * is 3.0 or more and less than 4.5. Good 2. ΔE * is 4.5 or more and less than 6.0. Practical use 1. ΔE * is 6.0 or more. Impractical

The evaluation results are shown in Tables 8 and 9. Examples C-1 to C-33 and Comparative Example C-1, which are pigment compositions containing copper phthalocyanine and calcium, have excellent dispersibility as compared with Comparative Example C-2 containing no copper phthalocyanine and calcium. became. However, Comparative Example C-1 containing 10021 ppm of copper had a large hue shift as compared with Comparative Example C-2 containing only metal-free phthalocyanine, and was not practical as a greenish blue pigment. Further, Comparative Example C-3 containing 10546 ppm of calcium had low dispersibility.
The reason why the dispersibility is excellent by containing copper phthalocyanine in the compound (1) is that the easily dispersible copper phthalocyanine is adsorbed on the surface of the compound (1) and dispersed from the surface state of the compound (1) which is difficult to disperse. It is presumed that the surface condition of copper phthalocyanine is easy to handle. Further, it is presumed that the presence of the divalent metal phthalocyanine on the surface allows the above effect to be exhibited even in a small amount, and the hue of the compound (1) is not impaired, resulting in a good greenish blue pigment.
Further, the reason why the dispersibility is excellent by containing the calcium salt in the compound (1) is that the dispersibility is improved by preventing the aggregation of the compound (1) and reducing the secondary aggregation of the pigment composition. Infer. This is because the compound (1) has a strong π-π interaction, so that secondary agglomeration in which the primary particles of the pigment agglomerate easily occurs even after the pigment is formed, but it is divalent such as a calcium salt during drying. It is presumed that the presence of the metal salt plays a role in preventing the secondary aggregation of the pigment, the particles of the compound (1) are easily loosened at the time of dispersion, and the dispersibility is improved.
Comparing C-12, C-19, and C-20 with different calcium salts, the dispersibility was most improved when calcium sulfate was used. It is presumed that this is because calcium sulfate is difficult to dissolve in water and easily precipitates when the pigment composition is dried, and calcium sulfate precipitates well between the layers before the dry aggregation of the pigment occurs, thereby suppressing the aggregation of the pigment. .. It is presumed that C-23, C-26, and C-27, which have different calcium salts, also have the highest dispersibility when calcium sulfate is used for the same reason.
Further, Examples C-1 to C-10 and C-32 containing only copper phthalocyanine in compound (1) and Examples C-11 to C-21 and C- in compound (1) containing copper phthalocyanine and a calcium salt. Comparing 33 in the case of containing the same amount of copper phthalocyanine, Examples C-11 to C-21 and C-33 containing copper phthalocyanine and a calcium salt had higher dispersibility. By combining the effect of modifying the surface condition of the copper phthalocyanine compound (1) and the effect of preventing the secondary aggregation of the calcium salt pigment, a pigment composition having even better dispersibility can be obtained. I presume that it was done.

<3> Evaluation of water-based flexo ink

[Synthesis Example 2] (Synthesis of Aqueous Urethane Resin A)
82.3 parts of polytetramethylene glycol having a number average molecular weight of 2,000 and a number average molecular weight of 2, in a four-necked 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas introduction tube, a stirrer, and a thermometer. 3 parts of 000 polyethylene glycol, 13 parts of dimethylolbutanoic acid, and 1.7 parts of 1,4-cyclohexanedimethanol were charged, replaced with dry nitrogen, and heated to 100 ° C. Under stirring, 33.3 parts of isophorone diisocyanate was added dropwise over 20 minutes, and the temperature was gradually raised to 140 ° C. (NCO / OH = 0.98). The reaction was further carried out for 30 minutes to obtain a urethane resin. Next, while cooling, 399.8 parts of distilled water containing 5.3 parts of 28% ammonia water was added to obtain an aqueous urethane resin A (weight average molecular weight of about 40,000, solid content of 25%, acid value of 36.9). (MgKOH / g), hydroxyl value 11.1 (mgKOH / g)).

<Manufacturing of water-based flexo ink>
[Example E-1]
(Manufacturing of water-based flexo ink 1)
A 45 parts of water-based urethane resin A, 15 parts of pigment composition [1-1], 2 parts of polyethylene wax (W310 manufactured by Mitsui Chemicals, Inc., particle size 9.5 μm, softening point 132 ° C., needle penetration method hardness 0.8), adipic acid 0.2 parts of acid dihydrazide, 0.2 parts of ammonia water (28%), 18.8 parts of water, and 18.8 parts of isopropanol were dispersed with an Eiger mill (manufactured by Eiger) until the particle size was 10 μm or less with a grind gauge. , Aqueous flexo ink 1 was produced.

[Examples E-2 to E-32, Comparative Examples E-1 to E-3]
(Manufacturing of water-based flexo inks 2-34)
In the method for preparing the water-based flexo ink 1 described in Example E-1, the water-based flexo ink is the same as in Example E-1 except that the pigment composition [1-1] is changed as shown in Table 10. Got 2-34

[Example E-33]
(Manufacturing of water-based flexo ink 35)
All except that 15 parts of the pigment composition [1-1] of Example E-1 were changed to 14.985 parts of the pigment composition [2-2] and 0.015 parts of the pigment composition [2-3]. Aqueous flexo ink 35 was obtained in the same manner as in Example E-1.

[Example E-33]
(Manufacturing of water-based flexo ink 36)
All except that 15 parts of the pigment composition [1-1] of Example E-1 were changed to 14.985 parts of the pigment composition [3-13] and 0.015 parts of the pigment composition [2-3]. Aqueous flexo ink 36 was obtained in the same manner as in Example E-1.

<Evaluation method and evaluation criteria>
Printing in Examples and Comparative Examples was performed as follows.
Flexographic rotation printing: Using a center drum type 6-color flexographic printing machine "SOLOFLEX" manufactured by Windmirror & Helscher, printing was performed on a plastic film at a speed of 100 m / min and dried at 60 to 70 ° C. to obtain a printed matter. As the Anilox roll, 350 lines / cm is used, and as the plate body, DuPont's "Sirel DPU" (thickness 1.14 mm) is made into a solid plate, and double-sided tape (Toyo Ink Co., Ltd. "DF7382T" is used. It was used by pasting it with a thickness of 0.50 mm).

