Carbon black composition, colorant, ink, and method for producing carbon black composition

Abstract

To provide a carbon black composition, a colorant, an ink, and a method for producing a carbon black composition that exhibit favorable storage stability and resistance to retorting.SOLUTION: The carbon black composition contains carbon black and a copper phthalocyanine sulfonic acid derivative, the copper phthalocyanine sulfonic acid derivative including a compound expressed by general formula (1), the compound expressed by general formula (1) being such that the molar ratio (SN2 / SN1) of compound (SN2) with n=2 to compound (SN1) with n=1 is less than 0.40. In general formula (1), M denotes a cation species, and n denotes 1 or 2.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a carbon black composition, a colorant, an ink, and a method for producing the carbon black composition. [Background technology]

[0002] Carbon black has traditionally been used as a colorant to impart a black color to ink. For example, Patent Document 1 discloses a method for producing surface-treated carbon black, which comprises pre-pulverizing carbon black (a) in water with a dispersant (c) and then oxidizing the carbon black in liquid phase with a hypochlorite solution (b). This production method is disclosed to produce a dispersion with little precipitation and high yield, and to produce carbon black that has good long-term storage stability. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-84597 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when carbon black produced by the production method described in Patent Document 1 is used in ink, there is room for improvement in the storage stability and retort resistance of the ink.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a carbon black composition, a colorant, an ink, and a method for producing a carbon black composition that have good storage stability and retort resistance. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] A coating composition comprising carbon black and a copper phthalocyanine sulfonic acid derivative, The copper phthalocyanine sulfonic acid derivative contains a compound represented by the following general formula (1): A carbon black composition, wherein, in the compound represented by the general formula (1), the molar ratio (SN2 / SN1) of a compound (SN1) where n=1 to a compound (SN2) where n=2 is less than 0.40.

[0007] [ka] [In general formula (1), M represents a cation species, and n represents 1 or 2.] [2] The carbon black composition according to [1], wherein the content of the copper phthalocyanine sulfonic acid derivative is 0.01 to 2.0 parts by mass per 100 parts by mass of the carbon black. [3] The carbon black composition according to [1] or [2], wherein the carbon black is surface-treated with elemental iron.

[0008] [4] A colorant containing the carbon black composition according to any one of [1] to [3]. [5] An ink containing the carbon black composition according to any one of [1] to [3].

[0009] [6] A method for producing the carbon black composition according to any one of [1] to [3], comprising the steps of: A method for producing a carbon black composition, comprising a mixing step of mixing carbon black with a copper phthalocyanine sulfonic acid derivative. [7] The method for producing a carbon black composition according to [6], wherein water is further mixed in the mixing step. [8] A preparation step of preparing a dried carbon black and a dried copper phthalocyanine sulfonic acid derivative before the mixing step, [6] The method for producing a carbon black composition according to [6], wherein the mixing step is carried out by mixing the dried carbon black with the dried copper phthalocyanine sulfonic acid derivative. [9] a slurrying step, prior to the mixing step, of mixing a basic compound and water with the carbon black and the copper phthalocyanine sulfonic acid derivative, respectively, to obtain a slurry of the carbon black and a slurry of the copper phthalocyanine sulfonic acid derivative; [6] The method for producing a carbon black composition according to [6], wherein the mixing step is carried out by mixing a slurry of the carbon black with a slurry of the copper phthalocyanine sulfonic acid derivative. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a carbon black composition, a colorant, an ink, and a method for producing a carbon black composition that have good storage stability and retort resistance. DETAILED DESCRIPTION OF THE INVENTION

[0011] (Carbon Black Composition) The carbon black composition of the present embodiment contains carbon black and a copper phthalocyanine sulfonic acid derivative.

[0012] <Carbon black> The carbon black may be any carbon black used as a pigment, produced by a known method such as a contact method, a furnace method, or a thermal method. Commercially available carbon black products include the #2600 series, #2300 series, #1000 series, #900 series, and MA series manufactured by Mitsubishi Chemical Corporation, the COLOR-BLACK series, SPECIAL-BLACK series, PRINTEX series, HIBLACK series, NEROX series, and NIPex series manufactured by Orion Engineered Carbons, the SUNBLACK series, #70 series, and #80 series manufactured by Asahi Carbon Co., Ltd., and the TOKABLACK #7000 series and #8000 series manufactured by Tokai Carbon Co., Ltd.

[0013] The carbon black is preferably surface-treated. Examples of the surface treatment include oxidation treatment. Examples of the oxidation treatment include the Fenton reaction.

[0014] The carbon black is preferably carbon black that has been surface-treated with iron elements.

[0015] The carbon black may be used alone or in combination of two or more kinds. The carbon black content is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the total amount of the carbon black composition of this embodiment. The carbon black content is preferably 99.9 mass % or less based on the total amount of the carbon black composition of this embodiment.

[0016] When the carbon black content is equal to or greater than the above-mentioned preferable lower limit, the retort resistance is further improved. When the carbon black content is equal to or less than the above-mentioned preferable upper limit, the storage stability is further improved.

