WO2006061995A1 - Aqueous pigment dispersion, ink-jet recording ink, and recording method and textile printing method using the same - Google Patents

Aqueous pigment dispersion, ink-jet recording ink, and recording method and textile printing method using the same Download PDF

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Publication number
WO2006061995A1
WO2006061995A1 PCT/JP2005/021561 JP2005021561W WO2006061995A1 WO 2006061995 A1 WO2006061995 A1 WO 2006061995A1 JP 2005021561 W JP2005021561 W JP 2005021561W WO 2006061995 A1 WO2006061995 A1 WO 2006061995A1
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Prior art keywords
ink
pigment dispersion
styrene
weight
pigment
Prior art date
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PCT/JP2005/021561
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French (fr)
Japanese (ja)
Inventor
Shunji Maekawa
Hiroki Tanaka
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Kiwa Chemical Industry Co., Ltd.
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Publication of WO2006061995A1 publication Critical patent/WO2006061995A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing
    • 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
    • C09D11/322—Pigment inks
    • 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
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • D06P1/5257—(Meth)acrylic acid

Definitions

  • the present invention relates to an aqueous pigment dispersion, an ink jet recording ink using the same, a recording method, and a textile printing method. More specifically, in an inkjet recording method, an aqueous pigment-based ink jet recording ink excellent in prevention of clogging of nozzles of a recording head and ink storage stability, an aqueous pigment dispersion used in the ink, and The present invention relates to a recording method and a printing method using the ink.
  • Aqueous inkjet recording ink generally takes the form of a water-soluble dye solution or a liquid in which a water-insoluble colorant is dispersed in water or an aqueous solution containing a water-soluble organic solvent.
  • ink jet recording ink using a pigment is used.
  • item (1) is particularly important.
  • the on-demand system has a problem in that ejection failure occurs during continuous operation for a long period of time because the ejection of nozzle force ink is temporarily stopped even during continuous operation.
  • Patent Document 1 As a document concerning redispersibility of pigment ink, for example, Patent Document 1 below uses a ternary copolymer having an acid value of 90 to 130 made of acrylic acid, styrene, and ⁇ -methylstyrene as an aqueous resin. A water-based ink is described. However, the ink of Patent Document 1 has insufficient redispersibility because the acid value of the aqueous resin is low.
  • Patent Document 2 discloses that the acid value in the form of a free acid of a styrene-acrylic acid copolymer is 150 mgKOHZg or more and less than 250 mgKO HZg, A water-based ink composition is described in which the ratio of the styrene-acrylic acid copolymer to the insoluble pigment is 5% by weight or more and less than 20% by weight.
  • Patent Document 3 listed below uses an organic polymer compound (A) having a Tg higher than 50 ° C and an acid value of 100 to 300 KOHmgZg and a weight average molecular weight of 2,000-30,000, and a pigment.
  • a specific organic polymer compound (B) is further added after being dispersed in water.
  • the ratio of the styrene / acrylic acid copolymer to the water-insoluble dye is 5% by weight or more and less than 20% by weight, redispersibility is not sufficient in the case of pigment ink.
  • Katsuta In the invention described in Patent Document 3, ammonia and a basic solvent are actually used as the neutralizing agent for the styrene-acrylic acid copolymer.
  • ammonia and a basic solvent are actually used as the neutralizing agent for the styrene-acrylic acid copolymer.
  • the ink using the neutralized polymer dispersant as the pigment dispersant was not sufficiently redispersible.
  • Patent Document 4 shown below contains a pigment, a resin dispersant, and a resin emulsion, and the weight ratio of the pigment to the resin dispersant is 20: 1 to 5: 2.
  • a neutralizing agent for a rosin dispersant organic amines and aqueous ammonia are described, and an ink using a polymer dispersant neutralized with these neutralizing agents as a pigment dispersant is: Redispersibility was not enough.
  • Patent Document 1 JP-A-8-253716
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-294789
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-292838
  • Patent Document 4 JP-A-9-176533
  • the present invention solves the problems of the conventional water-based pigment-based ink jet recording inks as described above, while maintaining the originally required storage stability and performance of high-quality recorded images, etc.
  • ink jet recording with good re-dispersibility which provides stable ejection even during long-time continuous operation with excellent anti-clogging and good dispersion stability, even after the device has been stopped for a long time.
  • An aqueous pigment dispersion suitable for ink, an ink jet recording ink using the pigment dispersion, and a recording method and a printing method using the ink are provided.
  • the present inventors easily redisperse a highly reliable pigment ink composition that is less likely to cause nozzle clogging in an inkjet head when the ink having the same composition is calorie even after the ink has dried.
  • the object can be achieved by selecting a specific polymer dispersant and a specific neutralizer. This is the headline and the present invention.
  • the aqueous pigment dispersion of the present invention contains water, a pigment, and a polymer dispersant, and the content of the polymer dispersant is 30 to 100% by weight with respect to the pigment.
  • the polymer dispersant contains styrene having an acid value of 160 to 300 mg KOHZg and a weight average molecular weight of 8,000 to 20,000. It is a polymer dispersant obtained by neutralizing a (meth) acrylic acid copolymer with an alkali metal hydroxide.
