WO2016121588A1 - 酸化カーボンブラック水性分散体の製造方法およびインクジェットインキ用酸化カーボンブラック水性分散体の製造方法 - Google Patents
酸化カーボンブラック水性分散体の製造方法およびインクジェットインキ用酸化カーボンブラック水性分散体の製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
- C09C1/565—Treatment of carbon black ; Purification comprising an oxidative treatment with oxygen, ozone or oxygenated compounds, e.g. when such treatment occurs in a region of the furnace next to the carbon black generating reaction zone
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/487—Separation; Recovery
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/005—Carbon black
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Definitions
- the present invention relates to a method for producing an oxidized carbon black aqueous dispersion and a method for producing an oxidized carbon black aqueous dispersion for an inkjet ink composition.
- the ink jet recording method is a method of ejecting ink droplets from a fine nozzle head to record characters and images on the surface of a recording medium such as paper. It is non-contact with a wide variety of recording media including plain paper. Printing has an advantage that an image can be easily formed on demand without producing a printing plate.
- ink-jet ink composition ink-jet printer ink composition
- organic solvent-based ink compositions Water-based inkjet ink compositions and solventless inkjet ink compositions are becoming widespread.
- an anionic functional group such as a group, —SO 3 — group, —PO 4 2- group, and the like, and further by the presence of an alkaline counter ion, it is self-dispersed in an aqueous inkjet ink composition.
- Obtainable acidic carbon black has been proposed.
- the applicant granulated and pulverized carbon black fine particles by a wet method, and then oxidized carbon black fine particles provided with acidic functional groups on the surface by wet oxidation treatment of the obtained pulverized product in an aqueous medium.
- Patent Document 1 International Publication No. 2011/007730
- carbon black is produced by various methods such as furnace method, channel method, thermal method, etc. using heated fuel oil, dry distillation component of coal, aromatic hydrocarbon oil obtained by petroleum refining process, etc. as raw materials.
- these raw materials contain polyvalent metal components such as Fe, Ni, and Ca, these polyvalent metal components are contained as impurities in the resulting carbon black in a further concentrated state. It will be.
- a metal component contained in cooling water used in the carbon black production process or a metal component eluted due to metal corrosion of production equipment may be mixed into the carbon black.
- a polyvalent metal ion may mix in carbon black aqueous dispersion, and especially anionic functional group (( When an acidic carbon black having an acidic functional group) is used, the polyvalent metal ion and the anionic functional group provided on the surface of the acidic carbon black are combined to form a colloidal hydrolyzate. It has been found that when colloidal hydrolyzate becomes a foreign substance, when used in an ink jet ink composition, a metal may be deposited at the nozzle portion, or an insoluble material may be precipitated in the ink jet ink composition.
- a method for removing the metal component mixed in the carbon black aqueous dispersion As a method for removing the metal component mixed in the carbon black aqueous dispersion, a method of treating with an ion exchange resin or a method of repeatedly washing with pure water can be considered.
- the exchange capacity of the ion exchange resin is not so large, and the ion exchange resin must be regenerated frequently, and according to the study by the present inventors, when the removal target is a polyvalent metal ion, a plurality of ion exchange resins must be regenerated. It was found that it was difficult to remove even after washing with recycled water.
- anion functional groups such as —COO 2 — , —SO 3 — , and —PO 4 2— groups formed on the surface of oxidized carbon black constituting the aqueous dispersion of carbon black capture metal ions by chelating action. Therefore, it is considered that it is difficult to elute easily by washing with an ion exchange resin or pure water.
- the chelating agent is a metal impurity in an ionic state in water. Although it can be trapped, it is difficult to remove polyvalent metal ions trapped by anionic functional groups on the surface of carbon black, and in particular, divalent metal ions such as Ni ions, Zn ions, Ca ions, and Mg ions are removed. It turned out to be difficult.
- the present invention provides a method for easily producing an aqueous oxidized carbon black dispersion in which polyvalent metal ions are highly removed and can exhibit excellent dispersion stability, and an inkjet ink composition It is an object of the present invention to provide a method for producing an aqueous oxidized carbon black dispersion.
- the present inventors diligently studied.
- the aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface is one or more selected from water-soluble chelating agents or salts thereof.
- the separation and removal step of separating and removing the polyvalent metal ion chelate complex from the mixed solution obtained in the neutralization step by using a separation membrane, thereby producing an oxidized carbon black aqueous dispersion.
- the present inventors have found that the problem can be solved, and have completed the present invention based on this knowledge.
- the present invention (1) For an aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface, In the presence of one or more selected from a water-soluble chelating agent or a salt thereof, an alkali metal hydroxide is mixed and neutralized by heating, or after mixing an alkali metal hydroxide and neutralized by heating, the water-soluble chelating agent or its salt A neutralization step of mixing one or more selected from salts; A method for producing an aqueous dispersion of oxidized carbon black, characterized by sequentially performing a separation and removal step of separating and removing the polyvalent metal ion chelate complex from the mixed liquid obtained in the neutralization step using a separation membrane; (2) The method for producing an aqueous dispersion of oxidized carbon black according to (1), wherein in the neutralization step, the alkali metal hydroxide is mixed with the aqueous slurry of oxidized carbon black so as to have a pH of 6 to 12.
- An aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface is oxidized from the water-soluble chelating agent or a salt thereof under pH 2 to pH 4 conditions after the carbon black is oxidized by a liquid phase method.
- An aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface is oxidized from the water-soluble chelating agent or a salt thereof under pH 2 to pH 4 conditions after the carbon black is oxidized by a liquid phase method.
- an alkali metal hydroxide is mixed with an aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface in the presence of one or more water-soluble chelating agents or salts thereof.
- Anion on the surface of oxidized carbon black by neutralizing by heating or by performing a neutralization step of mixing one or more selected from a water-soluble chelating agent or a salt thereof after mixing with alkali metal hydroxide for heat neutralization
- the polyvalent metal ions trapped by the functional group are gradually trapped by the chelating agent and exchanged for alkali metal ions, and then the polyvalent metal ions trapped by the chelating agent in the separation and removal step are separated and removed.
- a high degree of dispersibility due to the repulsive force of the alkali metal ions can be imparted to black. Therefore, according to the present invention, it is possible to provide a method for easily producing an aqueous oxidized carbon black dispersion from which polyvalent metal ions are highly removed and exhibit excellent dispersion stability, and an inkjet ink. A method for producing an aqueous oxidized carbon black dispersion for a composition can be provided.
- the method for producing an aqueous dispersion of oxidized carbon black according to the present invention comprises an aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface, in the presence of one or more selected from water-soluble chelating agents or salts thereof.
- the separation and removal step of separating and removing the polyvalent metal ion chelate complex from the mixed solution obtained in the sum step using a separation membrane is sequentially performed.
- the carbon black constituting the oxidized carbon black is not particularly limited, and examples thereof include furnace black, channel black, acetylene black, and thermal black. Any of acidic, neutral and basic may be used. When carbon black is acidic, it may be used as it is as oxidized carbon black, or may be used as oxidized carbon black after further oxidation treatment to a desired level.
- the carbon black is preferable because of its high carbon content, high blackness derived from the amorphous structure, high drying speed, high storage stability, and low cost compared to peach black and lamp black. Can be used.