(1) Dispersibility The shorter the production time of the water-based flexo ink, the higher the dispersibility. When the dispersion time of Comparative Example E-2 was 100%, the dispersibility of each pigment composition was evaluated according to the following criteria.

(Evaluation criteria)
5. Dispersion time less than 25% (very good)
4. Dispersion time 25% or more and less than 50% (good)
3. 3. Dispersion time is 50% or more and less than 75% (slightly good)
2. 2. Dispersion time is 75% or more and less than 100% (practical, but slightly defective)
1. 1. Dispersion time is 100% or more (defective)

(2) Ink stability After the ink was stored at a constant temperature of 40 ° C. for 3 months, the Zahn Cup No. The viscosity over time was measured using 4 (25 ° C.), and the difference from the finished (initial) viscosity was evaluated. The evaluation criteria are shown below. The practical level is 3 or higher.

(Evaluation criteria)
5. 3. The difference between the finished viscosity and the viscosity over time is less than 2 seconds. 3. The difference between the finished viscosity and the viscosity over time is 2 seconds or more and less than 4 seconds. 2. The difference between the finished viscosity and the viscosity over time is 4 seconds or more and less than 6 seconds. The difference between the finished viscosity and the viscosity over time is 6 seconds or more and less than 8 seconds. The difference between the finished viscosity and the viscosity over time is 8 seconds or more.

(3) Hue Ink is spread on PET film (polyethylene terephthalate film, E-5102, 12 μm manufactured by Toyo Spinning Co., Ltd.) with a mayer bar, and superimposed on white colored paper (Biko-chart coated N2C manufactured by BYK Co., Ltd.). The color was measured with a colorimeter capable of measuring the light beam (CM-700d manufactured by Konica Minolta Co., Ltd.), the color difference (ΔE *) was obtained based on Comparative Example E-2, and the evaluation was performed according to the following criteria.

(Evaluation criteria)
5. ΔE * is less than 1.5. Very good 4. ΔE * is 1.5 or more and less than 3.0. Very good 3. ΔE * is 3.0 or more and less than 4.5. Good 2. ΔE * is 4.5 or more and less than 6.0. Practical use 1. ΔE * is 6.0 or more. Impractical

The evaluation results are shown in Table 10. Examples E-1 to E-33 and Comparative Example E-1, which are pigment compositions containing copper phthalocyanine and calcium, have dispersibility and stability over time as compared with Comparative Example E-2 containing no copper phthalocyanine or calcium. Was an excellent result. However, Comparative Example E-1 containing 10021 ppm of copper had a large hue shift as compared with Comparative Example E-2 containing only metal-free phthalocyanine, and was not practical as a greenish blue pigment. In addition, Comparative Example E-3 containing 10546 ppm of calcium had low dispersibility and stability over time.
The reason why the dispersibility and stability over time are excellent by containing copper phthalocyanine in the compound (1) is that the easily dispersible copper phthalocyanine is adsorbed on the surface of the compound (1) and the surface of the compound (1) is difficult to disperse. From the state, it is presumed that the surface state of copper phthalocyanine is easy to disperse. Further, it is presumed that the presence of the divalent metal phthalocyanine on the surface allows the above effect to be exhibited even in a small amount, and the hue of the compound (1) is not impaired, resulting in a good greenish blue pigment.
Further, the reason why the dispersibility is excellent by containing the calcium salt in the compound (1) is that the dispersity and the stability over time are achieved by preventing the aggregation of the compound (1) and reducing the secondary aggregation of the pigment composition. I presume that has improved. This is because the compound (1) has a strong π-π interaction, so that secondary agglomeration in which the primary particles of the pigment agglomerate easily occurs even after the pigment is formed, but it is divalent such as a calcium salt during drying. It is presumed that the presence of the metal salt plays a role in preventing the secondary aggregation of the pigment, the particles of the compound (1) are easily loosened during dispersion, and the dispersibility and stability over time are improved.
Comparing Examples E-12, E-19, and E-20 with different calcium salts, the dispersibility and stability over time were most improved when calcium sulfate was used. It is presumed that this is because calcium sulfate is difficult to dissolve in water and easily precipitates when the pigment composition is dried, so that calcium sulfate precipitates well between the layers before the dry aggregation of the pigment occurs, and the aggregation of the pigment is suppressed. do. It is presumed that Examples E-23, E-26, and E-27 also have the highest dispersibility and stability over time when calcium sulfate is used for the same reason.
Further, Examples C-1 to C-10 and C-32 containing only copper phthalocyanine in compound (1) and Examples C-11 to C-21 and C- in compound (1) containing copper phthalocyanine and a calcium salt. Comparing 33 in the case of containing the same amount of copper phthalocyanine, Examples C-11 to C-21 and C-33 containing copper phthalocyanine and a calcium salt had higher dispersibility and stability over time. This is a pigment with even better dispersibility and stability over time by combining the effect of modifying the surface condition of the copper phthalocyanine compound (1) and the effect of preventing the secondary aggregation of the calcium salt pigment. It is presumed that the composition was obtained.

<4> Evaluation of active energy ray-curable ink

<Manufacturing of Inactive Resin Varnish>
30 parts of diallyl phthalate resin (Daiso Dup A manufactured by Daiso Corporation) having a weight average molecular weight of 50,000 was dissolved in 70 parts of ditrimethylolpropane tetraacrylate and heated and mixed (80 ° C.) to prepare a resin varnish A. ..

<Making active energy ray-curable ink>
[Example F-1]
(Manufacturing of active energy ray-curable ink 1)
15 parts of pigment composition [1-1], 9.7 parts of EO (3) modified trimetrol propanetriacrylate, 9.2 parts of dimethylol propanetetraacrylate, 23 parts of dipentaerythritol hexaacrylate, 2 parts of Omnirad 369. 2 parts of Omnirad 907, 2 parts of OmniradDETX, 2 parts of OmniradEMK, 0.5 part of solid wax (polytetrafluoroethylene wax), 1 part of talc, 0 part of polymerization inhibitor (N-nitrosophenylhydroxylamine aluminum) .3 parts and 33.3 parts of resin varnish A are mixed, stirred and mixed using a butterfly mixer, and then dispersed on three rolls so that the maximum particle size is 7.5 μm or less, and the active energy ray is used. Curable ink 1 was produced.