  • the ink for inkjet recording of the present invention is characterized by using the above-described aqueous pigment dispersion for inkjet recording.
  • the ink jet recording method of the present invention is characterized by printing on a paper product using the ink for ink jet recording of the present invention.
  • the ink jet textile printing method of the present invention is characterized by printing on a textile product using the ink for ink jet recording of the present invention.
  • An ink for ink jet recording using the aqueous pigment dispersion of the present invention provides an ink with good redispersibility while maintaining the performance of originally required storage stability, high quality recorded images, and the like. It is excellent in preventing clogging of the nozzles, and has an effect that stable discharge can be obtained by normal cleaning even when the operation of the apparatus is stopped for a long time even during a long continuous operation.
  • the aqueous pigment dispersion of the present invention is useful for the ink, and various additives and water are added as necessary at the time of ink adjustment to adjust the pigment concentration to be suitable for the intended use.
  • the ink is suitable for obtaining ink and has good storage stability until ink adjustment.
  • the redispersibility of the obtained ink is improved, it is excellent in preventing clogging of the nozzle by the obtained ink, and the operation of the apparatus is prolonged even during continuous operation of the ink jet recording plotter for a long time. Even after a pause, the stable cleaning can be obtained by normal cleaning, which is useful.
  • the ink jet recording method and the ink jet printing method using the ink for ink jet recording of the present invention can prevent nozzle clogging while maintaining the performance of a high-quality recorded image or the like. It is excellent, and even during continuous operation for a long time, stable discharge can be obtained by normal cleaning even after the operation of the device is stopped for a long time.
  • the styrene- (meth) acrylic acid copolymer used for the polymer dispersant has an acid value of 200 to 250 mgKOHZg.
  • the styrene (meth) acrylic acid copolymer used for the polymer dispersant has a weight average molecular weight of 10,000 to 18,000. Is preferred.
  • the styrene- (meth) acrylic acid copolymer is preferably a copolymerized resin manufactured by a continuous bulk polymerization method.
  • a silicon-based nonionic surfactant As a surface conditioner, a silicon-based nonionic surfactant, an alcohol alkoxylate-based nonionic surfactant, and an acetylene glycol-based nonionic surfactant are used. And at least one selected from the group consisting of an agent and a fluorine-based nonionic surfactant.
  • the surface conditioner is a polyether-modified polydimethylsiloxane which is a kind of the silicone-based noion surfactant. .
  • the aqueous pigment dispersion of the present invention preferably contains glycerin as a water-soluble organic solvent.
  • the water-based pigment dispersion of the present invention preferably contains polyether-modified polydimethylsiloxane and glycerin, and the content power of the polyether-modified polydimethylsiloxane is preferably the total amount of the aqueous pigment dispersion.
  • the content of glycerin is preferably 10 to 30% by weight relative to the total amount of the aqueous pigment dispersion.
  • the content of the styrene mono (meth) acrylic acid copolymer is 1 to 6% by weight with respect to the total amount of the ink.
  • the styrene (meth) acrylic acid copolymer is obtained by neutralizing the copolymer with an alkali metal hydroxide.
  • the content of the styrene (meth) acrylic acid copolymer is a content when converted to a state before neutralization with an alkali metal hydroxide.
  • the content of styrene (meth) acrylic acid copolymer and the content of polymer dispersant mean this.
  • the content of the polymer dispersant is 30 to: LOO weight relative to the pigment which is a ratio in the aqueous pigment dispersion of the present invention. % Or more than the above ratio when adjusting the ink by adding a polymer dispersant.
  • the content of the styrene (meth) acrylic acid copolymer is in the range of 1 to 6% by weight with respect to the total amount of the ink. I like it.
  • the ink for ink jet recording of the present invention is an ink for ink jet recording in which the ink for ink jet recording contains glycerin. It is preferably 50% by weight.
  • the ink for ink jet recording of the present invention is an ink for ink jet recording in which the ink for ink jet recording contains a surface conditioner, and the content of the surface conditioner is based on the total amount of the ink. Preferable to be 0.05 to 2% by weight.
  • the surface conditioner is a polyether-modified polydimethylsiloxane.
  • the ink for inkjet recording of the present invention preferably further contains a resin emulsion.
  • the present invention is described in further detail below.
  • the polymer dispersant used in the present invention is for dispersing a pigment in an aqueous medium.
  • the styrene (meth) acrylic acid copolymer having an acid value of 160 to 300 mgKOHZg and a weight average molecular weight of 8,000 to 20,000 is used. It is a polymer dispersant obtained by neutralizing a polymer with an alkali metal hydroxide.
  • (meth) acrylic acid means "! acrylic acid "... and Z or” ... "methacrylic acid” ... To do.
  • styrene (meth) acrylic acid copolymer examples include styrene acrylic acid copolymer, styrene acrylic acid acrylic ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid acrylic ester.
  • examples include copolymers, styrene ⁇ -methylstyrene acrylic acid copolymers, and styrene ⁇ -methylstyrene-methacrylic acid copolymers.
  • the styrene- (meth) acrylic acid-based copolymer used in the present invention has an acid value of 160 to 300 mgKOHZg, preferably 200 to 250 mgKOH / g.