- ultrafine carbon blacks such as furnace black and channel black can obtain high resolution and excellent print quality when used as an aqueous pigment dispersion in an ink composition for an ink jet printer.
- the carbon black preferably has a nitrogen adsorption specific surface area (N 2 SA) of 25 to 300 m 2 / g, more preferably 100 to 300 m 2 / g, and 100 to 180 m 2 / g. Is more preferable.
- N 2 SA nitrogen adsorption specific surface area
- the carbon black is preferably one DBP absorption is 120 cm 3/100 g or more, more preferably those which are 120 ⁇ 180cm 3 / 100g, more preferably those which are 130 ⁇ 170cm 3 / 100g.
- the N 2 SA and DBP absorption amount of carbon black is within the above range, colloidal characteristics in an aqueous medium are improved, and when the obtained oxidized carbon black aqueous dispersion is used in an ink-jet ink composition, it is water-based. Excellent dispersibility in the medium and ink performance can be exhibited.
- N 2 SA of carbon black is defined as “carbon black for rubber—basic characteristics—part 2, determination of specific surface area—nitrogen adsorption method, single point method” as defined in JIS K6217-2.
- the DBP absorption amount means a value measured according to “Carbon Black for Rubber—Basic Properties—Part 4, Determination of DBP Absorption” defined in JISK6217-4.
- the average particle size of carbon black is preferably 30 to 300 nm, more preferably 40 to 270 nm, and even more preferably 50 to 250 nm.
- the average particle size of carbon black means a particle size of 50% (volume average particle size D50) in the integrated particle size distribution measured by a laser diffraction particle size distribution measuring device. To do.
- carbon black examples include Seest 9, Seast 6, Talker Black # 4500, Talker Black # 8500, Talker Black # 8500F, Talker Black # 7550SB, Talker Black # 7550F (above Tokai Carbon Co., Ltd.), # 650 , # 750, MA600, # 44B, # 44, # 45B, MA7, MA11, # 47, # 45, # 33, # 45L, # 47, # 50, # 52, MA77, MA8 (above Mitsubishi Chemical Corporation) Manufactured), FW200, FW2V, FWI, FW18PS, NIpex180IQ, FW1, Special Black6, S160, S170 (manufactured by Orion Engineered Carbons), Black Pearls 1000M, Black Pearls 800, Black Pearls 880, onarch 1300, Monarch 700, Monarch 880, CRX 1444, Regal 330R, Regal 660R, Regal 660, Regal 415R, Regal 415, Black Pearls 4630, Monarch 4630 (
- the oxidized carbon black is an anion on the surface by a method of oxidizing the carbon black with an oxidizing agent, a method of sulfonation, a method of reacting a diazonium salt, or the like.
- Functional groups (acidic groups) can be introduced.
- the oxidation treatment with an oxidizing agent can be performed by a known method such as a liquid phase method or a gas phase method.
- an oxidizing agent for example, peroxydiacids such as nitric acid, sulfuric acid, chloric acid, peroxosulfuric acid, peroxoboric acid, peroxocarbonic acid, peroxophosphoric acid, permanganic acid, dichromic acid, Examples include chlorous acid, perchloric acid, hypohalous acid, hydrogen peroxide, phosphonic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, and salts of these acids. Examples thereof include alkali metal salts such as lithium, sodium and potassium, and ammonia salts.
- carbon black having an anionic functional group (acidic group) on the surface can be obtained by introducing carbon black into a dispersion containing the oxidizing agent and performing a stirring treatment.
- the solvent for dispersing the oxidizing agent is preferably an aqueous medium, and examples of the aqueous medium include water and water-soluble organic solvents, but water, particularly deionized water is preferable from the viewpoint of economy and safety.
- a surfactant may be added to the dispersion containing the oxidizing agent, and any of anionic, nonionic, and cationic types may be used as the surfactant. be able to.
- the degree of liquid phase oxidation is adjusted by adjusting the oxidant concentration in the dispersion containing the oxidant, the ratio of the amount of carbon black particles added to the oxidant aqueous solution, the oxidation treatment temperature, the treatment time, the stirring speed, etc. Can be controlled.
- the liquid phase oxidation is performed, for example, by adding and mixing carbon black particles in an aqueous oxidizer solution having a adjusted concentration in an appropriate quantitative ratio, and at a temperature of about room temperature to 90 ° C., preferably 60 to 90 ° C. It can be carried out by stirring for 20 hours to form a slurry.
- the carbon black particles may be wet-oxidized or dry-oxidized in advance, and the carbon black particles can be efficiently dispersed in the aqueous oxidizer solution by wet-oxidizing or dry-oxidizing in advance. Liquid phase oxidation treatment can be performed uniformly and efficiently.
- a method of introducing an anionic functional group (acidic group) on the surface of carbon black by a method of reacting with a diazonium salt is carried out by a diazo coupling method on the surface of carbon black, and various methods via a benzene ring on the surface of carbon black.
- An anionic functional group of, for example, —C 6 H 4 —COOH, —C 6 H 4 —SO 3 H, —C 6 H 4 —PO 4 2- H 2 For example, as described in JP-T-2000-512329.
- the oxidation treatment by the gas phase method can be performed by exposing the carbon black particles to a gas atmosphere such as ozone, air, NOx, SOx, etc. According to the gas phase method, the drying cost is not incurred. There are advantages such as easy operation compared with the liquid phase method.
- the neutralization reaction step described later can proceed smoothly and efficiently.
- the reduction salt can be removed using a separation membrane such as an ultrafiltration membrane (UF), a reverse osmosis membrane (RO), and an electrodialysis membrane. It is desirable to purify the reduced salt so that the conductivity is less than 5 mS / cm when the carbon black dispersion concentration is 20% by mass, for example. Insufficient separation and purification leads to a decrease in water dispersibility and dispersion stability, an increase in viscosity of the dispersion, and equipment corrosion due to the dispersion.
- UF ultrafiltration membrane
- RO reverse osmosis membrane
- the reduction salt removal treatment is performed by oxidizing carbon black by a liquid phase method, then preferably under conditions of pH 2 to pH 4, more preferably pH 2.1 to pH 3.9, and further preferably pH 2.3 to pH 3.8.
- the treatment is preferably carried out after mixing the treatment liquid with one or more water-soluble chelating agents or salts thereof.
- anionic functional groups (acidic functional groups) selected from a —COO 2 — group, —SO 3 — group, —PO 4 2- group, etc. on the surface of carbon black, the pH in the liquid phase is increased as described above. Easy to maintain and control over the range.
- the water-soluble chelating agent is not particularly limited, but is preferably an aminocarboxylic acid or a salt thereof.
- aminocarboxylic acid or a salt thereof examples include ethylenediaminetetraacetic acid [EDTA], nitrilotriacetic acid, diethylenetriaminepentaacetic acid [DTPA], hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid [TTHA], and 1,3-propanediamine tetra Acetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid [CyDTA], hydroxyethyleneiminodiacetic acid, dihydroxyethylglycine, glycol ether diamine tetraacetic acid, ethylenediamine dioltohydroxyphenylacetic acid [EDDDHA], ethylenediamine-N, N ′ -Bis [(2-hydroxy-5-methylphenyl) acetic acid] [EDDHMA], N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-2acetic acid [HBED], N, N'-bis (2-
- ethylenediaminetetraacetate is preferable and specific examples of ethylenediaminetetraacetate include sodium ethylenediaminetetraacetate and potassium ethylenediaminetetraacetate.