[0017] For example, the carbon black content is preferably 90% by mass or more and 99.9% by mass or less, more preferably 95% by mass or more and 99.9% by mass or less, and even more preferably 98% by mass or more and 99.9% by mass or less, based on the total amount of the carbon black composition of this embodiment.

[0018] <Copper phthalocyanine sulfonic acid derivatives> Copper phthalocyanine sulfonic acid derivatives can be obtained, for example, by sulfonating a copper phthalocyanine pigment with concentrated sulfuric acid or fuming sulfuric acid, or by sulfochlorinating a copper phthalocyanine pigment with chlorosulfonic acid and then hydrolyzing it with water. Examples of copper phthalocyanine pigments include copper phthalocyanine crude (β-type) obtained by a known method such as heating and reacting phthalodinitrile with cuprous chloride in the presence of a catalyst (phthalodinitrile method), which is then pulverized by dry grinding and then converted into β-type crystals by solvent pigmentation, and β-type copper phthalocyanine obtained by subjecting copper phthalocyanine crude to a heating and grinding treatment (kneader grinding) using inorganic salt crystals together with a solvent. Commercially available copper phthalocyanine pigments may be used.

[0019] The copper phthalocyanine sulfonic acid derivatives include compounds represented by the following general formula (1): In the compound represented by the general formula (1), the molar ratio (SN2 / SN1) of the compound (SN1) where n=1 to the compound (SN2) where n=2 is less than 0.40.

[0020] [ka] [In general formula (1), M represents a cation species, and n represents 1 or 2.]

[0021] In the general formula (1), M represents a cationic species. The cationic species are hydrogen ions (H + ), alkali metal ions (Li + , Na + , K. + ), alkaline earth metal ions (Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ ), aluminum ions (Al 3+ ) etc. Here, when the cationic species is a polyvalent ion, the bonding state is not clear, but it is presumed that the polyvalent ion is bonded to copper phthalocyanine in the same manner as the S atom in the general formula (1), or to another anion. Specifically, the other anion is a hydroxide ion (HO - ), sulfate ions (SO4 2- ), hydrogen sulfate ion (SO3(OH) - ), halide ions (F- , Cl - , Br - , I - ), copper phthalocyanine cyanine sulfonate ion (a copper phthalocyanine cyanine sulfonate ion different from the copper phthalocyanine having an S atom bonded thereto in general formula (1)), and the like. Therefore, when M in the general formula (1) is an alkaline earth metal ion (Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ ), aluminum ions (Al 3+ ), etc., simply M is an alkaline earth metal ion (Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ ), aluminum ions (Al 3+ ) but also includes cationic species in which the alkaline earth metal ion, aluminum ion, etc. is bonded to the other anions described above.

[0022] A compound represented by general formula (1) in which M is a polyvalent ion can be obtained, for example, by reacting copper phthalocyanine sulfonic acid in which M in general formula (1) is a hydrogen ion with a metal salt such as an alkaline earth metal salt or an aluminum salt. Therefore, when M is a polyvalent ion, M in general formula (1) can also be considered to be a cation species derived from the metal salt used as a raw material. For example, M can also be considered to be a cation species derived from an alkaline earth metal salt (e.g., magnesium sulfate, magnesium chloride, calcium sulfate, calcium chloride) or an aluminum salt (e.g., aluminum sulfate, aluminum chloride).

[0023] In the general formula (1), M is preferably a hydrogen ion, a sodium ion, or an aluminum ion from the viewpoint of further improving storage stability.

[0024] In the general formula (1), n represents 1 or 2. In the compound represented by the general formula (1), the molar ratio (SN2 / SN1) of the compound (SN1) where n = 1 and the compound (SN2) where n = 2 is less than 0.40, preferably 0.01 or more and less than 0.40, more preferably 0.01 or more and 0.35 or less, still more preferably 0.1 or more and 0.25 or less, and particularly preferably 0.1 or more and 0.15 or less. When SN2 / SN1 is less than 0.40, the storage stability and retort resistance of the carbon black composition are good. When SN2 / SN1 is within the above preferred range, the storage stability and retort resistance are further improved.

[0025] In this specification, SN2 / SN1 can be calculated as follows. Weigh 25 mg of the copper phthalocyanine sulfonic acid derivative into a 100 mL volumetric flask and make up to 100 mL with dimethyl sulfoxide (DMSO, manufactured by Kanto Chemical Co., Inc.). Disperse this in an ultrasonic disperser for 30 minutes, shake it by hand for 1 minute, and then filter it through an HPLC disk (manufactured by Sampratech Co., Ltd., Ekclo Disk 13CR, material: PTFE, pore size: 0.45 μm). Then, perform HPLC analysis of the obtained sample under the following conditions. <HPLC analysis conditions> Instrument name: High-performance liquid chromatogram EXTREMA (manufactured by JASCO Corporation) Column: SHISEIDO CAPCELL PAK C 18 UG 120, C18, 3 μm, 4.6×100 mm Column temperature: 50 °C Mobile phase A / B: Acetonitrile / 1 vol% aqueous solution of dibutylammonium acetate Gradient: Acetonitrile 30% → 17 minutes → 90% (held for 3 minutes) Mobile phase flow rate: 0.4 mL / min Sample injection volume: 1 μL Measurement wavelength: 668 nm The copper phthalocyanine sulfonic acid compound with n = 2 corresponds to the peak with a retention time of 5 to 12 minutes, and the copper phthalocyanine sulfonic acid compound with n = 1 corresponds to the peak with a retention time of 12 to 19 minutes. The area of each peak group is calculated, and SN2 / SN1 can be determined.