The details of the materials used are as follows.

[Polymer initiator]
Omnirad 369: iGM RESINS, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone · Omnirad 907: iGM RESINS, 2-methyl-4'-methylthio-2- Morpholine propiophenone / OmniradDETX: iGM RESINS, 2,4-dimethylthioxanthone / OmniradEMK: iGM RESINS, 4,4'-bis (diethylamino) benzophenone

[Abrasion resistant agent]
(Solid wax)
-Teflon (registered trademark) modified polyethylene wax Polytetrafluoroethylene wax, "Fluoroslip 511" manufactured by Shamrock, melting point: 126 ° C)

[Other ingredients]
(Constitution pigment)
・ Talc: High Filler 5000PJ (manufactured by Matsumura Sangyo Co., Ltd.)

[Examples F-2 to F-31, Comparative Examples F-1 to F-3]
(Manufacturing of active energy ray-curable inks 2-34)
Active energy ray-curable inks 2 to 34 were prepared in the same manner as in Example F-1 except that the pigments shown in Table 11 were used instead of the pigment composition [1-1].

[Example F-32]
(Manufacturing of active energy ray-curable ink 35)
All except that 15 parts of the pigment composition [1-1] of Example F-1 were changed to 14.985 parts of the pigment composition [2-2] and 0.015 parts of the pigment composition [2-3]. An active energy ray-curable ink 35 was obtained in the same manner as in Example F-1.

[Example F-33]
(Manufacturing of active energy ray-curable ink 36)
All except that 15 parts of the pigment composition [1-1] of Example F-1 were changed to 14.985 parts of the pigment composition [3-13] and 0.015 parts of the pigment composition [2-3]. An active energy ray-curable ink 36 was obtained in the same manner as in Example F-1.

The performance of the obtained active energy ray-curable ink was evaluated by the following method. The results are shown in Table 11.

[Method of preparing test sample]
A solid image of the obtained ink composition was printed on Tokubishi Art Paper, which is a base material, using a RI tester (manufactured by Tester Sangyo Co., Ltd.) in a filling amount of 0.25 ml. Then, the ink composition was cured with a conveyor speed of 60 m / min, an LED lamp (“XP-9” manufactured by Air Motion System Co., Ltd., an irradiation distance of 10 mm, and an output of 70%) to prepare a test sample. The RI tester is a testing machine that prints ink on paper or film, and can adjust the amount of ink transfer and the printing pressure.

[Dispersity]
The shorter the production time of the active energy ray-curable ink, the higher the dispersibility. When the dispersion time of Comparative Example F-2 was 100%, the dispersibility of each pigment composition was evaluated according to the following criteria.

(Evaluation criteria)
5. Dispersion time less than 25% (very good)
4. Dispersion time 25% or more and less than 50% (good)
3. 3. Dispersion time is 50% or more and less than 75% (slightly good)
2. 2. Dispersion time is 75% or more and less than 100% (practical)
1. 1. Dispersion time is 100% or more (defective)

[Gloss]
Using the test piece prepared by the above method, the gloss value (based on JIS Z 8741) at the 60 ° reflection angle of the surface on which the ink composition was developed was measured with a gloss meter GM62D manufactured by Murakami Color Research Institute. It is evaluated that the level is 3 or more and there is no practical problem. When the pigment is well dispersed, the gloss is improved.
(Evaluation criteria)
5: Gloss value is 70 or more and 4: Gloss value is 65 or more and less than 70 3: Gloss value is 60 or more and less than 65 2: Gloss value is 55 or more and less than 60 1: Gloss value is less than 55 be

[Hue evaluation]
Regarding the hue, the test piece prepared by the above method was used to measure the color using a colorimeter capable of measuring the total luminous flux (CM-700d manufactured by Konica Minolta), and the color difference was based on Comparative Example F-2. (ΔE *) was obtained and evaluated according to the following criteria.

(Evaluation criteria)
5. ΔE * is less than 1.5. Very good 4. ΔE * is 1.5 or more and less than 3.0. Very good 3. ΔE * is 3.0 or more and less than 4.5. Good 2. ΔE * is 4.5 or more and less than 6.0. Practical use 1. ΔE * is 6.0 or more. Impractical

The evaluation results are shown in Table 11. Examples F-1 to F-33 and Comparative Example F-1, which are pigment compositions containing copper phthalocyanine and calcium, are superior in dispersibility and gloss as compared with Comparative Example F-2 containing no copper phthalocyanine or calcium. The result was. However, Comparative Example F-1 containing 10021 ppm of copper had a large hue shift as compared with Comparative Example F-2 containing only metal-free phthalocyanine, and was not practical as a greenish blue pigment. Further, Comparative Example F-3 containing 10546 ppm of calcium had low dispersibility and low gloss.

The reason why the dispersibility and gloss are excellent by containing copper phthalocyanine in the compound (1) is that the copper phthalocyanine that is easily dispersed is adsorbed on the surface of the compound (1) and the surface state of the compound (1) that is difficult to disperse. It is presumed that the surface condition of copper phthalocyanine is easy to disperse. Further, it is presumed that the presence of the divalent metal phthalocyanine on the surface allows the above effect to be exhibited even in a small amount, and the hue of the compound (1) is not impaired, resulting in a good greenish blue pigment.
Further, the reason why the dispersibility is excellent by containing the calcium salt in the compound (1) is that the dispersibility and gloss are improved by preventing the aggregation of the compound (1) and reducing the secondary aggregation of the pigment composition. I guess I did. This is because the compound (1) has a strong π-π interaction, so that secondary agglomeration in which the primary particles of the pigment agglomerate easily occurs even after the pigment is formed, but it is divalent such as a calcium salt during drying. It is presumed that the presence of the metal salt plays a role in preventing the secondary aggregation of the pigment, the particles of the compound (1) are easily loosened at the time of dispersion, and the dispersibility and gloss are improved.
Comparing Examples F-12, F-19, and F-20 having different calcium salts, the dispersibility and gloss were most improved when calcium sulfate was used. It is presumed that this is because calcium sulfate is difficult to dissolve in water and easily precipitates when the pigment composition is dried, so that calcium sulfate precipitates well between the layers before the dry aggregation of the pigment occurs, and the aggregation of the pigment is suppressed. do. It is presumed that Examples F-23, F-26, and F-27 also have the highest dispersibility and gloss when calcium sulfate is used for the same reason.
Further, Examples F-1 to F-10 and F-32 containing only copper phthalocyanine in compound (1) and Examples F-11 to F-21 and F- containing copper phthalocyanine and a calcium salt in compound (1). Comparing 33 in the case of containing the same amount of copper phthalocyanine, Examples F-11 to F-21 and F-33 containing copper phthalocyanine and a calcium salt had higher dispersibility and gloss. By combining the effect of modifying the surface condition of the copper phthalocyanine compound (1) and the effect of preventing the secondary aggregation of the calcium salt pigment, a pigment composition having even better dispersibility can be obtained. I presume that it was done.