- the contact amount of the water-soluble chelating agent or the salt thereof with the oxidized carbon black is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the oxidized carbon black solid content. Preferably, it is 1.0 part by mass or more.
- the contact amount of the water-soluble chelating agent or the salt thereof with oxidized carbon black is preferably 15 parts by mass or less and more preferably 12.5 parts by mass or less with respect to 100 parts by mass of the oxidized carbon black solid content. Preferably, it is 10 parts by mass or less.
- the contact amount of the water-soluble chelating agent or the salt thereof with the oxidized carbon black is less than 0.1 parts by mass with respect to 100 parts by mass of the oxidized carbon black solid content, the complex formation between the polyvalent metal ion and the water-soluble chelating agent is possible.
- the amount exceeds 15 parts by mass with respect to 100 parts by mass of the oxidized carbon black solid content, it becomes difficult to further increase the complex formation amount, which is uneconomical.
- the contact temperature is preferably 40 ° C. or higher, more preferably 50 ° C., and further preferably 60 ° C.
- the contact time is preferably 30 minutes or longer, more preferably 1 hour or longer, and further preferably 3 hours or longer.
- the water-soluble chelating agent contains polyvalent metal ions contained in the liquid phase, particularly Fe 3+ , Al 3+ , Cr 3+ and the like.
- the polyvalent metal ion chelate complex forms a polyvalent metal ion chelate complex by binding with the valent metal ion, and this polyvalent metal ion chelate complex can be preliminarily separated during the removal treatment of the reduced salt. The amount can be easily reduced.
- the oxidized carbon black slurry obtained by the above-described reduction salt removal treatment is formed on the surface of the carbon black by acidic functional groups such as —COO 2 — , —SO 3 — , and —PO 4 2— groups.
- the pH is maintained at 2 to 4 even after the purification treatment. For this reason, even if a chelate complex with a polyvalent metal ion centered on a trivalent metal ion remains in the slurry after removing the reduced salt, the water-soluble chelating agent and the polyvalent metal ion Therefore, it is possible to suppress the capture of polyvalent metal ions on the surface of carbon black in the subsequent neutralization step.
- the oxidized carbon black thus obtained is preferably a self-dispersing carbon black having an acidic group on the surface.
- Self-dispersing carbon black having acidic groups on the surface is a group in which at least one hydrophilic group containing acidic groups is bonded to the surface of carbon black directly or via other atomic groups and suspended in water. When dispersed into a turbid dispersion, it can maintain a stable dispersion without adding a surfactant or polymer compound, meaning that the surface tension of the dispersion shows almost the same value as water. .
- the amount of acidic hydroxyl groups of oxidized carbon black is preferably 350 to 1500 ⁇ mol / g, more preferably 470 to 1150 ⁇ mol / g, and 600 to 900 ⁇ mol. More preferably, it is / g.
- the amount of acidic hydroxyl groups of oxidized carbon black means the sum of the amount of carboxyl groups (—COO ⁇ ) and the amount of hydroxyl groups (—O ⁇ ) of oxidized carbon black. .
- an acidic hydroxyl group is important as a functional group on the surface of the carbon black particles, and in particular, a carboxyl group and a hydroxyl group play a large role.
- the amount of acidic hydroxyl groups in the particles can be regarded as substantially the sum of the amount of carboxyl groups and the amount of hydroxyl groups.
- the oxidized carbon black preferably has a carboxyl group equivalent of 300 ⁇ mol / g to 1200 ⁇ mol / g, more preferably 400 ⁇ mol / g to 900 ⁇ mol / g. More preferably, it is 500 ⁇ mol / g to 700 ⁇ mol / g.
- the oxidized carbon black preferably has a hydroxyl group content of 50 ⁇ mol / g to 300 ⁇ mol / g, preferably 70 ⁇ mol / g to 250 ⁇ mol / g. More preferably, it is 100 ⁇ mol / g to 200 ⁇ mol / g.
- the amount of hydroxyl groups is 2,2′-diphenyl-1-picrylhydrazyl (DPPH) dissolved in carbon tetrachloride to prepare a 5 ⁇ 10 ⁇ 4 mol / l solution.
- DPPH 2,2′-diphenyl-1-picrylhydrazyl
- the amount of —SO 3 H groups and —PO 4 H 2 groups may be appropriately selected.
- the amount of —SO 3 H group or —PO 4 H 2 group is determined by, for example, generating oxidized carbon black by the liquid phase method and then removing the reducing salt in the slurry generated by the liquid phase oxidation.
- the carbon black surface binding energy intensity using an X-ray photoelectron spectrometer (S-Probe ESCA 2803 type, manufactured by Surface Science Instruments) with the oxidized carbon black from which moisture has been removed being measured. It means a value obtained by identifying the —SO 3 H group and —PO 4 H 2 group and the same method as the amount of carboxyl group.
- the oxidized carbon black preferably has an average particle size of 30 to 300 nm when dispersed in water, more preferably 40 to 270 nm, and still more preferably 50 to 250 nm.
- the average particle size of oxidized carbon black is 50% of the integrated particle size in the volume-based integrated particle size distribution (volume average particle size D50) measured by a laser diffraction particle size distribution measuring device. means.
- the oxidized carbon black is subjected to a neutralization step in the form of an aqueous slurry.
- the aqueous medium in which the oxidized carbon black is dispersed include water and water-soluble organic solvents, but water, particularly deionized water is preferable from the viewpoint of economy and safety.
- the solid content concentration of oxidized carbon black in the aqueous slurry is preferably 1.0 to 20.0% by mass, more preferably 1.0 to 15.0% by mass, More preferably, it is ⁇ 10.0% by mass.
- the aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface thereof, the presence of one or more selected from water-soluble chelating agents or salts thereof
- the mixture is neutralized by mixing with an alkali metal hydroxide underneath, or mixed with an alkali metal hydroxide and neutralized with heat, and then subjected to a neutralization step of mixing one or more water-soluble chelating agents or salts thereof.
- water-soluble chelating agent examples include one or more selected from those described above. Further, the contact amount of the water-soluble chelating agent or a salt thereof with respect to 100 parts by mass of the oxidized carbon black solid content is the same as the contact amount described above.
- the mixing timing of the aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface and one or more selected from water-soluble chelating agents or salts thereof is the above (i) to (iii)
- the metal impurity component contained in the oxidized carbon black is gradually eluted and exchanged with an alkali metal by the heat neutralization treatment in the neutralization step.
- alkali metal hydroxide used in the neutralization step examples include one or more selected from sodium hydroxide, lithium hydroxide, and potassium hydroxide.
- the amount of alkali metal hydroxide used in the neutralization step can be appropriately determined according to the oxidized carbon black to be neutralized, but is pH 6.0 to pH 12.0 with respect to the aqueous slurry of oxidized carbon black.
- the alkali metal hydroxide is preferably mixed so that the pH is 7.0 to pH 12.0, more preferably the alkali metal hydroxide is mixed so that the pH is 8.0 to pH 12.0. It is further preferable to mix metals.