  • the acid value is less than 160, the solubility of the resin in water tends to deteriorate even when neutralized with an alkali metal hydroxide.
  • the acid value exceeds 300, the affinity with an aqueous medium increases. , Printing The water resistance of later printing tends to be poor.
  • the acid value of the styrene (meth) acrylic acid-based copolymer rosin represents the number of mg of KOH required to neutralize the coconut lg, and is measured according to JIS-K3054.
  • the styrene (meth) acrylic acid copolymer has a weight average molecular weight of 8000 to 20000, preferably 10,000 to 18,000. When the molecular weight force is less than 8000 / J, the redispersibility decreases, and when it exceeds 20000, the ability to disperse the pigment decreases, which is not preferable.
  • the weight average molecular weight of the styrene (meth) acrylic acid copolymer is measured by a GPC (gel permeation chromatograph) method.
  • the styrene (meth) acrylic acid copolymer is preferably a copolymerized resin manufactured by a continuous bulk polymerization method.
  • Manufacture by a continuous bulk polymerization method provides a coagulant with an accurate and constant composition ratio of the copolymer, so it is possible to suppress the production of water-insoluble coagulant containing a large amount of monomer components without acid groups. Is preferable because it is stable.
  • neutralization is performed using a neutralizing agent.
  • the pH during neutralization is preferably adjusted to 8.5 to 10 and more preferably 8.5 to 9.0 from the viewpoint of solubility of the styrene (meth) acrylic acid copolymer.
  • an alkali metal hydroxide is used as the neutralizing agent.
  • the alkali metal hydroxide lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable.
  • alkali metal hydroxide By using alkali metal hydroxide as a neutralizing agent, the redispersibility of the ink can be improved.
  • an organic base such as amines or ammonia is used as the alkali source, it becomes impossible to obtain an ink having excellent ink redispersibility, continuous ejection stability, and ejection properties after standing for a long time.
  • the styrene (meth) acrylic acid copolymer is obtained by neutralizing a solid resin with an alkali metal hydroxide in advance from the viewpoint of workability at the time of pigment dispersion and ink concentration adjustment. It is preferable to use after preparing a 20 to 30% by weight aqueous solution of rosin.
  • the amount of the styrene (meth) acrylic acid copolymer used in the production of the aqueous pigment dispersion is preferably 30 to LOO parts by weight with respect to 100 parts by weight of the pigment. More preferably, it is 30-80 weight part, More preferably, it is 30-60 weight part. When the amount is 30 parts by weight or more, the pigment can be sufficiently dispersed, and when the amount is 100 parts by weight or less, an increase in viscosity at the time of pigment dispersion can be prevented.
  • the amount used here is the same as defined by the content of the styrene (meth) acrylic acid copolymer, and the styrene (meth) acrylic acid copolymer is an alkali metal hydroxide as described above.
  • the above-mentioned copolymer obtained by neutralization with an ionic compound is used.
  • the amount of the styrene (meth) acrylic acid copolymer used above is the same as that before neutralization with an alkali metal hydroxide. This is the amount used when converted.
  • the pigment used in the present invention is not particularly limited, and examples thereof include carbon black and organic pigments.
  • Examples of carbon black include furnace black and channel black. These carbon blacks can be used alone or in combination with multiple types of carbon black.
  • organic pigments examples include soluble azo pigments, insoluble azo pigments, insoluble bisazo pigments, condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments. Thioindigo pigments, anthraquinone pigments and quinophthalone pigments.
  • One kind of these organic pigments may be used, or a plurality of kinds of organic pigments may be used in combination.
  • the amount of the pigment used is preferably 5 to 30% by weight based on the total weight of the aqueous pigment dispersion. More preferably, it is 10 to 25% by weight.
  • a surface conditioner during the production of the aqueous pigment dispersion.
  • the surface conditioner include silicon-based nonionic surfactants, alcohol alkoxylate-based nonionic surfactants, acetylene glycol-based nonionic surfactants, and fluorine-based nonionic surfactants.
  • Polyether-modified polydimethylsiloxane which is a surfactant is preferred.
  • the amount of the surface conditioner used is preferably 0.5 to 3% by weight based on the total weight of the aqueous pigment dispersion. More preferably, it is 1.0 to 2.5% by weight. It is preferable to add the surface conditioner in this range during the production of the pigment dispersion because the wettability of the pigment is improved and the dispersion can be performed more smoothly.
  • a water-soluble organic solvent when producing the aqueous pigment dispersion.
  • glycerin diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, propylene glycol and the like are preferable.
  • the amount of the water-soluble organic solvent used in the production of the aqueous pigment dispersion prevents the surface of the dispersion from drying during the production of the pigment dispersion, and improves the storage stability of the pigment dispersion until it is converted into an ink.
  • the content is preferably 10 to 30% by weight based on the total weight of the aqueous pigment dispersion. More preferably, it is 15 to 25% by weight.
  • the aqueous pigment dispersion of the present invention is suitable for adjusting the pigment concentration suitable for the intended use by adding various additives and water at the time of ink adjustment, and also has good storage stability until ink adjustment. It is.