<5> Toner evaluation Negatively charged toner was prepared and evaluated.

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

[Comparative Example G-1]
(Manufacturing of Negatively Charged Toner 2)
Negatively charged toner 2 was obtained in the same manner as in Example G-1 except that the pigment composition [3-2] used in Example G-1 was changed to the pigment composition [2-2].

The obtained negatively charged toner 1 and negatively charged toner 2 were each sliced to a thickness of 0.9 μm using a microtome to form a sample. Next, the dispersed state of the pigment was observed for each sample using a transmission electron microscope. As a result, the pigment is more uniformly distributed and dispersed in the negatively charged toner 1 using the pigment composition [3-2] than in the negatively charged toner 2 using the pigment composition [2-2]. It was confirmed that the sex was good.

<6> Evaluation of water-based inkjet ink A water-based inkjet ink was prepared and evaluated as follows.

[Example H-1]
(Preparation of Aqueous Coloring Composition for Inkjet (hereinafter referred to as "Aqueous Coloring Composition for IJ") 1)
The following raw materials and 200 parts of 1.25 mm diameter zirconia beads were placed in a 200 ml glass bottle and dispersed in a paint shaker manufactured by Red Devil Co., Ltd. for 6 hours.
-Pigment composition [3-2]: 19.0 parts-Styrene-acrylic acid copolymer (BASF Japan, John Krill 61J): 16.4 parts-Surfactant (Kao, Emargen 420): 5.0 parts ・ Ion-exchanged water: 59.6 parts Then, the zirconia beads were removed from the above dispersion liquid to obtain an aqueous coloring composition 1 for IJ.

(Preparation of water-based inkjet ink (hereinafter referred to as "water-based IJ ink") 1)
The following raw materials were stirred and mixed for 30 minutes using a high speed mixer to obtain a mixture.
-Aqueous coloring composition for IJ 1: 12.5 parts-Styrene-acrylic acid copolymer (manufactured by Gifu Cellac Mfg. Co., Ltd., Emmapoly-TYN-40, non-volatile content 44.8%): 2.5 parts-Surfactant (Made by Kao, Emargen 420): 2.0 parts, ion-exchanged water: 64.9 parts Next, diethylene glycol monobutyl ether was appropriately added to the above mixture, and the viscosity at 25 ° C. was 2.5 mPa · s (25 ° C.). The surface tension was adjusted to 40 mN / m, then filtered using a 1.0 μm polymer filter, and further filtered using a 0.45 μm polymer filter to obtain water-based IJ ink 1.

[Comparative Example H-1]
Aqueous coloring composition 2 for IJ, aqueous, in the same manner as in Example H-1, except that the pigment composition [3-2] used in Example H-1 was changed to the pigment composition [2-2]. IJ ink 2 was obtained.

(Evaluation method of viscosity stability)
The initial viscosity of each water-based IJ ink at 25 ° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosities after aging at 25 ° C. for 4 weeks and after aging at 50 ° C. for 4 weeks were measured. Using each measured value, the rate of increase in viscosity with respect to the initial viscosity was calculated and used as an index of viscosity stability.

It was confirmed that Example H-1 containing the pigment composition [3-2] has higher stability over time as compared with Comparative Example H-1 containing the pigment composition [2-2]. .. It is presumed that this is because the pigment composition [2-2] has a higher dispersibility than the pigment composition [3-2].

<7> Evaluation of water-based paint A water-based paint was prepared and evaluated as follows.

[Example I-1]
<Preparation of water-based coloring composition>
The following raw materials and 70 parts of 1.25 mm diameter zirconia beads were placed in a 70 ml glass bottle and dispersed over 60 minutes using a paint shaker manufactured by Red Devil to obtain a dispersion liquid.
-Pigment composition [3-2]: 3.15 parts-Polyester-modified acrylic acid polymer (ADDITOR XW 6528, manufactured by Allnex): 5.25 parts-Wetting agent (ADDITOR XW 6374, manufactured by Allnex): 0. 95 parts ・ Defoaming agent (ADDITOR XW 6211 manufactured by Allnex): 0.63 parts ・ Ion-exchanged water: 21.52 parts Next, the zirconia beads were removed from the above dispersion liquid to obtain an aqueous coloring composition 1. ..

<Preparation of water-based paint>
(1) Preparation of Water-based Paint 1-1 The following raw materials were stirred using a high-speed stirrer to obtain water-based paint 1-1 (stored at 25 ° C. for 1 week).
-Water-based coloring composition 1 (stored at 25 ° C for 1 week): 4.8 parts-Watersol S-751 (acrylic resin for baking paint manufactured by DIC): 60.0
Department ・ Cymel 303 (Melamine resin manufactured by Mitsui Cytec Co., Ltd.): 45.0 parts

(2) Preparation of Water-based Paint 1-2 The following raw materials were stirred using a high-speed stirrer to obtain water-based paint 1-2 (stored at 50 ° C. for 1 week).
-Water-based coloring composition 1 (stored at 50 ° C for 1 week): 4.8 parts-Watersol S-751 (acrylic resin for baking paint manufactured by DIC): 60.0
Department ・ Cymel 303 (Melamine resin manufactured by Mitsui Cytec Co., Ltd.): 45.0 parts

<Making PET film coating>
Preparation of PET film coating Water-based paint 1-1 and water-based paint 1-2 were coated on Lumirror 100T60 (polyester terephthalate (PET) film, 100 μm thickness) using a 6-mil applicator. After painting, the PET film was dried at room temperature for 18 hours. Then, it was dried at 60 ° C. for 5 minutes and at 140 ° C. for 20 minutes to obtain PET film coating 1-1 and PET film coating 1-2 having a film thickness of 70 μm.