- the aqueous slurry of oxidized carbon black is mixed with an alkali metal hydroxide so as to have a pH of 6.0 to pH 12.0, and neutralized by heating to obtain polyvalent metal ions trapped on the oxidized carbon black surface, particularly two Valent metal ions (divalent iron ions, zinc ions, nickel ions, magnesium ions, calcium ions, etc.) are eluted and exchanged with alkali hydroxide, and the eluted polyvalent metal ions are water-soluble chelating agent and polyvalent metal ion chelate. Since the complex is formed, becomes water-soluble, and dissolves in the slurry, it can be easily removed by membrane separation.
- Alkali hydroxide is preferably added in the form of an aqueous solution to an aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface.
- an aqueous medium for forming an aqueous solution water or water-soluble
- water, particularly deionized water is preferable from the viewpoint of economy and safety.
- the alkali hydroxide is heat neutralized by mixing the alkali hydroxide with an aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface.
- the heating temperature at the time of heat neutralization is preferably 30 ° C. to 95 ° C., more preferably 60 ° C. to 95 ° C., and further preferably 80 ° C. to 95 ° C.
- the time for mixing and holding the aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface, alkali hydroxide and water-soluble chelating agent is preferably 30 minutes to 12 hours, It is more preferably 1 to 8 hours, and further preferably 2 to 5 hours.
- the aqueous slurry of oxidized carbon black is mixed with an alkali metal hydroxide so as to have a pH of 6.0 to 12.0, and neutralized at the temperature and time described above, whereby a large amount of oxide carbon black trapped on the oxidized carbon black surface is obtained.
- Divalent metal ions especially divalent metal ions (divalent iron ions, zinc ions, nickel ions, magnesium ions, calcium ions, etc.) are exchanged with alkali metal ions, and the polyvalent metal ions exchanged with these alkali metal ions are water-soluble.
- a separation and removal step which is the next step.
- the polyvalent metal ion chelate complex is separated and removed from the mixed solution obtained in the neutralization step using a separation membrane. A removal process is performed.
- the separation membrane used in the separation and removal step is not particularly limited, but is preferably an ultrafiltration membrane (UF), a reverse osmosis membrane (RO) or an electrodialysis membrane.
- UF ultrafiltration membrane
- RO reverse osmosis membrane
- the separation membrane can separate and remove the polyvalent metal ions captured on the oxidized carbon black surface as a polyvalent metal ion chelate complex, and at the same time, can remove residual salts due to excess alkali hydroxide outside the system. At the same time, it is effective in suppressing reaggregation of oxidized carbon black particles.
- the separation treatment in the separation and removal step may be performed to such an extent that the residual salt due to the polyvalent metal ion chelate complex or excess alkali hydroxide can be sufficiently removed out of the system.
- the concentration of oxidized carbon black particles is 20 When it is mass%, it is preferable to carry out until the electrical conductivity of the aqueous dispersion becomes 5 mS / cm or less, and more preferably until it becomes 2 mS / cm or less.
- the method for producing an aqueous carbon black dispersion for an ink-jet ink composition according to the present invention is characterized in that the oxidized carbon black aqueous dispersion obtained by the method of the present invention is subjected to centrifugal separation to remove coarse particles. To do.
- the oxidized carbon black aqueous dispersion obtained by the method of the present invention may have large undispersed lumps and coarse particles such as coarse particles, classification and removal by centrifugation is preferable.
- a centrifuge which performs a centrifugation process One or more types chosen from a vertical centrifuge, a horizontal centrifuge, etc. can be mentioned. Centrifugation may be performed by adjusting the centrifugal force and flow rate of the centrifuge according to the number of target maximum particle diameters.
- an inkjet ink by further adjusting the concentration or adding an additive to the oxidized carbon black aqueous dispersion or the carbon black aqueous dispersion for inkjet ink composition obtained by the method of the present invention. it can.
- the concentration can be adjusted by adding or removing the aqueous dispersion to a target concentration. For example, if the concentration of oxidized carbon black is adjusted to 0.1 to 20% by mass, Good.
- additive one or more selected from preservatives, humectants, resins, surfactants and the like can be mentioned.
- the humectant is not particularly limited, but has a water dispersibility, such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, dipropylene glycol, polyethylene glycol, polypropylene glycol, amide. And one or more selected from ether, carboxylic acid, ester, alcohol, organic sulfide, organic sulfoxide, sulfone, alcohol derivative, carbitol, butyl carbitol, cellosolve, ether derivative, amino alcohol, ketone and the like.
- the ink-jet ink composition contains a humectant, it is possible to suppress clogging by suppressing the evaporation rate of the aqueous medium in the ink composition.
- the resin is not particularly limited.
- the fixability of the oxidized carbon black to the printing substrate can be improved.
- the surfactant is not particularly limited, and any of anionic, nonionic, and cationic surfactants can be used.
- anionic surfactants include fatty acid salts, One or more selected from alkyl sulfates, alkylaryl sulfonates, and the like, and as the nonionic surfactant, one or more selected from polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, and the like are cationic surfactants One or more selected from alkylamine salts, quaternary ammonium salts, and the like.
- an alkali metal hydroxide is mixed with an aqueous slurry of oxidized carbon black having one or more anionic functional groups on the surface in the presence of one or more water-soluble chelating agents or salts thereof.
- Anion on the surface of oxidized carbon black by neutralizing by heating or by performing a neutralization step of mixing one or more selected from a water-soluble chelating agent or a salt thereof after mixing with alkali metal hydroxide for heat neutralization
- the polyvalent metal ions trapped by the functional group are gradually trapped by the chelating agent and exchanged for alkali metal ions, and then the polyvalent metal ions trapped by the chelating agent in the separation and removal step are separated and removed.
- a high degree of dispersibility due to the repulsive force of the alkali metal ions can be imparted to black. Therefore, according to the present invention, it is possible to provide a method for easily producing an aqueous oxidized carbon black dispersion from which polyvalent metal ions are highly removed and exhibit excellent dispersion stability, and an inkjet ink. A method for producing an aqueous oxidized carbon black dispersion for a composition can be provided.
- Example 1 (1) Preparation of oxidized carbon black-containing slurry 150 g of carbon black (TB # 4500, manufactured by Tokai Carbon Co., Ltd.) was added to 3000 ml of a 2.0 N aqueous solution of sodium persulfate using deionized water, and the reaction temperature was 90 ° C. The surface of carbon black was subjected to liquid phase oxidation by treatment at a stirring speed of 300 rpm for 3 hours. Next, the reduced salt in the obtained slurry was washed with water and desalted and purified using an ultrafiltration membrane (AHP-1010, manufactured by Asahi Kasei Co., Ltd., molecular weight cut off 50000) until the conductivity was less than 3 mS / cm.
- AHP-1010 ultrafiltration membrane
- the pH of the resulting slurry containing oxidized carbon black was pH 3.
- sodium ethylenediaminetetraacetate was added per oxidized carbon black solid content (based on 100% by mass of oxidized carbon black solid content). 5% by mass was added and reacted at a reaction temperature of 25 ° C. and a stirring speed of 300 rpm for 15 minutes.
- the carbon black slurry obtained by the reaction with sodium dihydrogentetraacetate was washed with an ultrafiltration membrane (AHP-1010 manufactured by Asahi Kasei Co., Ltd., molecular weight cut off 50000) until the electrical conductivity dropped below 3 mS / cm.