  • the redispersibility of the obtained ink is improved, it is excellent in preventing nozzle clogging by the obtained ink, and the operation of the apparatus is prolonged even during continuous operation of an ink jet recording plotter for a long time. Even after a period of time pause, stable ejection can be obtained by a predetermined normal cleaning designated by the ink jet recording plotter, which is useful.
  • the ink for inkjet recording of the present invention is prepared using the aqueous pigment dispersion.
  • the content of the styrene (meth) acrylic acid copolymer is 0.5 with respect to the total weight of the ink for the purpose of maintaining good dispersibility and storage stability of the pigment.
  • ⁇ 8 wt% is preferred. More preferably 1 to 6% by weight, Particularly preferred is 2 to 4% by weight.
  • the content of the pigment of the present invention is generally preferably 0.5 to 8% by weight based on the total weight of the ink, since dispersion stability is maintained and a necessary printing density is obtained. More preferably, it is 0.5 to 6% by weight.
  • examples of the water-soluble organic solvent used include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and butylene glycol.
  • Polyhydric alcohols such as hexylene glycol, thiodiglycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl etherenole, ethylene glycol monobutino enoate, diethylene glycol monomethyl ether, diethylene glycol mono Glycolols such as ethyl ether, diethyleneglycolone monobutinoleethenole, propyleneglycololemonomethinoleethenore Over Te le include methanol, ethanol, n - propyl alcohol, and isopropyl alcohol.
  • glycerin diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, and propylene glycol are preferable.
  • glycerin is preferred as a humectant.
  • the content of these water-soluble organic solvents is preferably 5 to 50% by weight with respect to the total weight of the ink from the viewpoint of adjusting the viscosity of the ink and preventing clogging due to the moisturizing effect. More preferably, it is 10 to 45% by weight, and particularly preferably 15 to 40% by weight.
  • a penetrating agent is further used in order to increase the permeability to the printing material. It is preferable to do this.
  • penetrants used in the ink of the present invention include nonionic surfactants such as acetylene glycol, acetylene alcohol, silicon, and polyoxyethylene alkyl ether, sodium alkyl sulfate, and sodium alkylbenzene sulfonate.
  • Surfactants such as sodium oleate and sodium dioctylsulfosuccinate, alkylene glycol monoalkyl ether, alkyle Water-soluble organic solvents such as ethylene glycol and monohydric alcohols are preferred.
  • the amount of the penetrating agent added is in the range of 0.05 to 2% by weight, preferably 0.1 to 1% by weight, based on the total weight of the ink. If it is less than 0.05% by weight, the effect is reduced, and if it exceeds 2% by weight, the effect is hardly improved. By adding these within this range, the dryness of the printed matter is improved, and even if continuous printing is performed, the previous printed portion is not transferred to the back side of the next print medium, and thus is particularly suitable for the inkjet printing method. High-speed printing is possible.
  • a resin emulsion is further added in order to increase the scratch resistance of the substrate. It is preferable to contain.
  • the ink for inkjet recording of the present invention can fix the pigment more strongly to various textiles by using a resin emulsion as a binder, particularly when dyeing various textiles by the inkjet printing method.
  • a resin emulsion as a binder
  • Various fastnesses such as abrasion resistance and washing resistance are improved, which is preferable.
  • the content of the resin emulsion is in the range of 0.5 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the ink. When the content of the resin emulsion is 0.5% by weight or more, the intended fastness can be obtained, and by setting it to 20% by weight or less, the viscosity of the ink can be prevented from being too high. No adverse effect.
  • the resin component of such a resin emulsion is an acrylic resin, a styrene one-aryl resin, a vinyl acetate resin, a styrene butadiene resin, or a salt vinyl resin. Butadiene-based resin, styrene-based resin, and the like.
  • rosin emulsions include, for example, trade names "John Crill 537”, “Jon Crill 775", “John Crill 7610”, etc., made of styrene-acrylic resin manufactured by Johnson Polymer Co., Ltd.
  • the ink for inkjet recording of the present invention uses a compound represented by the following chemical formula (I) (wherein R represents an alkyl group having 25 to 50 carbon atoms, and n represents 10 to LOO). can do.
  • R is preferably an alkyl group having 30 to 50 carbon atoms, and particularly preferably an alkyl group having 30 to 35 carbon atoms.
  • n is preferably 20 to: LOO, particularly preferably 30 to: LOO.
  • the alkyl group may be linear or branched, but the linear alkyl group is preferable.
  • the HLB of this compound is 10 or more, preferably 14-18, from the viewpoint of solubility in water.
  • the content of the compound of formula (I) is preferably 0.1 to 1.5% by weight, more preferably 0.1 to 1.0% by weight, based on the total amount of the ink.
  • the use in the range of 0.1 to 1.5% by weight is preferable because the added amount is too large and the viscosity of the ink becomes too high, and the effect of improving the redispersibility is exhibited.
  • additives may be added to the ink of the present invention as needed within a range not impeding the achievement of the object of the present invention.
  • surface modifiers hydrotropes, PH modifiers, viscosity modifiers, preservatives, fungicides, light stabilizers, chelating agents, antifoaming agents and the like.