[0026] The copper phthalocyanine sulfonic acid derivatives may be used alone or in combination of two or more. The content of the copper phthalocyanine sulfonic acid derivative is preferably 0.01 parts by mass or more, and more preferably 0.2 parts by mass or more, relative to 100 parts by mass of carbon black. The content of the copper phthalocyanine sulfonic acid derivative is preferably 2 parts by mass or less, and more preferably 1.7 parts by mass or less, per 100 parts by mass of carbon black.

[0027] When the content of the copper phthalocyanine sulfonic acid derivative is equal to or greater than the above-mentioned preferable lower limit, the storage stability is further improved. When the content of the copper phthalocyanine sulfonic acid derivative is equal to or less than the above-mentioned preferable upper limit, the retort resistance is further improved.

[0028] For example, the content of the copper phthalocyanine sulfonic acid derivative is preferably 0.01 parts by mass or more and 2 parts by mass or less, and more preferably 0.2 parts by mass or more and 1.7 parts by mass or less, relative to 100 parts by mass of carbon black.

[0029] The content of the copper phthalocyanine sulfonic acid derivative is preferably 0.01% by mass or more, and more preferably 0.2% by mass or more, based on the total amount of the carbon black composition of this embodiment. The content of the copper phthalocyanine sulfonic acid derivative is preferably 2% by mass or less, and more preferably 1.7% by mass or less, based on the total amount of the carbon black composition of this embodiment.

[0030] When the content of the copper phthalocyanine sulfonic acid derivative is equal to or greater than the above-mentioned preferable lower limit, the storage stability is further improved. When the content of the copper phthalocyanine sulfonic acid derivative is equal to or less than the above-mentioned preferable upper limit, the retort resistance is further improved.

[0031] For example, the content of the copper phthalocyanine sulfonic acid derivative is preferably 0.01% by mass or more and 2% by mass or less, and more preferably 0.2% by mass or more and 1.7% by mass or less, relative to the total amount of the carbon black composition of this embodiment.

[0032] The content of the compound represented by the general formula (1) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, of the total amount of the copper phthalocyanine sulfonic acid derivative. The carbon black composition of this embodiment may contain only the compound represented by the general formula (1) as the copper phthalocyanine sulfonic acid derivative.

[0033] <Optional ingredients> The carbon black composition of this embodiment may contain optional components. Optional components include surfactants, resins, rosins, organic pigment derivatives, inorganic pigments, and the like. Examples of the surfactant include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Examples of the resin include polyester resin, polyamide resin, styrene resin (PS resin, AS resin, ABS resin, etc.), acrylic resin, polyolefin resin (polyethylene resin, polyester resin, etc.), polyalkylene terephthalate resin (polyethylene terephthalate resin, polybutylene terephthalate resin, etc.), polyvinyl chloride resin, methylpentene resin, polycarbonate resin, polyurethane resin, polyacetal resin, fluororesin (PTFE resin, etc.), polyethersulfone resin, polyphenylene sulfide resin, polyetheretherketone resin, etc. Examples of the organic pigment derivatives include sulfonic acid organic pigment derivatives, amino group-containing organic pigment derivatives, and phthalimidomethyl group-containing organic pigment derivatives, each of which has a main skeleton such as a phthalocyanine pigment, a quinacridone pigment, a dioxazine pigment, a diketopyrrolopyrrole pigment, a quinophthalone pigment, a perylene pigment, or an azo pigment. Examples of the inorganic pigment include calcium carbonate, magnesium carbonate, precipitated barium sulfate, kaolin, clay, alumina white, and white carbon.

[0034] [Iron element content] The carbon black composition of this embodiment preferably contains elemental iron, for example, elemental iron derived from carbon black that has been surface-treated with elemental iron. The content of iron element is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, based on the total amount of the carbon black composition of this embodiment. The iron content is preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.2% by mass or less, based on the total amount of the carbon black composition of this embodiment. For example, the iron content is preferably from 0.01% by mass to 2% by mass, more preferably from 0.1% by mass to 1.5% by mass, and even more preferably from 0.3% by mass to 1.2% by mass, relative to the total amount of the carbon black composition of this embodiment. The iron element is not limited to simple iron (Fe), but may be in the form of an iron compound such as iron oxide (FeO, Fe2O3, etc.) or iron hydroxide (Fe(OH)2, Fe(OH)3, etc.).

[0035] If the iron content is within the above preferred range, the storage stability is further improved.

[0036] In this specification, the iron element content in the carbon black composition can be measured using an energy dispersive X-ray fluorescence analyzer PANalytical Epsilon5 (manufactured by Spectris).