- AHP-1010 manufactured by Asahi Kasei Co., Ltd., molecular weight cut off 50000
- Example 2 In Example 1 (1) and (2), the concentration of oxidized carbon black was 20 masses as in Example 1 except that disodium nitrilotriacetate was used instead of sodium dihydrogentetraacetate. % Oxidized carbon black water dispersion was prepared.
- Example 3 An oxidized carbon black aqueous dispersion in which the concentration of oxidized carbon black was 20% by mass was prepared in the same manner as in Example 1 except that the reaction temperature was changed from 95 ° C. to 60 ° C. in Example 1 (2).
- Example 1 Oxidized carbon black water having a concentration of oxidized carbon black of 20% by mass in the same manner as in Example 1 except that neither sodium ethylenediaminetetraacetate was added in Examples 1 (1) and (2). A dispersion was prepared.
- Example 2 An oxidized carbon black aqueous dispersion having a concentration of oxidized carbon black of 20% by mass was prepared in the same manner as in Example 1 except that sodium dihydrogentetraacetate was not added in Example 1 (2).
- Example 3 Oxidized carbon black water having a concentration of oxidized carbon black of 20% by mass in the same manner as in Example 1 except that the heat treatment was not performed in Example 1 (2) and the neutralization reaction was performed at room temperature (25 ° C.). A dispersion was prepared.
- the content of the metal component in the oxidized carbon black aqueous dispersion was calculated by the following method. The results are shown in Table 1.
- the content of each metal component is shown as the amount of metal ( ⁇ g) contained in 1 mL of an oxidized carbon black aqueous dispersion having a concentration of 20% by mass.
- a nitric acid solution was added to each oxidized carbon black aqueous dispersion for thermal decomposition, and the content of each metal component was measured by an inductively coupled plasma emission spectroscopic analyzer (ICPS-7510, manufactured by Shimadzu Corporation).
- ICPS-7510 inductively coupled plasma emission spectroscopic analyzer
- Table 1 The obtained results are shown in Table 1.
- the numerical values in the table are the amount of each metal ( ⁇ g) contained in 1 mL of the oxidized carbon black aqueous dispersion having an oxidized carbon black concentration of 20% by mass.
- ⁇ 0.1 means “less than 0.1 ⁇ g / mL”.
- the average particle size and the maximum particle size are 50% as a cumulative particle size in a volume-based cumulative particle size distribution measured using a heterodyne laser Doppler type particle size distribution analyzer (manufactured by Microtrack, UPA model 9340). Mean particle size D50) and 99% particle size (D99).
- the particle size distribution measuring device irradiates the particles that perform Brownian motion in the suspension with laser light, and measures the intensity of Brownian motion, that is, the particle size, from the degree of frequency modulation of the scattered light modulated by the Doppler effect. can do.
- ⁇ Print density> In each aqueous dispersion of oxidized carbon black, the dilution was adjusted so that the concentration of oxidized carbon black would be 3% by mass, printed on a copy paper (XEROX 4024 paper) with a # 6 bar coater, and a Macbeth densitometer (RD- 927) was used to measure the optical density (OD).
- the oxidized carbon black aqueous dispersions obtained in Examples 1 to 3 were mixed with an aqueous solution of oxidized carbon black in the presence of a water-soluble chelating agent and mixed with an alkali metal hydroxide for heat neutralization. And a step of separating and removing the polyvalent metal ion chelate complex from the mixed liquid obtained in the step using a separation membrane, Fe ions, Al ions, Cr ions, It can be seen that the polyvalent metal ions such as Ni ions, Zn ions, Ca ions, and Mg ions are all highly removed.
- the oxidized carbon black aqueous dispersions obtained in Examples 1 to 3 are prepared through the above-described steps, and are obtained by highly removing polyvalent metal ions.