  • a silicon-based nonionic surfactant an alcohol alkoxylate-based nonionic surfactant, an acetylene glycol-based nonionic surfactant, a fluorine-based nonionic surfactant
  • polyether-modified polydimethylsiloxane which is a silicone-based nonionic surfactant.
  • the premixing liquid is finely dispersed in a wet medium mill such as a sand mill to obtain an aqueous pigment dispersion.
  • aqueous pigment dispersion water, if necessary, a resin emulsion, a penetrant, a water-soluble organic solvent, the compound of the above chemical formula (I), and the like are added to adjust the concentration, and then the filter paper. Use it as an ink for ink jet recording after being filtered by etc.
  • the high molecular dispersant obtained from the styrene (meth) acrylic acid copolymer may be further added during the concentration adjustment in order to improve the redispersibility of the pigment.
  • the average particle size of the pigment obtained by the above method is preferably 200 nm or less, more preferably 50 to 150 nm.
  • the power exemplified for the pigment, the styrene (meth) acrylic acid copolymer, the neutralizer, the water-soluble organic solvent, the resin emulsion, the penetrant, and other components is limited to this example. It is not a thing.
  • part represents “weight part” unless otherwise specified
  • % represents “weight%” unless otherwise specified.
  • Pigment Dispersion 1 25 parts of Pigment Dispersion 1 and 16 parts of “Jonkrill 537” (made by Johnson Polymer Co., Ltd., styrene-acrylic resin, acid value 40, 46% solids of resin) as penetrant.
  • “BYK—DYNWET800” produced by Big Chemi ⁇ Japan Co., Ltd., alcohol alkoxylate surfactant
  • 0.5 parts 15 parts glycerin as water-soluble organic solvent, polyether-modified polydimethylsiloxane as surface conditioner
  • BY K-348 manufactured by Big Chemie Japan Co., Ltd.
  • An ink was prepared by adjusting the pigment concentration to 0.35% by adding 0.3 parts of water, 100 parts of the total amount of water.
  • yellow pigment (C. I. Pigment Yellow 74)
  • a pigment dispersion 2 was obtained by dispersing in the same manner as in Example 1 except that 15 parts were used.
  • the average particle size of the pigment was 93 nm.
  • Example 3 instead of the pigment dispersion 1 of Example 1, 20 parts of the pigment dispersion 2 in a water-soluble organic solution Except for using 17.5 parts of glycerin and 13 parts of “Jonkrill 775” (Johnson Polymer Co., Ltd., styrene acrylic resin, acid value 55, 45% solids). An ink with a pigment concentration adjusted to 3.0% was prepared in the same manner as in Example 1.
  • Example 3
  • a magenta pigment (C. I. Pigment Red 122) 1
  • a pigment dispersion 3 was obtained by dispersing in the same manner as in Example 1 except that 5 parts were used.
  • the average particle size of the pigment was 86 nm.
  • Example 1 instead of the pigment dispersion 1 of Example 1, 20 parts of the pigment dispersion 3, 17.5 parts of glycerin as a water-soluble organic solvent, and “Joncrill 775” (manufactured by John Son Polymer Co., Ltd.) Ink was prepared by adjusting the pigment concentration to 3.0% in the same manner as in Example 1, except that 13 parts of styrene-acrylic resin, acid value 55, and 45% solid content of resin were used.
  • a 25% aqueous solution of coconut resin C was obtained.
  • pigment dispersion 5 was obtained by dispersing in the same manner as in Example 1 except that 25% aqueous solution of rosin C was used instead of aqueous solution of rosin A in Example 1.
  • the average particle size of the pigment was 80 nm.
  • An ink having a pigment concentration adjusted to 3.75% was prepared in the same manner as in Example 1 except that 25 parts of the pigment dispersion 5 was used in place of the pigment dispersion 1 of Example 1.
  • a 25% aqueous solution of rosin oil D was obtained.
  • a pigment dispersion 6 was obtained by dispersing in the same manner as in Example 1 except that the above 25% aqueous solution of resin A was used in place of the aqueous solution of resin A in Example 1.
  • the average particle size of the pigment was 80 nm.
  • An ink having a pigment concentration adjusted to 3.75% was prepared in the same manner as in Example 1 except that 25 parts of Pigment Dispersion 6 was used instead of Pigment Dispersion 1 of Example 1.
  • pigment dispersion 7 was obtained by dispersing in the same manner as in Example 1 except that 25% aqueous solution of rosin E was used in place of aqueous solution of rosin A in Example 1.
  • the average particle size of the pigment is 80nm.
  • Example 1 Similar to Example 1 except that monoethanolamine (undiluted) is used as the neutralizing agent. A 25% aqueous solution F of a styrene- (meth) acrylic acid copolymer neutralized product having a pH adjusted to 8.7 was obtained. Next, a pigment dispersion 8 was obtained by dispersing in the same manner as in Example 1 except that the 25% aqueous solution of resin F was used in place of the aqueous solution of resin A in Example 1. The average particle size of the pigment is 80 nm.
  • Example 2 25% of a neutralized styrene- (meth) acrylic acid copolymer having a pH adjusted to 8.7, as in Example 1, except that diethanolamine (not diluted) was used as a neutralizing agent.
  • Aqueous fat solution G was obtained.