[Comparative Example I-1]
Water-based coloring composition 2 and water-based paint 2 in the same manner as in Example I-1 except that the pigment composition [3-2] used in Example I-1 was changed to the pigment composition [2-2]. -1, water-based paint 2-2, PET film coating 2-1 and PET film coating 2-2 were obtained.

(Evaluation method of hue stability over time)
Using a colorimeter (manufactured by Konica Minolta, CM-700d), a pet film coated with a water-based coloring composition paint stored at 25 ° C. for 1 week and a water-based coloring composition paint stored at 50 ° C. for 1 week was applied. The color was measured and the color difference (ΔE *) was obtained. In this evaluation, it is considered that the smaller the color difference (ΔE *) is, the better the dispersion stability is.

Compared with Comparative Example I-1 containing the pigment composition [2-2], Example I-1 containing the pigment composition [3-2] had a smaller ΔE *. That is, the pigment composition [3-2] has higher dispersibility and higher hue stability over time.

<Ink set and its characteristic evaluation>
An ink set was prepared using the obtained pigment composition, and its characteristics were evaluated.

(Synthesis Example 3) Polyurethane resin solution [PU2] 54.719 parts of polyester diol having a number average molecular weight of 2,000, 3.989 parts of isophorone diisocyanate, n acetic acid obtained from adipic acid and 3-methyl-1,5-pentanediol. 10.0 parts of propyl was reacted at 85 ° C. for 3 hours under a nitrogen stream, and 10.0 parts of n-propyl acetate was added and cooled to obtain 78.718 parts of a solvent solution of the terminal isocyanate prepolymer. Next, a solvent solution 78 of the obtained terminal isocyanate prepolymer was mixed with 1.031 parts of isophorondiamine, 0.261 parts of di-n-butylamine, 30.4 parts of n-propyl acetate and 19.6 parts of isopropyl alcohol. .718 parts were gradually added at room temperature and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin solution [PU2] having a non-volatile content of 30%, a weight average molecular weight of 60,000 and an amine value of 3.0 mgKOH / g. ..

(Synthesis Example 4) Polyurethane resin solution [PU3] PPA (number average molecular weight 2,000) while introducing nitrogen gas in a reactor equipped with a reflux cooling tube, a dropping funnel, a gas introduction tube, a stirrer, and a thermometer. 161.9 parts of poly (propylene glycol) adipatediol), 27.7 parts of 2,2-dimethylolbutanoic acid (DMBA), 96.4 parts of isophorone diisocyanate (IPDI), and 200 parts of methyl ethyl ketone (MEK). The reaction was carried out at 90 ° C. for 5 hours to obtain a resin solution of a urethane prepolymer having a terminal isocyanate group. To the obtained terminal isocyanate group urethane prepolymer resin solution, 13.6 parts of 2- (2-aminoethylamino) ethanol (AEA), 0.5 part of ethanolamine (MEA), and 350 parts of isopropyl alcohol (IPA) were added. The mixture was added dropwise at room temperature over 60 minutes, and further reacted at 70 ° C. for 3 hours. Further, the non-volatile content is adjusted using 150 parts of MEK, and a polyurethane resin having a non-volatile content of 30%, a weight average molecular weight of 35,000, Mw / Mn = 3.0, an acid value of 35.0 mgKOH / g, and a hydroxyl value of 25.7 mgKOH / g. A solution [PU3] was obtained.

[Manufacturing of gravure printing ink] (Example JC-1) 7,000 parts of pigment composition [1-1], 34.5 parts of polyurethane resin solution [PU2], 20 parts of N-propyl acetate, 5 parts of isopropyl alcohol. After stirring and mixing and kneading with a sand mill, 20 parts of a polyurethane resin solution [PU2], 11 parts of N-propyl acetate and 3 parts of isopropyl alcohol were added to obtain a cyan ink [JC-1].

(Examples JC-2 to JC-33, Production Examples JC-1 to JY-3, JY-1 to JY-6, JM-1 to JM-10) 7,000 parts of the pigment composition [1-1] , The inks shown in Table 12 were obtained in the same manner as in Example JC-1 except that the pigments shown in Table 12 and the amounts shown in Table 12 were changed.

Table 13 shows the pigments used in the production of the ink.

<Evaluation of viscosity stability of ink over time>
Put each of cyan ink [JC-1] to [JC-36], yellow ink [JY-1] to [JY-6], and magenta ink [JM-1] to [JM-10] in a closed container, and 40 It was stored at ° C for 14 days. Then, the viscosity was measured and evaluated by comparing the change in viscosity with that before storage. The viscosity was measured at 25 ° C. It was performed in 4 outflow seconds. The viscosity of each ink in the B-type viscometer before storage was in the range of 40 to 500 cps (25 ° C.). The results are shown in Table 15-1 and Table 15-2.
(Evaluation criteria)
◯: Viscosity change is less than 2 seconds (good)
Δ: Viscosity change is 2 seconds or more and less than 5 seconds (practical)
×: Viscosity change is 5 seconds or more (defective)

<Evaluation of Ink Set> (Examples JS-1 to JS-92, Comparative Examples JS-1 to JS-17) The obtained inks were combined as shown in Table 14 to form ink sets 1 to 109. ..
The obtained ink set was evaluated for trapping property and gamut by the following method. The results are shown in Table 15-1 and Table 15-2.

[Trapping property] (cyan ink / yellow ink)
Cyan ink and yellow ink were each diluted with a mixed solvent 1 (methyl ethyl ketone: N-propyl acetate: isopropanol = 40: 40: 20) so as to have a viscosity of 16 seconds (25 ° C., Zahn cup No. 3). ..
A printed matter was obtained by overlay printing in the order of cyan and yellow on the corona discharge treated surface of a corona discharge treated polyester film (E-5100 manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm (initial evaluation of trapping property).
The printing conditions were a temperature of 25 ° C., a humidity of 60%, a printing speed of 100 m / min, and a printing distance of 4000 m. Cyan ink uses Helio 175-line gradation version (plate type compressed, 75% solid pattern and 100% to 3% gradation pattern), and yellow ink uses Helio 175-line gradation version (plate type Elongate, 75% solid pattern and 100% to 100%). 3% gradation pattern) was used.
Further, cyan ink and yellow ink were each placed in a closed container and stored at 40 ° C. for 14 days, then diluted and printed in the same manner as described above to obtain a printed matter (evaluation of trapping property over time).