- Ink jet ink composition has little change in viscosity and change in average particle size and maximum particle size of aggregates, exhibits excellent dispersion stability, and is excellent in printing density, surface tension and electrical conductivity. It can be seen that it can exhibit excellent characteristics when used in the above.
- Example 1 Comparative Example 2
- Comparative Example 3 Comparative Example 3
- the oxidized carbon black aqueous dispersion obtained in Comparative Example 1 contains a polyvalent metal ion at a high concentration, and therefore, the fluctuation of the average particle diameter of the aggregate during heating is particularly large. Since it is not only inferior in dispersion stability but also inferior in print density and surface tension, it can be seen that it is not practical when used in an inkjet ink composition.
- ADVANTAGE OF THE INVENTION while being able to provide the method of manufacturing easily the oxidation carbon black aqueous dispersion which can remove the polyvalent metal ion highly and can exhibit the outstanding dispersion stability, it is for inkjet ink compositions.
- a method for producing an oxidized carbon black aqueous dispersion can be provided.
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Abstract
Description
インクジェット記録方式は、微細なノズルヘッドからインキ液滴を吐出して、文字や画像を紙などの記録媒体の表面に記録する方法であり、普通紙をはじめ多種多様な記録媒体に対して非接触で印刷することにより、印刷版をおこすことなくオンデマンドで容易に画像形成できる利点を有している。
また、カーボンブラックの製造工程で使用される冷却水に含まれる金属成分や製造設備の金属腐食などにより溶出する金属成分が、カーボンブラック中に混入してくる場合もある。
しかしながら、イオン交換樹脂の交換容量はさほど大きくなく、頻繁にイオン交換樹脂を再生しなければならず、また、本発明者等の検討によれば、除去対象が多価金属イオンである場合は複数回水で洗浄しても十分に除去し難いことが判明した。これは、カーボンブラック水性分散体を構成する酸化カーボンブラック表面に形成される-COO-基、-SO3 -基、-PO4 2-基等の陰イオン官能基がキレート作用によって金属イオンを捕捉するため、イオン交換樹脂や純水での洗浄では容易に溶離し難いためと考えられる。
し、本知見に基づいて本発明を完成するに至った。
(1)表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーに対し、
水溶性キレート剤またはその塩から選ばれる一種以上の存在下に水酸化アルカリ金属を混合して加熱中和するか、または水酸化アルカリ金属を混合して加熱中和した後に水溶性キレート剤またはその塩から選ばれる一種以上を混合する中和工程と、
当該中和工程で得られた混合液から分離膜を用いて多価金属イオンキレート錯体を分離除去する分離除去工程とを
順次施すことを特徴とする酸化カーボンブラック水性分散体の製造方法、
(2)前記中和工程において、前記酸化カーボンブラックの水性スラリーに対し、pH6~pH12になるように前記水酸化アルカリ金属を混合する上記(1)に記載の酸化カーボンブラック水性分散体の製造方法、
(3)前記水溶性キレート剤がアミノカルボン酸またはその塩である上記(1)に記載の酸化カーボンブラック水性分散体の製造方法、
(4)前記水溶性キレート剤がアミノカルボン酸またはその塩である上記(2)に記載の酸化カーボンブラック水性分散体の製造方法、
(5)前記表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーが、カーボンブラックを液相法で酸化処理した後、pH2~pH4の条件下で水溶性キレート剤またはその塩から選ばれる一種以上と混合し、次いで分離膜を用いて多価金属イオンを予備分離したものである上記(1)に記載の酸化カーボンブラック水性分散体の製造方法、
(6)前記表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーが、カーボンブラックを液相法で酸化処理した後、pH2~pH4の条件下で水溶性キレート剤またはその塩から選ばれる一種以上と混合し、次いで分離膜を用いて多価金属イオンを予備分離したものである上記(2)に記載の酸化カーボンブラック水性分散体の製造方法、
(7)前記表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーが、カーボンブラックを液相法で酸化処理した後、pH2~pH4の条件下で水溶性キレート剤またはその塩から選ばれる一種以上と混合し、次いで分離膜を用いて多価金属イオンを予備分離したものである上記(3)に記載の酸化カーボンブラック水性分散体の製造方法、
(8)前記分離膜が限外濾過膜(UF)、逆浸透膜(RO)または電気透析膜である上記(1)に記載の酸化カーボンブラック水性分散体の製造方法、
(9)前記分離膜が限外濾過膜(UF)、逆浸透膜(RO)または電気透析膜である上記(2)に記載の酸化カーボンブラック水性分散体の製造方法、
(10)前記分離膜が限外濾過膜(UF)、逆浸透膜(RO)または電気透析膜である上記(3)に記載の酸化カーボンブラック水性分散体の製造方法、
(11)上記(1)~(10)のいずれかに記載の方法により得られた酸化カーボンブラック水性分散体に遠心分離処理を施して粗粒分を除去することを特徴とするインクジェットインキ組成物用カーボンブラック水性分散体の製造方法
を提供するものである。
このため、本発明によれば、多価金属イオンが高度に除去され、優れた分散安定性を発揮し得る酸化カーボンブラック水性分散体を簡便に製造する方法を提供することができるとともに、インクジェットインキ組成物用酸化カーボンブラック水性分散体の製造方法を提供することができる。
上記カーボンブラックは、炭素含有量が高く、無定形構造に由来する黒色度が高く、ピーチブラックやランプブラック等に比較して乾燥速度が速く、保存安定性が高く、安価であることから、好ましく使用することができる。
また、カーボンブラックとしては、DBP吸収量が120cm3/100g以上であるものが好ましく、120~180cm3/100gであるものがより好ましく、130~170cm3/100gであるものがさらに好ましい。
なお、本出願書類において、カーボンブラックの平均粒径は、レーザー回折式粒度分布測定装置により測定された、体積基準積算粒度分布における積算粒度で50%の粒径(体積平均粒径D50)を意味する。
ズ社製)、Black Pearls 1000M、Black Pearls 800、Black Pearls 880、Monarch 1300、Monarch 700、Monarch 880、CRX 1444、Regal 330R、Regal 660R、Regal 660、Regal 415R、Regal 415、Black Pearls 4630、Monarch 4630(以上Cabot社製)、Raven 7000、Raven 3500、Raven 5250、Raven 5750、Raven 5000ULTRAII、HV 3396、Raven 1255、Raven 1250、Raven 1190、Raven 1000、Raven 1020、Raven 1035、Raven 1100ULTRA、Raven 1170、Raven 1200(以上Columbian社製)、DB1305(以上KOSCO社製)、SUNBLACK700、705、710、715、720、725、300、305、320、325、X25、X45(以上旭カーボン(株)製)、N220、N110、N234、N121(以上Sid Richardson社製)、ニテロン#300(以上新日化カーボン(株)製)、ショウブラックN134、N110、N220、N234、N219(以上昭和キャボット(株)製)などがあげられる。