  • pigment dispersion 9 was obtained by dispersing in the same manner as in Example 1 except that 25% aqueous solution of rosin G was used in place of aqueous solution of rosin A in Example 1.
  • the average particle size of the pigment was 80 ⁇ m.
  • Example 2 25% of the neutralized styrene- (meth) acrylic acid copolymer having a pH adjusted to 8.7, as in Example 1, except that triethanolamine (not diluted) was used as a neutralizing agent.
  • a water-absorbent solution H was obtained.
  • pigment dispersion 10 was obtained by dispersing in the same manner as in Example 1 except that 25% aqueous solution of rosin H was used instead of aqueous solution of rosin A in Example 1.
  • the average particle size of the pigment was 8 Onm.
  • a neutralized styrene- (meth) acrylic acid copolymer having a pH adjusted to 8.7 was prepared in the same manner as in Example 1 except that jetylethanolamine (not diluted) was used as a neutralizing agent.
  • a 25% aqueous resin solution I was obtained.
  • a pigment dispersion 11 was obtained by dispersing in the same manner as in Example 1, except that 25% aqueous solution of resin I was used instead of the aqueous solution of resin A in Example 1.
  • the average particle size of the pigment was 80 nm.
  • a pigment dispersion 12 was obtained by dispersing in the same manner as in Example 1, except that the 25% aqueous solution of rosin A used in Example 1 was changed to 12 parts.
  • the average particle size of the pigment was 80 nm.
  • a black ink having a pigment concentration adjusted to 3.75% was prepared in the same manner as in Example 1 except that 25 parts of Pigment Dispersions 7 to 13 were used in place of Pigment Dispersion 1 of Example 1.
  • Table 1 shows the types of styrene (meth) acrylic acid-based resins and alkali neutralizers used as dispersants in Examples 1 to 6 and Comparative Examples 7 to 13 described above.
  • Table 2 shows the ratio of components other than water for the ink yarns of Inks 1 to 6 in the above Examples and Inks 7 to 13 in Comparative Examples.
  • Y-74 is yellow pigment (CI Pigment Yellow 74)
  • R-122 is red pigment (CI Pigment Red 122).
  • B_15 3 is blue pigment (I. Pigment Blue 15: 3).
  • the neutralizing agents for styrene (meth) acrylic acid copolymers are as described in [Table 1].
  • Evaluation criteria ( ⁇ ) Redispersed promptly without agglomeration. ( ⁇ ) Some thin film aggregates are observed, but do not adhere to the glass surface. (X) A considerable amount of agglomerate is observed, and the dried ink remains on the glass surface.
  • JV2-130 piezo method manufactured by Mimaki Engineering Co., Ltd. as a commercially available large-format inkjet plotter, dot missing, etc. under the conditions of print resolution 720 X 720dpi, single color 'filled printing, print width 1200mm O Continuous printing was performed until printing failure was detected o
  • Evaluation criteria ( ⁇ ) No clogging for 5 hours or more. ( ⁇ ) Clogging occurred in 30 minutes to 1 hour. ( ⁇ )
  • the aqueous pigment dispersion of the present invention is useful in the production of inks for ink jet recording, and various additives and water are added as necessary at the time of ink adjustment to obtain a pigment concentration suitable for the intended use.
  • the redispersibility of the obtained ink is improved, it is excellent in preventing clogging of the nozzle by the obtained ink, and the operation of the apparatus is stopped for a long time even during continuous operation of a long-time inkjet recording plotter.
  • a pigment ink for ink-jet recording can be obtained, which can be stably discharged even after normal cleaning.
  • An ink for ink jet recording using the aqueous pigment dispersion of the present invention provides an ink having good redispersibility while maintaining the performance of originally required storage stability, high quality recorded images, and the like. Excellent nozzle clogging prevention, and is useful as a pigment ink for ink jet recording because stable discharge can be obtained by normal cleaning even during long periods of continuous operation even after the operation of the device has been stopped for a long time. .
  • ink jet recording method and the ink jet textile printing method using the ink for ink jet recording of the present invention while maintaining the performance of a high-quality recorded image and the like, it is excellent in preventing clogging of the nozzle, and for a long time. Even during continuous operation of the apparatus, stable ink jet recording and ink jet printing can be performed by ordinary cleaning even after the operation of the apparatus is stopped for a long time, and can be effectively used for ink jet recording and ink jet printing.

Abstract

This invention provides an aqueous pigment dispersion, which comprises water, a pigment, and 30 to 100% by weight, based on the pigment, of a polymeric dispersant produced by neutralizing a styrene-(meth)acrylic acid copolymer having an acid value of 160 to 300 mg-KOH/g and a weight average molecular weight of 8,000 to 20,000 with an alkali metal hydroxide, and an ink-jet recording ink using the aqueous pigment dispersion. The present invention also provides a pigment ink, which, while maintaining properties such as storage stability and high-grade recorded images, has excellent nozzle clogging preventive properties, good dispersion stability, and has good redispersibility, that is, can be stably ejected even after continuous operation for a long period of time and even after stoppage for a long period of time, and a starting aqueous pigment dispersion, and an ink-jet recording or textile printing method using the ink.