[0037] The carbon black composition of this embodiment preferably contains a copper phthalocyanine sulfonic acid derivative-coated carbon black. The copper phthalocyanine sulfonic acid derivative-coated carbon black can be produced by acid precipitation mixing, which will be described later.

[0038] <Application> The carbon black composition of this embodiment has good storage stability and retort resistance, and is therefore useful as a colorant or ink. As the ink, gravure ink, flexographic ink, UV ink, offset ink, and inkjet ink are preferred, and gravure ink is more preferred. As the gravure ink, polyurethane ink, polyamide / nitrocellulose ink, and acrylic ink are preferred, and polyurethane ink is more preferred. In polyurethane inks, polyurethane resins may be used in combination with chlorinated polyolefins. Specific examples of polyurethane inks include polyurethane inks containing a polyurethane resin, carbon black, and the copper phthalocyanine sulfonic acid derivative represented by the above-mentioned general formula (1). Examples of the polyurethane resin include Sanprene IB-501 (manufactured by Sanyo Chemical Industries, Ltd.).

[0039] A polyurethane ink according to one embodiment contains a polyurethane resin, carbon black, and a copper phthalocyanine sulfonic acid derivative represented by the general formula (1), 50 g of the polyurethane ink is transferred to a glass bottle (tableware bottle M-70, manufactured by Kashiwa Glass Co., Ltd.) and left to stand at 50°C for 7 days in a multi-safety dryer MSO-45TPH (manufactured by Futaba Chemical Co., Ltd.). The black precipitate that forms at the bottom of the glass bottle is scooped up with a spoon (Sandaia spoon, stainless steel, 40 spoons, manufactured by Shimizu Akira Co., Ltd.), air-dried to evaporate the solvent, and then weighed. The amount of precipitate on the spoon is preferably less than 0.5 g, more preferably less than 0.3 g, and even more preferably less than 0.1 g. This is a polyurethane ink.

[0040] A polyurethane ink according to one embodiment contains a polyurethane resin, carbon black, and a copper phthalocyanine sulfonic acid derivative represented by the general formula (1), The polyurethane ink was applied to nylon film (Unitika Emblem #1500, manufactured by Unitika Ltd.) using a No. 6 bar coater (manufactured by AS ONE Corporation), and the resulting applied film was sandwiched between white film (nylon film coated with white ink and laminated with polypropylene, manufactured by DIC Corporation). The film was then submerged in water in a 1L autoclave (manufactured by Taiatsu Glass Industries Co., Ltd.) and heated at 135°C for 30 minutes. The white film was then removed (peel off) from the nylon film sandwiched between the white films, and the applied nylon film adhering to the white film was wiped off with a Kimwipe S-200 (manufactured by Nippon Paper Crecia Co., Ltd.) soaked in ethanol (manufactured by Kanto Chemical Co., Ltd.). The intensity of the color that had migrated from the applied surface of the nylon film to the white film was measured using a spectrophotometer eXact Advanced (manufactured by X-Rite Inc.) under the following conditions. The color difference between the white film before and after the test was determined, and the color difference ΔE * is preferably less than 3.0, more preferably less than 2.5, and even more preferably less than 2.0. Measuring equipment: eXact Advanced (manufactured by X-Rite) Measurement mode: Single L * a * b * Color related values: M3 polarizing filter Density related values: M3 polarizing filter Illuminant / observer field of view: D50 / 2°

[0041] (Method of producing carbon black composition) The method for producing the carbon black composition of this embodiment includes a mixing step of mixing carbon black and a copper phthalocyanine sulfonic acid derivative.

[0042] [Mixing process] The mixing step in the method for producing the carbon black composition of this embodiment is a step of mixing carbon black with a copper phthalocyanine sulfonic acid derivative. The mixing temperature in the mixing step is preferably 15 to 90°C, more preferably 20 to 80°C, from the viewpoint of uniformly mixing the carbon black and the copper phthalocyanine sulfonic acid derivative. The mixing time in the mixing step is preferably from 0.1 to 180 minutes, more preferably from 0.2 to 120 minutes, from the viewpoint of uniformly mixing the carbon black and the copper phthalocyanine sulfonic acid derivative.

[0043] Examples of the mixing method include liquid mixing, solid mixing, and acid precipitation mixing.

[0044] <Liquid mixing> In the liquid mixing, carbon black, a copper phthalocyanine sulfonic acid derivative, and water are mixed. The amount of water used may be such that a slurry is obtained. The amount of water used is preferably 10 to 1000 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 10 to 50 parts by mass, per part by mass of carbon black. The amount is preferably 10 to 1000 parts by mass, more preferably 10 to 200 parts by mass, and even more preferably 50 to 150 parts by mass relative to 1 part by mass of the copper phthalocyanine sulfonic acid derivative.

[0045] In the carbon black composition produced by liquid mixing, the carbon black particles and the copper phthalocyanine sulfonic acid derivative particles are present in a state where they are thoroughly mixed together.

[0046] <Solid mixture> The solid mixing includes a preparation step of preparing a dried carbon black and a dried copper phthalocyanine sulfonic acid derivative before the mixing step. In the preparation step, for example, wet carbon black and wet copper phthalocyanine sulfonic acid derivative are dried to prepare dried carbon black and dried copper phthalocyanine sulfonic acid derivative.