液相法により酸化処理する場合は、酸化剤として、例えば、硝酸、硫酸、塩素酸、ペルオキソ硫酸、ペルオキソ硼酸、ペルオキソ炭酸、ペルオキソリン酸などのペルオキシ二酸や、過マンガン酸、重クロム酸、亜塩素酸、過塩素酸、次亜ハロゲン酸、過酸化水素、ホスホン酸、リン酸、亜リン酸、次亜リン酸や、これ等の酸の塩類などを挙げることができ、塩類としては、リチウム、ナトリウム、カリウムなどのアルカリ金属の塩あるいはアンモニア塩などが挙げられる。
上記酸化剤を分散する溶媒としては、水性媒体が好ましく、水性媒体としては水や水溶性の有機溶媒を挙げることができるが、経済性や安全性の面から水、特に脱イオン水が好ましい。
また、カーボンブラック粒子を均一に分散させるため、上記酸化剤を含む分散液には、界面活性剤を添加してもよく、界面活性剤としては、アニオン系、ノニオン系、カチオン系いずれも使用することができる。
上記液相酸化処理に際して、カーボンブラック粒子を予め湿式酸化あるいは乾式酸化してもよく、予め湿式酸化或いは乾式酸化することにより、カーボンブラック粒子を効率よく酸化剤水性溶液中に分散することができ、均一かつ効率的に液相酸化処理することができる。
還元塩を除去する程度は、例えばカーボンブラック分散濃度が20質量%であるときに5mS/cm未満の電導度となるように精製することが望ましい。分離精製が不充分であると、水分散性や分散安定性の低下や分散液の粘度上昇を招き、また分散液による設備腐食などを生じ易くなる。
カーボンブラック表面に-COO-基、-SO3-基および-PO4 2-基等から選ばれる一種以上の陰イオン官能基(酸性官能基)を形成することにより、液相中のpHを上記範囲に容易に維持、制御することができる。
上記アミノカルボン酸またはその塩としては、エチレンジアミン四酢酸塩が好ましく、エチレンジアミン四酢酸塩の具体例としては、エチレンジアミン四酢酸ナトリウム、エチレンジアミン四酢酸カリウムが挙げられる。
一方、酸化カーボンブラックに対する水溶性キレート剤またはその塩の接触量は、酸化カーボンブラック固形分量100質量部に対し、15質量部以下であることが好ましく、12.5質量部以下であることがより好ましく、10質量部以下であることがさらに好ましい。
酸化カーボンブラックに対する水溶性キレート剤またはその塩の接触量は、酸化カーボンブラック固形分量100質量部に対し0.1質量部未満であると、多価金属イオンと水溶性キレート剤との錯体形成が十分に行われ難くなり、酸化カーボンブラック固形分量100質量部に対し15質量部を超えると、錯体形成量がそれ以上増加し難くなることから、不経済になる。
また、接触時間は、30分間以上が好ましく、1時間以上がより好ましく、3時間以上がさらに好ましい。
このため、還元塩の除去処理を行った後にスラリー中に三価金属イオンを中心とする多価金属イオンとのキレート錯体が残存した場合であっても、水溶性キレート剤と多価金属イオンとのキレート結合が維持され、引き続く中和工程においてカーボンブラック表面に多価金属イオンが捕捉されることを抑制することができる。
表面に酸性基を有する自己分散型カーボンブラックとは、酸性基を含む少なくとも一種の親水性基がカーボンブラックの表面に直接、若しくは他の原子団を介して結合したものであって、水中に懸濁して分散液とした際に界面活性剤や高分子化合物を添加することなく安定した分散状態を保持することができ、その分散液の表面張力がほとんど水と同等の値を示すものを意味する。
本発明に係る酸化カーボンブラック水性分散体の製造方法において、酸化カーボンブラックの酸性水酸基量は、酸化カーボンブラックのカルボキシル基(-COO-)量およびヒドロキシル基(-O-)量の和を意味する。酸化カーボンブラックの水性媒体への分散性等を考慮した場合、カーボンブラック粒子表面の官能基としては、酸性水酸基が重要であり、特にカルボキシル基およびヒドロキシル基が大きな役割を果たすことから、酸化カーボンブラック粒子の酸性水酸基量は、実質的にカルボキシル基量とヒドロキシル基量との和とみなすことができる。
なお、本出願書類において、カルボキシル基量は、0.976mol/dm3の炭酸水素ナトリウム0.5dm3に、酸化カーボンブラック2gを添加して、6時間振騰した後、三価カーボンブラックを反応液からろ過分離し、濾液を0.05mol/dm3の水酸化ナトリウム水溶液にて中和滴定したときの値を意味する。
なお、本出願書類において、ヒドロキシル基量は、2、2′-ジフェニル-1-ピクリルヒドラジル(DPPH)を四塩化炭素中にて溶解して5×10-4mol/l溶液を作製し、該溶液中に酸化カーボンブラック粒子を0.1~0.6g添加し、60℃の恒温槽中にて6時間攪拌した後、濾別し、濾液を紫外線吸光光度計で測定して吸光度から算出した方法を意味する。
なお、本出願書類において、-SO3H基量や-PO4H2基量は、例えば、液相法により酸化カーボンブラックを生成した後、液相酸化により生成したスラリー中の還元塩を除去し、さらには水分を除去した酸化カーボンブラックを測定対象とし、X線光電子分光装置(Surface Science Instruments 社製 S-Probe ESCA 2803型)を用いてカーボンブラック表面の結合エネルギーの強度を測定することにより、-SO3H基や-PO4H2基を同定した上で、カルボキシル基量と同じ方法で求めた値を意味する。
なお、本出願書類において、酸化カーボンブラックの平均粒径は、レーザー回折式粒度分布測定装置により測定された、体積基準積算粒度分布における積算粒度で50%の粒径(体積平均粒径D50)を意味する。
上記酸化カーボンブラックを分散する水性媒体としては水や水溶性の有機溶媒を挙げることができるが、経済性や安全性の面から水、特に脱イオン水が好ましい。
また、上記水性スラリー中の酸化カーボンブラックの固形分濃度は、1.0~20.0質量%であることが好ましく、1.0~15.0質量%であることがより好ましく、1.0~10.0質量%であることがさらに好ましい。
(i)表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーに対し、水溶性キレート剤またはその塩から選ばれる一種以上を混合した後、水酸化アルカリ金属を混合して加熱中和処理してもよいし、
(ii)表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーに対し、水溶性キレート剤またはその塩から選ばれる一種以上と水酸化アルカリ金属とを同時に混合して加熱中和処理してもよいし、
(iii)表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーに対し、水酸化アルカリ金属を混合して加熱中和処理した後、水溶性キレート剤またはその塩から選ばれる一種以上を混合してもよい。
酸化カーボンブラックの水性スラリーに対し、pH6.0~pH12.0になるように水酸化アルカリ金属を混合し、加熱中和することにより、酸化カーボンブラック表面に捕捉された多価金属イオン、特に二価金属イオン(二価鉄イオン、亜鉛イオン、ニッケルイオン、マグネシウムイオン、カルシウムイオン等)が溶出して水酸化アルカリと交換され、溶出した多価金属イオンが水溶性キレート剤と多価金属イオンキレート錯体を形成し水溶性となってスラリー中に溶解するため、膜分離により容易に除去することができる。
加熱中和する際の加熱温度は、30℃~95℃が好ましく、60℃~95℃がより好ましく、80℃~95℃がさらに好ましい。
また、中和工程において、表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリー、水酸化アルカリおよび水溶性キレート剤を混合し、保持する時間は、30分間~12時間が好ましく、1~8時間がより好ましく、2~5時間がさらに好ましい。
上記分離膜により、酸化カーボンブラック表面に捕捉された多価金属イオンを多価金属イオンキレート錯体として分離除去することができ、同時に余剰の水酸化アルカリによる残塩を系外に除去することができるとともに、酸化カーボンブラック粒子の再凝集を抑制する上でも有効である。
遠心分離処理を施す遠心分離機としては、特に限定されないが、縦型遠心分離機、横型遠心分離機等から選ばれる一種以上を挙げることができる。
遠心分離処理は、目的とする最大粒子径の存在数に応じて、遠心分離機の遠心力や流量を調整して行えばよい。
インクジェットインキ組成物が保湿剤を含有することにより、インキ組成物中の水性媒体の蒸発速度を抑えて閉塞を抑制することができる。
インクジェットインキ組成物が樹脂を含有することにより、酸化カーボンブラックの印刷基材に対する定着性を向上させることができる。
このため、本発明によれば、多価金属イオンが高度に除去され、優れた分散安定性を発揮し得る酸化カーボンブラック水性分散体を簡便に製造する方法を提供することができるとともに、インクジェットインキ組成物用酸化カーボンブラック水性分散体の製造方法を提供することができる。
以下に本発明の内容を具体的な例を比較例とともに挙げつつ説明する。ただし、本発明はこれら例に限定されるものではない。
なお、以下の実施例および比較例において、pHはJIS Z8802に規定する方法により求めた。
(1)酸化カーボンブラック含有スラリーの調製
カーボンブラック(東海カーボン(株)製、TB#4500)150gを、脱イオン水を用いた過硫酸ナトリウム2.0N水溶液3000mlに添加し、反応温度90℃、撹拌速度300rpmで3時間処理することにより、カーボンブラックの表面を液相酸化した。
次いで、得られたスラリー中の還元塩を限外濾過膜(旭化成(株)製、AHP-1010、分画分子量50000)を用いて電導度3mS/cmを下回るまで水洗洗浄して脱塩精製した。得られた酸化カーボンブラックを含むスラリーのpHはpH3であった。