Description

明 細 書  Specification
水性顔料分散体、インクジェット記録用インク並びにこれを用いた記録方 法及び捺染方法  Aqueous pigment dispersion, ink jet recording ink, and recording method and printing method using the same
技術分野  Technical field
[0001] 本発明は、水性顔料分散体、これを用いたインクジェット記録用インク並びに記録 方法及び捺染方法に関する。より詳しくは、インクジェット記録方式における、記録へ ッドのノズルの目詰まり防止性及びインクの保存安定性に優れた、水性顔料系インク ジェット記録用インク、当該インクに用いられる水性顔料分散体、並びに当該インクを 用いた記録方法及び捺染方法に関する。  The present invention relates to an aqueous pigment dispersion, an ink jet recording ink using the same, a recording method, and a textile printing method. More specifically, in an inkjet recording method, an aqueous pigment-based ink jet recording ink excellent in prevention of clogging of nozzles of a recording head and ink storage stability, an aqueous pigment dispersion used in the ink, and The present invention relates to a recording method and a printing method using the ink.
背景技術  Background art
[0002] 水性のインクジェット記録用インクは、水溶性染料の溶液、または水不溶性色材を 水または水溶性有機溶剤を含む水溶液に分散させた液の形態をとるのが一般的で あるが、特に、耐光性を要求される場合には、顔料を用いたインクジェット記録用イン クが使用されている。  [0002] Aqueous inkjet recording ink generally takes the form of a water-soluble dye solution or a liquid in which a water-insoluble colorant is dispersed in water or an aqueous solution containing a water-soluble organic solvent. When light resistance is required, ink jet recording ink using a pigment is used.
[0003] これらの顔料を使用したインクジェット記録用インクの性能に要求される項目として、  [0003] As items required for the performance of ink jet recording ink using these pigments,
(1)インクジェット記録用プロッター（プリンター）のノズルの目詰まり防止、吐出安定 性、（2)インクの保存安定性、（3)インク吐出時の方向性、吐出量及びドットの形状が 一定した高品位な記録画像、（4)インクの乾燥性、定着性 (5)高印字濃度、などが挙 げられる。  (1) Prevention of clogging of nozzles of inkjet plotter (printer), ejection stability, (2) storage stability of ink, (3) directionality when ejecting ink, high ejection volume and dot shape are constant Good quality recorded images, (4) ink drying and fixing properties, and (5) high print density.
[0004] インクジェット記録方式は、インクを細いノズル力 インクの小滴として噴射する必要 があるため、前記項目中（1)が特に重要である。特にオンデマンド型の方式では、連 続運転中でも一時的にノズル力 インクの噴射が停止されるため、長時間の連続運 転時に吐出不良が生じるという問題があった。  [0004] In the ink jet recording method, it is necessary to eject ink as a small nozzle force ink droplet, and therefore, item (1) is particularly important. In particular, the on-demand system has a problem in that ejection failure occurs during continuous operation for a long period of time because the ejection of nozzle force ink is temporarily stopped even during continuous operation.
[0005] また、顔料の場合、水溶性染料を使用する場合と違って、分散安定性の劣化による 沈殿物 (凝集物)の生成、ノズルにおける溶媒の蒸発等が原因となり、 目詰まりを起こ しゃすい。特に、装置の運転が長時間休止されるような状態に置かれたとき、溶媒の 蒸発に伴う目詰まりが発生しやすくなる。 [0006] そこで、溶媒の蒸発を抑えるために低揮発性の溶媒や保湿剤を加えたり、蒸発によ り溶媒の一部を失ったとしてもインク溜めより新しく供給されたインクに触れたとき再分 散できるようにするためにヒドロトロープ剤をカ卩えることが行われて 、る。これらの保湿 剤としては、グリセリン、ポリエチレングリコール等のダリコール類があり、ヒドロトロープ 剤としては、尿素、尿素誘導体類等がある。 [0005] Also, in the case of pigments, unlike when water-soluble dyes are used, clogging occurs due to the formation of precipitates (aggregates) due to deterioration of dispersion stability, evaporation of the solvent in the nozzle, and the like. Wow. In particular, when the apparatus is placed in a state where it is stopped for a long time, clogging due to evaporation of the solvent is likely to occur. [0006] Therefore, even if a low-volatile solvent or a humectant is added to suppress the evaporation of the solvent, or even when a part of the solvent is lost due to the evaporation, the ink is reused when the newly supplied ink is touched from the ink reservoir. A hydrotrope may be stored to allow for dispersion. These moisturizing agents include daricols such as glycerin and polyethylene glycol, and hydrotropes include urea and urea derivatives.
[0007] しカゝしながら、これらの添加剤を使用する場合、少量の添加では効果が得られず、 多量に用いるとインクの粘度の上昇、表面張力の著しい変化を生じ、さらには印刷物 の乾燥性を悪くするなどの問題が生じる。  [0007] However, when these additives are used, the effect is not obtained when added in a small amount, and when used in a large amount, the viscosity of the ink is increased and the surface tension is remarkably changed. Problems such as poor drying properties occur.