[0047] In the carbon black composition produced by liquid mixing, the carbon black and the copper phthalocyanine sulfonic acid derivative are present in the carbon black composition as a mixture of particles and aggregates.

[0048] <Acid precipitation mixture> The acid precipitation mixing includes, prior to the mixing step, a slurrying step in which a basic compound and water are mixed with carbon black and a copper phthalocyanine sulfonic acid derivative, respectively, to obtain a carbon black slurry and a copper phthalocyanine sulfonic acid derivative slurry; a mixing step in which the carbon black slurry and the copper phthalocyanine sulfonic acid derivative slurry are mixed; and a precipitation step in which an acidic compound is added to coat the carbon black with the copper phthalocyanine sulfonic acid derivative.

[0049] Examples of basic compounds include alkali metal hydroxides and alkaline earth metal hydroxides. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide. The basic compound may be used in an amount that will give the slurry a desired pH. The pH of the slurry in the slurrying step is preferably 8 to 14, more preferably 8 to 10, from the viewpoint of dissolving the copper phthalocyanine sulfonic acid derivative.

[0050] Examples of the acidic compound include hydrogen halide, sulfuric acid, and nitric acid. Examples of hydrogen halides include hydrogen chloride, hydrogen fluoride, hydrogen bromide, and hydrogen iodide. The acidic compound may be used in an amount sufficient to give the slurry a desired pH. The pH of the slurry in the precipitation step is preferably 1 to 6, more preferably 5 to 6, from the viewpoint of precipitating the copper phthalocyanine sulfonic acid derivative.

[0051] The amount of water used may be such that a slurry is obtained. The amount of water used is preferably 10 to 1000 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 10 to 50 parts by mass, per part by mass of carbon black. The amount is preferably 10 to 1000 parts by mass, more preferably 10 to 200 parts by mass, and even more preferably 20 to 150 parts by mass relative to 1 part by mass of the copper phthalocyanine sulfonic acid derivative.

[0052] In the carbon black composition produced by acid precipitation mixing, the carbon black is present in the composition in a state where it is coated with a copper phthalocyanine sulfonic acid derivative.

[0053] Among the above, the mixing step in the method for producing the carbon black composition of this embodiment is preferably liquid mixing or acid precipitation mixing, and more preferably acid precipitation mixing.

[0054] [Optional process] The method for producing the carbon black composition of this embodiment may include any step other than the mixing step described above. The optional steps may include, after the mixing step, a filtration step of performing filtration, a water washing step of performing water washing, a drying step of performing drying, and a pulverization step of performing pulverization. If necessary, the cationic species of the copper phthalocyanine sulfone derivative can be changed by using a metal salt. The metal salt used may be one that can be changed to the desired cation species. Examples of metal salts include aluminum sulfate, aluminum chloride, sodium sulfate, sodium chloride, potassium sulfate, potassium chloride, magnesium sulfate, magnesium chloride, calcium sulfate, and calcium chloride. The amount of the metal salt used is preferably 0.01 to 10.00 parts by mass, and more preferably 0.1 to 1.0 part by mass, per part by mass of the copper phthalocyanine sulfonic acid derivative. In this specification, the term "dry" means that the moisture content of the object is preferably less than 3% by mass, more preferably less than 2% by mass, and even more preferably less than 1% by mass. The moisture content can be measured using a heat-drying moisture meter, an infrared moisture meter, or the like. [Example]

[0055] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[0056] [Preparation of Carbon Black (CB1)] 150 parts by mass of commercially available neutral carbon black was added to 500 parts by mass of water, and the mixture was stirred for 1 hour to wet the carbon black with water. Next, 2500 parts by mass of water was further added and stirred for 1 hour, after which 6.72 parts by mass of iron (II) sulfate heptahydrate (manufactured by Kanto Chemical Co., Inc.) was added and stirred for a further 30 minutes. To this was added 214.3 parts by mass of 35% by mass hydrogen peroxide (manufactured by Kanto Chemical Co., Inc.), and after stirring for 1 hour, 1.59 parts by mass of iron (II) sulfate heptahydrate was added, and the mixture was further stirred for 1 hour. Subsequently, the carbon black slurry was filtered and washed with water to obtain wet carbon black (CB1) (solid content: 28.0% by mass).

[0057] [Preparation of Carbon Black (CB2)] 150 parts by mass of commercially available neutral carbon black was added to 500 parts by mass of water, and the mixture was stirred for 1 hour to wet the carbon black with water. Next, 2500 parts by mass of water was further added and stirred for 1 hour, after which 3.36 parts by mass of iron (II) sulfate heptahydrate (manufactured by Kanto Chemical Co., Inc.) was added and stirred for a further 30 minutes. To this was added 214.3 parts by mass of 35% by mass hydrogen peroxide (manufactured by Kanto Chemical Co., Inc.), and after stirring for 1 hour, 0.80 parts by mass of iron (II) sulfate heptahydrate was added, and the mixture was further stirred for 1 hour. Subsequently, the carbon black slurry was filtered and washed with water to obtain wet carbon black (CB2) (solid content: 27.5% by mass).