上記水洗洗浄した酸化カーボンブラックを含むスラリー(酸化カーボンブラック固形分濃度5質量%)に対し、エチレンジアミン四酢酸二水素ナトリウムを、酸化カーボンブラック固形分当たり(酸化カーボンブラック固形分100質量%に対し)5質量%添加し、反応温度25℃、撹拌速度300rpmで15分間反応させた。
上記エチレンジアミン四酢酸二水素ナトリウムと反応させて得られたカーボンブラックスラリーを限外濾過膜(旭化成(株)製AHP-1010、分画分子量50000)で電導度3mS/cmを下回るまで水洗洗浄して脱塩精製することにより、多価金属イオンを予備分離した酸化カーボンブラック含有スラリーを得た。
上記(1)で得られた多価金属イオンを予備分離した酸化カーボンブラック含有スラリー中に、エチレンジアミン四酢酸二水素ナトリウムを、酸化カーボンブラック固形分当たり(酸化カーボンブラック固形分100質量%に対し)5質量%添加するとともに、スラリーのpHが11になるように水酸化ナトリウム水溶液を添加し、反応温度95℃、撹拌速度300rpmで3時間中和反応を行った。
上記(2)で中和反応を行って得られた混合液に対し、再び限外濾過膜(旭化成(株)製AHP-1010、分画分子量50000)を用いて残存する塩とキレート錯体を水洗洗浄するとともに濃縮処理して、酸化カーボンブラックの濃度が20質量%である酸化カーボンブラック水分散体を調製した。
実施例1(1)および(2)において、エチレンジアミン四酢酸二水素ナトリウムに代えて、いずれもニトリロ三酢酸二ナトリウムを使用した以外は、実施例1と同様にして酸化カーボンブラックの濃度が20質量%である酸化カーボンブラック水分散体を調製した。
実施例1(2)において、反応温度を95℃から60℃に変更した以外は、実施例1と同様にして酸化カーボンブラックの濃度が20質量%である酸化カーボンブラック水分散体を調製した。
実施例1(1)および(2)において、エチレンジアミン四酢酸二水素ナトリウムをいずれも添加しなかった以外は、実施例1と同様にして酸化カーボンブラックの濃度が20質量%である酸化カーボンブラック水分散体を調製した。
実施例1(2)においてエチレンジアミン四酢酸二水素ナトリウムを添加しなかった以外は、実施例1と同様にして酸化カーボンブラックの濃度が20質量%である酸化カーボンブラック水分散体を調製した。
実施例1(2)において加熱処理を行わず、常温(25℃)で中和反応を行った以外は、実施例1と同様にして酸化カーボンブラックの濃度が20質量%である酸化カーボンブラック水分散体を調製した。
各酸化カーボンブラック水分散体に硝酸液を加えて熱分解した上で、誘導結合プラズマ発光分光分析装置((株)島津製作所製、ICPS-7510)により各金属成分の含有量を測定した。
なお、表1において、「<0.1」は、「0.1μg/mL未満」を意味する。
各酸化カーボンブラック水分散体を密閉容器(容量100ml)に収容し、60℃の保温器中で2週間に亘って保持したときの、加熱開始直後および2週間経過後の酸化カーボンブラック水分散体の粘度変化を測定した。
上記粘度は回転振動式粘度計(山一電機(株)製、VM-100A-L)を用いて測定した。
上記のとおり各酸化カーボンブラック水分散体を密閉容器(容量100ml)に収容し、60℃の保温器中で2週間に亘って保持したときの、加熱開始直後および2週間経過後の平均粒子径および最大粒子径を各々測定した。
上記平均粒子径および最大粒子径は、ヘテロダインレーザドップラー方式粒度分布測定装置(マイクロトラック社製、UPA model9340)を用いて測定したときの、体積基準積算粒度分布における積算粒度で50%の粒子径(平均粒子径D50)および99%の粒子径(D99)を意味する。上記粒度分布測定装置により、懸濁液中でブラウン運動を行っている粒子にレーザ光を照射し、ドップラー効果により変調した散乱光の周波数の変調度合いからブラウン運動の激しさ、すなわち粒子径を測定することができる。
各酸化カーボンブラック水分散体において、酸化カーボンブラックの濃度が3質量%になるように各々希釈調整し、♯6バーコータによりコピー紙(XEROX4024紙)に印字し、マクベス濃度計(コルモーゲン社製 RD-927)を用いて光学濃度(O.D.)を測定した。
各酸化カーボンブラック水分散体の表面張力を、表面張力測定器((株)島津製作所製、DN)により測定した。
各酸化カーボンブラック水分散体の電気伝導度を、電気伝導度測定装置(東亜電波工業(株)製、CM-40V)により測定した。
また、表2より、実施例1~実施3で得られた酸化カーボンブラック水分散液は、上記工程を経て調製されてなる、多価金属イオンが高度に除去されてなるものであることから、粘度変化や凝集体の平均粒子径および最大粒子径の変化が少なく、優れた分散安定性を示すものであるとともに、さらに、印字濃度、表面張力および電気伝導度に優れるために、インクジェットインキ組成物に使用したときに優れた特性を発揮し得るものであることが分かる。
また、表2より、比較例1で得られた酸化カーボンブラック水分散液は、多価金属イオンを高い濃度で含むものであることから、特に加温時の凝集体の平均粒子径の変動が大きく、分散安定性に劣るばかりか、印字濃度や表面張力に劣るものであるので、インクジェットインキ組成物に使用したときに実用に耐えないものであることが分かる。
Claims (11)
- 表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーに対し、
水溶性キレート剤またはその塩から選ばれる一種以上の存在下に水酸化アルカリ金属を混合して加熱中和するか、または水酸化アルカリ金属を混合して加熱中和した後に水溶性キレート剤またはその塩から選ばれる一種以上を混合する中和工程と、
当該中和工程で得られた混合液から分離膜を用いて多価金属イオンキレート錯体を分離除去する分離除去工程とを
順次施すことを特徴とする酸化カーボンブラック水性分散体の製造方法。 - 前記中和工程において、前記酸化カーボンブラックの水性スラリーに対し、pH6~pH12になるように前記水酸化アルカリ金属を混合する請求項1に記載の酸化カーボンブラック水性分散体の製造方法。
- 前記水溶性キレート剤がアミノカルボン酸またはその塩である請求項1に記載の酸化カーボンブラック水性分散体の製造方法。
- 前記水溶性キレート剤がアミノカルボン酸またはその塩である請求項2に記載の酸化カーボンブラック水性分散体の製造方法。
- 前記表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーが、カーボンブラックを液相法で酸化処理した後、pH2~pH4の条件下で水溶性キレート剤またはその塩から選ばれる一種以上と混合し、次いで分離膜を用いて多価金属イオンを予備分離したものである請求項1に記載の酸化カーボンブラック水性分散体の製造方法。
- 前記表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーが、カーボンブラックを液相法で酸化処理した後、pH2~pH4の条件下で水溶性キレート剤またはその塩から選ばれる一種以上と混合し、次いで分離膜を用いて多価金属イオンを予備分離したものである請求項2に記載の酸化カーボンブラック水性分散体の製造方法。
- 前記表面に一種以上の陰イオン官能基を有する酸化カーボンブラックの水性スラリーが、カーボンブラックを液相法で酸化処理した後、pH2~pH4の条件下で水溶性キレート剤またはその塩から選ばれる一種以上と混合し、次いで分離膜を用いて多価金属イオンを予備分離したものである請求項3に記載の酸化カーボンブラック水性分散体の製造方法。
- 前記分離膜が限外濾過膜(UF)、逆浸透膜(RO)または電気透析膜である請求項1に記載の酸化カーボンブラック水性分散体の製造方法。
- 前記分離膜が限外濾過膜(UF)、逆浸透膜(RO)または電気透析膜である請求項2に記載の酸化カーボンブラック水性分散体の製造方法。
- 前記分離膜が限外濾過膜(UF)、逆浸透膜(RO)または電気透析膜である請求項3に記載の酸化カーボンブラック水性分散体の製造方法。
- 請求項1~請求項10のいずれかに記載の方法により得られた酸化カーボンブラック水性分散体に遠心分離処理を施して粗粒分を除去することを特徴とするインクジェットインキ組成物用カーボンブラック水性分散体の製造方法。
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Also Published As
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ES2769751T3 (es) | 2020-06-29 |
CN107207890A (zh) | 2017-09-26 |
EP3252111A1 (en) | 2017-12-06 |
KR20170110086A (ko) | 2017-10-10 |
JP2016141704A (ja) | 2016-08-08 |
JP6548109B2 (ja) | 2019-07-24 |
EP3252111B1 (en) | 2019-12-25 |
US20180022926A1 (en) | 2018-01-25 |
EP3252111A4 (en) | 2018-10-17 |
US10927262B2 (en) | 2021-02-23 |
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