(Cyan ink / Magenta ink)
Cyan ink and magenta ink were each diluted with the above-mentioned mixed solvent 1 so as to have a viscosity of 16 seconds (25 ° C., Zahn cup No. 3).
A printed matter was obtained by overlay printing in the order of cyan and magenta on the corona discharge treated surface of a corona discharge treated polyester film (E-5100 manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm (initial evaluation of trapping property).
The printing conditions were a temperature of 25 ° C., a humidity of 60%, a printing speed of 100 m / min, and a printing distance of 4000 m. Cyan ink uses Helio 175-line gradation version (plate type compressed, 75% solid pattern and 100% to 3% gradation pattern), and magenta ink uses Helio 175-line gradation version (plate type Elongate, 75% solid pattern and 100% to 100%). 3% gradation pattern) was used.
Further, cyan ink and magenta ink were each placed in a closed container and stored at 40 ° C. for 14 days, then diluted and printed in the same manner as described above to obtain a printed matter (evaluation of trapping property over time).

The trapping property of the obtained gradation overprinted portion of the printed matter was observed using a microscope (VHX-5000) manufactured by KEYENCE, and evaluated according to the following criteria.
◯: Printing unevenness occurs at a plate depth of less than 70% (good)
Δ: Printing unevenness occurs when the plate depth is 70% or more and less than 80% (usable).
X: Printing unevenness occurs at a plate depth of 80% or more, or all the overlapping inks become halftone dots and do not spread wet (cannot be used).

[Gamut evaluation] (Initial evaluation)
Cyan ink, magenta ink, and yellow ink were diluted with the above-mentioned mixed solvent 1 so as to have a viscosity of 16 seconds (25 ° C., Zahn cup No. 3). Using each diluted ink, print in the order of cyan, magenta, and yellow printing, and print the single-color solid part (cyan, magenta, yellow) and the single-color solid printing layer (cyan x magenta, cyan x yellow, yellow x magenta). A printed matter having was obtained. The printing conditions are shown below.

(Printing conditions)
Printing machine: Fuji Machinery 5-color machine Cyan version: Helio 175L / inch, stylus angle 120 °, Elongate magenta version: Helio 175L / inch, stylus angle 120 °, compressed yellow version: Helio 175L / inch, stylus angle 120 °, Compressed printing speed: 150 m / min Substrate: Corona-treated biaxially stretched polypropylene (OPP) film (Pyrene P-2161, 20 μm manufactured by Toyo Spinning Co., Ltd.)
Drying temperature: 50 ° C

With respect to the obtained printed matter, the density value of the monochromatic solid portion (yellow, magenta, cyan) of the printed matter was measured using Gretag Macbeth D196. In addition, using a SpectroEye manufactured by gretagmacbeth as a measuring device, the monochromatic solid part and the overprinting part were measured under the conditions of a D50 light source, a two-degree observation field of view, a white background (using a standard white plate), and no filters.
In a two-dimensional space with a * as the horizontal axis and b * as the vertical axis, a single-color solid part (yellow, magenta, cyan) and a single-color solid overprint part (cyan x magenta, cyan x yellow, yellow x magenta) total A hexagon was created by plotting the values of a * vs. b * of 6 colors, and the area was calculated. The area ratio in each Example / Comparative Example was divided by the area in the reference Comparative Example JS-2, and the area ratio was evaluated according to the following criteria. -Indicates that it has not been evaluated.
(Evaluation criteria)
◯: Area ratio is 90% or more (good)
Δ: Area ratio is 85% or more and less than 90% (usable)
X: Area ratio is less than 85% (cannot be used)

(Evaluation over time)
Cyan ink, magenta ink, and yellow ink were each placed in a closed container and stored at 40 ° C. for 14 days, then diluted and printed in the same manner as in the initial evaluation to obtain a printed matter.

The color of the obtained printed matter was measured in the same manner as in the above initial evaluation.
In a two-dimensional space with a * as the horizontal axis and b * as the vertical axis, a single-color solid part (yellow, magenta, cyan) and a single-color solid overprint part (cyan x magenta, cyan x yellow, yellow x magenta) total A hexagon was created by plotting the values of a * vs. b * in six colors. The area ratio of each Example / Comparative Example in the time-dependent evaluation was divided by the area of the initial evaluation, and the area ratio was evaluated according to the following criteria. -Indicates that it has not been evaluated.
(Evaluation criteria)
◯: Area ratio is 98% or more (good)
Δ: Area ratio is 95% or more and less than 98% (practical)
X: Area ratio is less than 95% (defective)

According to Tables 15-1 and 15-2, the gravure printing ink set of the present invention has a gamut ratio equal to or higher than that of the conventional ink set, and has good color reproducibility. rice field. In addition, the viscosity stability of the cyan ink over time was improved, and the storage stability of the cyan ink as an ink set was good. Further, the trapping property and the color reproducibility (gamut) of each color were also evaluated well over time, and the storage stability as an ink set was also good.

On the other hand, Comparative Example JS-1 is unsuitable due to deterioration of hue, and Comparative Examples JS-2 to JS-17 have poor viscosity stability with time of cyan ink, and the trapping property and color reproducibility (Gamat) of each color are also poor. Since the evaluation over time was poor, the storage stability of the ink set was poor, and the problem of the present application could not be solved.

<Manufacturing of clear ink> (Preparation of clear ink [1]) 87 parts of polyurethane resin solution [PU3] (nonvolatile content 30%), 5 parts of ethyl acetate (EA), 5 parts of IPA, silica ("P-" manufactured by Mizusawa Chemical Co., Ltd. 73 ”, hydrophilic silica particles having an average particle diameter of 3.8 μm) were stirred and mixed using a disper to obtain a clear ink [1].