[0058] (Synthesis Example 1) Synthesis of copper phthalocyanine sulfonic acid compound 1 (Cu-Pc / SA-1) 361 parts by mass of 98% by mass sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 88 parts by mass of 25% by mass fuming sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a 500 mL separable flask and mixed by stirring. Next, 50 parts by mass of copper phthalocyanine (manufactured by DIC Corporation) was gradually added to the sulfuric acid and dissolved. Thereafter, the temperature was raised to 95°C over 1 hour while stirring, and after maintaining at 95°C for 12 hours, the sulfuric acid slurry was taken out into 3000 mL of ice water prepared in a 5 L beaker. The removed sulfuric acid slurry was heated to 60°C, stirred and maintained at the same temperature for 1 hour, filtered, and washed with water to obtain a wet copper phthalocyanine sulfonic acid compound 1 (SN2 / SN1=0.12) (solid content: 20.7% by mass).

[0059] (Synthesis Example 2) Synthesis of copper phthalocyanine sulfonic acid compound 2 (Cu-Pc / SA-2) The same operation as in Synthesis Example 1 was carried out, except that the amount of 98% by mass sulfuric acid was changed to 331 parts by mass and the amount of 25% by mass fuming sulfuric acid was changed to 119 parts by mass, thereby obtaining a wet copper phthalocyanine sulfonic acid compound 2 (SN2 / SN1=0.11) (solid content: 20.0% by mass).

[0060] (Synthesis Example 3) Synthesis of copper phthalocyanine sulfonic acid compound 3 (Cu-Pc / SA-3) The same operation as in Synthesis Example 2 was carried out except that the reaction temperature of the removed sulfuric acid slurry was changed to 100°C, thereby obtaining a wet copper phthalocyanine sulfonic acid compound 3 (SN2 / SN1 = 0.22) (solid content: 20.1 mass%).

[0061] (Synthesis Example 4) Synthesis of Copper Phthalocyanine Sulfonic Acid Compound 4 (Cu-Pc / SA-4) The same operations as in Synthesis Example 3 were carried out except that the amount of 98% by mass sulfuric acid was changed to 274 parts by mass and the amount of 25% by mass fuming sulfuric acid was changed to 176 parts by mass, and wet copper phthalocyanine sulfonic acid compound 4 (SN2 / SN1 = 0.30) (solid content: 20.5% by mass) was obtained.

[0062] (Synthesis Example 5) Synthesis of Copper Phthalocyanine Sulfonic Acid Compound 5 (Cu-Pc / SA-5) The same operations as in Synthesis Example 2 were carried out except that the reaction temperature of the extracted sulfuric acid slurry was changed to 85°C, and wet copper phthalocyanine sulfonic acid compound 5 (SN2 / SN1 = 0.05) (solid content: 20.7% by mass) was obtained.

[0063] (Synthesis Example 6) Synthesis of Copper Phthalocyanine Sulfonic Acid Compound 6 (Cu-Pc / SA-6) The same operations as in Synthesis Example 3 were carried out except that the amount of 98% by mass sulfuric acid was changed to 217 parts and the amount of 25% by mass fuming sulfuric acid was changed to 233 parts, and copper phthalocyanine sulfonic acid compound 6 (SN2 / SN1 = 0.40) (solid content: 21.1% by mass) was obtained.

[0064] (Cu-Pc / SA-1) to (Cu-Pc / SA-6), SN2 / SN1 was calculated as follows. (Cu-Pc / SA-1) to (Cu-Pc / SA-6) in the wet state were weighed into a 100 mL volumetric flask so that the solid content was 25 mg, and made up to 100 mL with dimethyl sulfoxide (DMSO, manufactured by Kanto Chemical Co., Inc.). This was dispersed with an ultrasonic disperser for 30 minutes, shaken by hand for 1 minute, and then filtered through an HPLC disk (manufactured by Sampratech Co., Ltd., Ekicrodisk 13CR, material: PTFE, pore size: 0.45 μm). Then, HPLC analysis of the obtained sample was carried out under the following conditions. <HPLC Analysis Conditions> Instrument name: High Performance Liquid Chromatogram EXTREMA (manufactured by JASCO Corporation) Column: SHISEIDO CAPCELL PAK C 18 UG 120, C18, 3μm, 4.6×100mm Column temperature: 50℃ Mobile phase A / B: Acetonitrile / 1 vol% dibutylammonium acetate aqueous solution Gradient: 30% acetonitrile → 17 min → 90% (hold for 3 min) Mobile phase flow rate: 0.4mL / min Sample injection volume: 1 μL Measurement wavelength: 668nm The copper phthalocyanine sulfonic acid compound with n=2 corresponds to a peak with a retention time of 5 to 12 minutes, and the copper phthalocyanine sulfonic acid compound with n=1 corresponds to a peak with a retention time of 12 to 19 minutes. The area of each peak group was calculated to determine SN2 / SN1.