<Manufacturing of Detachable Adhesive> (Preparation of Laminated Adhesive Solution [1]) In a four-mouth separable flask, 82 parts of terephthalic acid, 682 parts of isophthalic acid, 236 parts of adipic acid, 236 parts of ethylene glycol, 525 parts of neopentyl glycol and 405 parts of 1,6-hexanediol were charged, and an esterification reaction was carried out at 220 to 260 ° C. After distilling a predetermined amount of water, the pressure was gradually reduced to 1 mmHg or less, and a deglycolation reaction was carried out at 240 to 260 ° C. for 5 hours. Then, 2 parts of isophorone diisocyanate was gradually added, and the reaction was carried out at 150 ° C. for about 2 hours to obtain a polyester polyurethane polyol. To 100 parts of this polyester polyurethane polyol, 2.83 parts of trimellitic anhydride was added, and the mixture was reacted at 180 ° C. for about 2 hours. Then, it was diluted with ethyl acetate to a non-volatile content of 50% to obtain a partially acid-modified polyester polyol solution having a number average molecular weight of 6,000 and an acid value of 16.5 mgKOH / g.
100 parts of the obtained polyol solution and 7.94 parts of HDI Biuret's non-volatile content 95% ethyl acetate solution were mixed, and ethyl acetate was added to obtain a laminated adhesive solution [1] having a non-volatile content of 30%.

<Manufacturing of Packaging Material> (Example JP-1) Packaging Material 1 Cyan ink [JC-1], magenta ink [JM-1], and yellow ink [JY-1] are mixed with the above-mentioned mixed solvent 1 to have a viscosity of 16. It was diluted to the second (25 ° C., Zahn cup No. 3).
Using each diluted ink, a gravure calibration 5-color machine equipped with a gravure plate with a plate depth of 20 μm, black ink (Rio Alpha R92 ink (manufactured by Toyo Ink Co., Ltd.)), cyan ink [JC-1], magenta ink [ A corona-treated stretched polypropylene film (OPP substrate) having a thickness of 20 μm using an ink set 201 containing JM-1], yellow ink [JY-1], and white ink (Rioalpha R631 white (manufactured by Toyo Ink Co., Ltd.)). On the other hand, black ink, cyan ink [JC-1], magenta ink [JM-1], yellow ink [JY-1], and white ink are overprinted in this order, and each unit is dried at 50 ° C. , A printed matter having the composition of "OPP base material / black, cyan, magenta, yellow or white print layer" was obtained.
Next, a urethane-based laminated adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd., a non-volatile content 30% ethyl acetate solution) was applied onto the printed layer of the obtained printed matter so that the coating amount after drying was 2.0 g / m ² . After being coated and dried, an unstretched polyethylene (PE) film having a thickness of 50 μm is laminated on the adhesive layer to form an “OPP base material / 5-color layered printing layer / adhesive layer / PE base material”. Obtained a packaging material 1.

(Examples JP-2 to JP-92) Packaging materials 2-92 Example JP except that the ink set 201 used in Example JP-1 was changed to the ink set shown in Table 16-1 and Table 16-2. In the same manner as in No. 1, packaging materials 2-92 having a desorbing layer were obtained.

(Example JP-101) Packaging material 101 The above-mentioned clear ink [1] is prepared to have a viscosity of 15 seconds (25 ° C., Zahn cup No. 3) by using an EA / IPA mixed solvent (mass ratio 70/30). Diluted to.
Cyan ink [JC-1], magenta ink [JM-1], and yellow ink [JY-1] are diluted with the above-mentioned mixed solvent 1 so that the viscosity becomes 16 seconds (25 ° C., Zahn cup No. 3). did.
Using each diluted ink, a gravure calibration five-color machine equipped with a gravure plate with a plate depth of 20 μm, clear ink [1], cyan ink [JC-1], magenta ink [JM-1], and yellow ink [ Using an ink set 301 containing [JY-1], clear ink [1], cyan ink [JC-1], magenta ink [JM-1], and yellow ink were applied to a corona-treated stretched polypropylene film having a thickness of 20 μm. Overprinting is performed in the order of [JY-1], and each unit is dried at 50 ° C. to form an "OPP substrate / desorption layer (clear ink) / cyan, magenta or yellow printing layer". , A printed matter containing a layer having desorption property was obtained.
Next, a laminate adhesive solution [1] was applied onto the printed layer of the obtained printed matter using a dry laminating machine, and an aluminum-deposited unstretched polypropylene (VMCPP) film having a thickness of 25 μm at a line speed of 40 m / min. A packaging material 101 having a detachable layer, which is composed of an OPP substrate / a print layer having a detachable property / a three-color laminated printing layer / an adhesive layer having a detachable property / a VMCPP substrate. Obtained.

(Examples JP-102 to JP-192) Packaging materials 102 to 192 Example JP except that the ink set 301 used in Example JP-101 was changed to the ink set shown in Table 17-1 and Table 17-2. In the same manner as in −101, packaging materials 102 to 192 having a desorbing layer were obtained.

By using the gravure printing ink set of the present invention, a packaging material could be produced.

<Manufacturing of water-based inkjet ink> (Example KC-1)
(Preparation of Aqueous Coloring Composition for Inkjet (hereinafter referred to as "Aqueous Coloring Composition for IJ") [KC-1])
The following materials and 200 parts of 1.25 mm diameter zirconia beads were placed in a 200 ml glass bottle and dispersed in a paint shaker manufactured by Red Devil for 6 hours.
-Pigment composition [1-1]: 19.000 parts-Styrene-acrylic acid copolymer (BASF Japan, John Krill 61J): 16.4 parts-Surfactant (Kao, Emargen 420): 5.0 parts-Ion-exchanged water: 59.6 parts Then, the zirconia beads were removed from the above dispersion to obtain an aqueous coloring composition for IJ [KC-1].

(Preparation of water-based inkjet ink (hereinafter referred to as "water-based IJ ink") [KC-1])
33 parts of aqueous coloring composition for IJ [KC-1], 5 parts of butyl diglycol, 15 parts of 1,2-propanediol, 8.8 parts of Joncryl HPD96 (water-soluble resin manufactured by BASF Japan), 1.25 parts of Chemipearl W400S (manufactured by Mitsui Chemicals, water-based dispersion of reolefin), 0.5 parts of Surfactant DF110D (manufactured by Nissin Chemical Industries, antifoaming agent), BYK-348 (manufactured by Big Chemy Japan) , Silicon-based surfactant) (1 part), triethanolamine (0.1 part), Proxel GXL (manufactured by London, preservative) (0.15 part), ion-exchanged water (35.2 parts) mixed with a high-speed mixer. Filtration was performed with a 0.5 μm membrane filter to obtain an aqueous IJ ink [KC-1].