[0065] (Examples 1 to 7 and Comparative Example 1) Preparation of carbon black compositions by liquid mixing 1 Wet carbon black and water (20 parts by mass per 1 part by mass of carbon black) were placed in a 1 L beaker, and the mixture was heated to 60°C over 1 hour with stirring to obtain a carbon black slurry. Separately, a 50 mL beaker was charged with a wet copper phthalocyanine sulfonic acid derivative (any one of Cu-Pc / SA-1 to Cu-Pc / SA-6) shown in Table 1 and water (90 parts by mass per 1 part by mass of the copper phthalocyanine sulfonic acid derivative), and the mixture was stirred at room temperature for 1 hour to obtain a slurry of the copper phthalocyanine sulfonic acid derivative. Next, the slurry of copper phthalocyanine sulfonic acid derivative was added to the slurry of carbon black, and the mixture was stirred at 60° C. for 1 hour. The mixture was filtered, washed with water, dried overnight at 98°C, and pulverized to obtain the carbon black composition of each example.

[0066] Example 8 Preparation of carbon black compositions by liquid mixing 2 Wet carbon black and water (20 parts by mass per 1 part by mass of carbon black) were placed in a 1 L beaker, and the mixture was heated to 60°C over 1 hour with stirring to obtain a carbon black slurry. Separately, wet Cu-Pc / SA-1 and water (90 parts by mass per part by mass of Cu-Pc / SA-1) were placed in a 50 mL beaker and stirred at room temperature for 1 hour. Aluminum sulfate 14-18 hydrate (Kanto Chemical Co., Inc.) (0.5 parts by mass per part by mass of Cu-Pc / SA-1) was then added and stirred for 1 hour to obtain a slurry of a copper phthalocyanine sulfonic acid derivative (a compound in which the cation species of Cu-Pc / SA-1 was changed to aluminum ions). Next, the slurry of copper phthalocyanine sulfonic acid derivative was added to the slurry of carbon black, and the mixture was stirred at 60° C. for 1 hour. This was filtered, washed with water, dried overnight at 98°C, and pulverized to obtain the carbon black composition of Example 8.

[0067] Examples 9 to 12 -Production of carbon black composition by acid precipitation mixing Wet carbon black and water were placed in a 2 L beaker, heated to 60°C over 1 hour with stirring, and then adjusted to pH 9.0 with a 20% by weight aqueous solution of sodium hydroxide to obtain a carbon black slurry. The amount of water was 20 parts by weight per part by weight of carbon black. Separately, a 50 mL beaker was charged with a wet copper phthalocyanine sulfonic acid derivative (Cu-Pc / SA-1 or Cu-Pc / SA-3) shown in Table 1 and water, and the mixture was stirred at room temperature for 1 hour. The pH was then adjusted to 9.0 with a 20% by mass aqueous solution of sodium hydroxide to obtain a slurry of the copper phthalocyanine sulfonic acid derivative. The amount of the aqueous solution was 30 parts by mass per part by mass of the copper phthalocyanine sulfonic acid derivative. Next, the copper phthalocyanine sulfonic acid compound slurry is added to the carbon black slurry, and the mixture is stirred at 60° C. for 1 hour. Subsequently, the pH of the slurry was adjusted to 5.5 with a 20% by mass aqueous solution of hydrochloric acid to precipitate the copper phthalocyanine sulfonic acid derivative on the surface of the carbon black, and the mixture was stirred for 1 hour. The mixture was filtered, washed with water, dried overnight at 98°C, and pulverized to obtain the carbon black composition of each example.

[0068] Example 13 - Manufacturing of carbon black compositions by solid mixing The carbon black and the wet copper phthalocyanine sulfonic acid derivative (Cu-Pc / SA-1) were each dried at 98°C overnight to obtain dried carbon black (moisture content: less than 1% by mass) and dried copper phthalocyanine sulfonic acid derivative (moisture content: less than 1% by mass). Next, the entire amounts of the dried carbon black and the dried copper phthalocyanine sulfonic acid derivative were placed in a large mill cup (volume 200 mL) of a portable laboratory mill LAB MILL (manufactured by Osaka Chemical Co., Ltd.) and operated for 30 seconds to pulverize and mix, thereby obtaining the carbon black composition of Example 13.

[0069] <Evaluation test> (Preparation of polyurethane ink) 20 g of the produced carbon black composition, 11.5 g of polyurethane resin Sanprene IB-501 (manufactured by Sanyo Chemical Industries, Ltd.), 6.8 g of ethyl acetate (manufactured by Kanto Chemical Co., Ltd.), 3.7 g of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.), 2.5 g of n-propanol (manufactured by Kanto Chemical Co., Ltd.), 8.5 g of ethoxypropanol (manufactured by Kanto Chemical Co., Ltd.), and 180 g of 1 / 8-inch steel beads (manufactured by Mochigi Steel Ball Bearing Co., Ltd.) were placed in a 250 mL wide-mouth polyethylene bottle, and the mixture was dispersed for 30 minutes using a paint shaker (manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a dispersion. Next, a polyurethane resin solution prepared by premixing 11.5 g of polyurethane resin Sanprene IB-501, 8.9 g of ethyl acetate, 2.0 g of isopropanol, and 10.6 g of propyl acetate was added to the dispersion and dispersed for an additional 5 minutes to obtain a polyurethane ink.

[0070] (Storage stability test) 50 g of the prepared polyurethane ink was transferred to a glass bottle (tableware bottle M-70, manufactured by Kashiwa Glass Co., Ltd.) and left to stand at 50°C for 7 days in a multi-safety dryer MSO-45TPH (manufactured by Futaba Chemical Co., Ltd.). The black precipitate that formed at the bottom of the glass bottle was scooped up with a medicine spoon (Sandia stainless steel spoon, 40 spoons, manufactured by Shimizu Akira Co., Ltd.), air-dried to evaporate the solvent components, and then the weight of the precipitate was measured and rated on a five-point scale from 1 to 5. A rating of 5 indicates a good result with little precipitation, while a rating of 1 indicates a bad result with a large amount of precipitation. The results are shown in Table 1. 5: The amount of sediment on the spoon is less than 0.1g 4: The amount of sediment on the spoon is 0.1g or more but less than 0.3g 3: The amount of sediment on the spoon is 0.3g or more but less than 0.5g 2: The amount of sediment on the spoon is 0.5g or more but less than 1.0g 1: The amount of sediment on the spoon is 1.0g or more

[0071] (Retort resistance test) The prepared polyurethane ink was spread onto nylon film (Unitika Emblem #1500, Unitika Ltd.) using a No. 6 bar coater (As One Corporation), and the resulting spread was sandwiched between white film (nylon film coated with white ink and laminated with polypropylene, DIC Corporation). This was submerged in water in a 1L autoclave (manufactured by Taiatsu Glass Industry Co., Ltd.) and heated at 135°C for 30 minutes.The white film was then removed (peel off) from the nylon film sandwiched between the white films, and the color of the nylon film adhering to the white film was wiped off with a Kimwipe S-200 (manufactured by Nippon Paper Crecia Co., Ltd.) soaked in ethanol (manufactured by Kanto Chemical Co., Ltd.).The intensity of the color that had migrated from the colored surface of the nylon film to the white film was judged on a five-point scale from 1 to 5. The intensity of the transferred color was determined by measuring the color difference of the white film before and after the test using a spectrophotometer eXact Advanced (manufactured by X-Rite) under the following conditions. Measuring equipment: eXact Advanced (manufactured by X-Rite) Measurement mode: Single L * a * b * Color related values: M3 polarizing filter Density related values: M3 polarizing filter Illuminant / observer field of view: D50 / 2° A rating of 5 indicates a small degree of migration and is good, while a rating of 1 indicates a large degree of migration and is bad. The results are shown in Table 1. 5: Color difference ΔE * is less than 2.0 4: Color difference ΔE * is 2.0 or more and less than 2.5 3: Color difference ΔE * is 2.5 or more and less than 3.0 2: Color difference ΔE * is 3.0 or more and less than 3.5 1: Color difference ΔE * is 3.5 or more

[0072] [Table 1]

[0073] As shown in Table 1, it was confirmed that the carbon black compositions of Examples 1 to 17 had better storage stability and retort resistance than the carbon black composition of Comparative Example 1.

Claims

1. Contains carbon black and a copper phthalocyanine sulfonic acid derivative, The copper phthalocyanine sulfonic acid derivative contains a compound represented by the following general formula (1): a carbon black composition, wherein, in the compounds represented by general formula (1), the molar ratio (SN2 / SN1) of a compound (SN1) where n=1 to a compound (SN2) where n=2 is less than 0.

40. 【Chemical 1】 [In general formula (1), M represents a cation species, and n represents 1 or 2.]

2. 2. The carbon black composition according to claim 1, wherein the content of the copper phthalocyanine sulfonic acid derivative is 0.01 to 2.0 parts by mass per 100 parts by mass of the carbon black.

3. 2. The carbon black composition according to claim 1, wherein the carbon black is surface-treated with elemental iron.

4. A colorant comprising the carbon black composition according to claim 1 or 2.

5. An ink comprising the carbon black composition according to claim 1 or 2.

6. A method for producing the carbon black composition according to claim 1 or 2, comprising the steps of: A method for producing a carbon black composition, comprising a mixing step of mixing carbon black with a copper phthalocyanine sulfonic acid derivative.

7. 7. The method for producing a carbon black composition according to claim 6, wherein water is further mixed in the mixing step.

8. a preparation step of preparing a dried carbon black and a dried copper phthalocyanine sulfonic acid derivative before the mixing step, 7. The method for producing a carbon black composition according to claim 6, wherein the mixing step is carried out by mixing the dried carbon black with the dried copper phthalocyanine sulfonic acid derivative.

9. a slurrying step, prior to the mixing step, of mixing a basic compound and water with the carbon black and the copper phthalocyanine sulfonic acid derivative, respectively, to obtain a slurry of the carbon black and a slurry of the copper phthalocyanine sulfonic acid derivative; 7. The method for producing a carbon black composition according to claim 6, wherein the mixing step is carried out by mixing a slurry of the carbon black with a slurry of the copper phthalocyanine sulfonic acid derivative.

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