(Examples KC-2 to KC-35, Production Examples KC-1 to KC-3, KY-1 to KY-5, KM-1 to KM-6)
(Aqueous Coloring Compositions for IJ [KC-2]-[KC-38], [KY-1]-[KY-5], [KM-1]-[KM-6], and Aqueous IJ Inks [KC-] 2]-[KC-38], [KY-1]-[KY-5], [KM-1]-[KM-6] preparation)
Table 18 shows the same as Example KC-1 except that 19.000 parts of the pigment composition [1-1] of Example KC-1 was changed to the pigments shown in Table 18 and the amounts shown in Table 18. Aqueous coloring compositions for IJ [KC-2]-[KC-38], [KY-1]-[KY-5], [KM-1]-[KM-6], and aqueous IJ inks [[KC-]. 2] to [KC-38], [KY-1] to [KY-5], and [KM-1] to [KM-6] were obtained.

Table 19 shows the pigments used in the production of the ink.

<Evaluation of viscosity stability of ink over time>
Water-based IJ inks [KC-1] to [KC-38], [KY-1] to [KY-5], [KM-1] to [KM-6] E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) The initial viscosity at 25 ° C. was measured using an ELD type viscometer "). Similarly, the viscosities after aging at 25 ° C. for 4 weeks and after aging at 50 ° C. for 4 weeks were measured. Using each measured value, the rate of increase in viscosity with respect to the initial viscosity was calculated, used as an index of viscosity stability, and evaluated according to the following criteria. The results are shown in Table 21-1 and Table 21-2. It is considered that the smaller the viscosity increase rate is, the better the viscosity stability is, and if it is "4", "3" and "2" in the following evaluation criteria, it is a practical level.

(Evaluation criteria for viscosity stability)
4: Viscosity increase rate is less than 15%.
3: The viscosity increase rate is 15% or more and less than 25%.
2: The viscosity increase rate is 25% or more and less than 40%.
1: The viscosity increase rate is 40% or more.

<Evaluation of Ink Set> [Examples KS-1 to KS-62, Comparative Examples KS-1 to KS-12] The obtained water-based IJ inks are combined as shown in Table 20, and the ink sets 401 to 474 are combined. And said.
Gamut was evaluated for the obtained ink set by the following method. The results are shown in Table 21-1 and Table 21-2.

[Gamut evaluation] (Initial evaluation)
With a line-pass type inkjet printer using an inkjet head (Kyocera's "KJ4B series") with a width resolution of 600 dpi and a maximum ejection frequency of 30 kHz, yellow ink, magenta ink, and cyan ink of each ink set are used. Fill the head and put it on coated paper (OK top coat N manufactured by Oji Paper Co., Ltd., basis weight 104.7 g / m ² ) with a resolution of 600 x 600 dpi, and a color chart image (Chart image for printer made by X-rite "TC3". .5 CMYK i1_i0 ") was printed to prepare a printed matter for evaluation.

The color chart portion of the obtained evaluation printed matter was color-measured using a spectrophotometer (X-Rite i1 i0 Pro) and a color measurement tool (X-Rite Mechanism Tool and profilemaker), and L * a * b * The color reproduction area in the color space was plotted. The measurement conditions were light source D50, 2 degree visual field, and measurement optics 45/0 °. The area was calculated from each of the obtained plots. The area ratio in each Example / Comparative Example was divided by the area in the reference Comparative Example KS-2, and the area ratio was evaluated according to the following criteria.
(Evaluation criteria)
◯: Area ratio is 90% or more (good)
Δ: Area ratio is 85% or more and less than 90% (usable)
X: Area ratio is less than 85% (cannot be used)

(Evaluation over time)
Each water-based IJ ink was placed in a closed container, stored at 50 ° C. for 4 weeks, and then printed in the same manner as in the initial evaluation to prepare a printed matter for evaluation. The color of the obtained printed matter was measured in the same manner as in the initial evaluation, and the area was obtained from each of the obtained plots. The area ratio of each Example / Comparative Example in the time-dependent evaluation was divided by the area of the initial evaluation, and the area ratio was evaluated according to the following criteria.
(Evaluation criteria)
◯: Area ratio is 98% or more (good)
Δ: Area ratio is 95% or more and less than 98% (practical)
X: Area ratio is less than 95% (defective)

According to Tables 21-1 and 21-2, the water-based IJ ink set of the present invention has a gamut ratio equal to or higher than that of the conventional ink set, and has good color reproducibility. rice field. In addition, the viscosity stability of the cyan ink over time was improved, and the storage stability of the cyan ink as an ink set was good. Further, in terms of color reproducibility (Gamut), the evaluation over time was good, and the storage stability as an ink set was good.

On the other hand, Comparative Example KS-1 is unsuitable due to deterioration of hue, and Comparative Examples KS-2 to KS-12 have poor viscosity stability over time of cyan ink, and evaluation over time is also poor in color reproducibility (Gamat). Therefore, the storage stability as an ink set is poor, and the problem of the present application cannot be solved.

Claims (14)

A pigment composition containing 10 to 5000 ppm of the compound (1) represented by the following formula (1) and a divalent metal.
Equation (1)

The pigment composition according to claim 1, wherein the divalent metal is one or more of copper and calcium. The pigment composition according to claim 2, wherein the copper is derived from copper phthalocyanine. A coloring composition comprising the pigment composition and the dispersion medium according to any one of claims 1 to 3. A molding composition comprising the coloring composition according to claim 4. A toner comprising the coloring composition according to claim 4. A coating material comprising the coloring composition according to claim 4. An ink containing the coloring composition according to claim 4. An ink set containing at least yellow ink, cyan ink, and magenta ink.
An ink set in which the cyan ink is an ink containing the coloring composition according to claim 4. A gravure printing ink set containing at least yellow ink, cyan ink, and magenta ink.
A gravure printing ink set in which the cyan ink is an ink containing the coloring composition according to claim 4. The gravure printing ink set according to claim 10, further comprising a clear ink. A printed matter comprising a substrate and a printed layer formed from the gravure printing ink set of claim 10. A printed matter comprising a substrate, a printing layer formed from yellow ink, cyan ink, and magenta ink in the gravure printing ink set according to claim 11, and a desorption layer formed from clear ink. A packaging material comprising the printed matter according to claim 12 or 13.