[0008] 顔料インクの再分散性に関する文献としては、例えば、下記特許文献 1には、水性 榭脂としてアクリル酸，スチレン， αメチルスチレンよりなる酸価 90〜130の三元共重 合体を用いる水性インクが記載されている。しかし、特許文献 1のインクでは、水性榭 脂の酸価が低 、ため再分散性は不十分であった。  [0008] As a document concerning redispersibility of pigment ink, for example, Patent Document 1 below uses a ternary copolymer having an acid value of 90 to 130 made of acrylic acid, styrene, and α-methylstyrene as an aqueous resin. A water-based ink is described. However, the ink of Patent Document 1 has insufficient redispersibility because the acid value of the aqueous resin is low.
[0009] 顔料インクに高分子分散剤を用いた例としては、下記特許文献 2には、スチレン アクリル酸系共重合体の遊離酸の形での酸価が 150mgKOHZg以上 250mgKO HZg未満であり、水不溶性色素に対するスチレン アクリル酸系共重合体の割合が 5重量％以上 20重量％未満である水性インク組成物が記載されている。また、下記 特許文献 3には、 Tgが 50°Cよりも高ぐ酸価が 100〜300KOHmgZgであり、重量 平均分子量が 2, 000-30, 000の有機高分子化合物 (A)を用いて顔料を水中に 分散させた後に、更に特定の有機高分子化合物 (B)を加える水性インク組成物の製 造方法が記載されている。しかしながら、前記特許文献 2に記載の発明では、水不溶 性色素に対するスチレン アクリル酸系共重合体の割合が 5重量％以上 20重量％ 未満のため、顔料インクの場合、再分散性が十分ではなカゝつた。また、前記特許文 献 3に記載の発明ではスチレン アクリル酸系共重合体の中和剤として、アンモニア 及び塩基性溶媒を使用した場合が実際には記載されているが、これらの中和剤で中 和した高分子分散剤を顔料の分散剤として使用したインクは、再分散性が十分では なかった。  [0009] As an example of using a polymer dispersant in a pigment ink, Patent Document 2 below discloses that the acid value in the form of a free acid of a styrene-acrylic acid copolymer is 150 mgKOHZg or more and less than 250 mgKO HZg, A water-based ink composition is described in which the ratio of the styrene-acrylic acid copolymer to the insoluble pigment is 5% by weight or more and less than 20% by weight. Patent Document 3 listed below uses an organic polymer compound (A) having a Tg higher than 50 ° C and an acid value of 100 to 300 KOHmgZg and a weight average molecular weight of 2,000-30,000, and a pigment. Describes a method for producing a water-based ink composition in which a specific organic polymer compound (B) is further added after being dispersed in water. However, in the invention described in Patent Document 2, since the ratio of the styrene / acrylic acid copolymer to the water-insoluble dye is 5% by weight or more and less than 20% by weight, redispersibility is not sufficient in the case of pigment ink. Katsuta. In the invention described in Patent Document 3, ammonia and a basic solvent are actually used as the neutralizing agent for the styrene-acrylic acid copolymer. However, with these neutralizing agents, The ink using the neutralized polymer dispersant as the pigment dispersant was not sufficiently redispersible.
[0010] また、下記特許文献 4には、顔料、榭脂分散剤、榭脂ェマルジヨンを含有し、顔料と 榭脂分散剤との重量比が 20： 1〜5： 2である水性インク組成物が記載されて ヽる。し かし、榭脂分散剤の中和剤として、有機アミン類及びアンモニア水が記載されている 力、これらの中和剤で中和した高分子分散剤を顔料の分散剤として使用したインクは 、再分散性が十分ではな力つた。 [0010] Further, Patent Document 4 shown below contains a pigment, a resin dispersant, and a resin emulsion, and the weight ratio of the pigment to the resin dispersant is 20: 1 to 5: 2. Is written. Shi However, as a neutralizing agent for a rosin dispersant, organic amines and aqueous ammonia are described, and an ink using a polymer dispersant neutralized with these neutralizing agents as a pigment dispersant is: Redispersibility was not enough.
特許文献 1 :特開平 8— 253716  Patent Document 1: JP-A-8-253716
特許文献 2：特開 2001— 294789号公報  Patent Document 2: Japanese Patent Laid-Open No. 2001-294789
特許文献 3：特開 2003 - 292838号公報  Patent Document 3: Japanese Patent Laid-Open No. 2003-292838
特許文献 4：特開平 9— 176533号公報  Patent Document 4: JP-A-9-176533
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0011] 本発明は、上記の様な従来の水性顔料系インクジェット記録用インクの問題点を解 決し、本来要求される保存安定性、高品位な記録画像等の性能を維持しつつ、ノズ ルの目詰まり防止性に優れ、分散安定性が良ぐ長時間の連続運転時においても、 装置の運転を長時間休止した後でも安定した吐出が得られる再分散性の良いインク ジ ット記録用インクに好適な水性顔料分散体、前記顔料分散体を用いたインクジ ット記録用インク並びに当該インクを用いた記録方法及び捺染方法を提供するもの である。 [0011] The present invention solves the problems of the conventional water-based pigment-based ink jet recording inks as described above, while maintaining the originally required storage stability and performance of high-quality recorded images, etc. For ink jet recording with good re-dispersibility, which provides stable ejection even during long-time continuous operation with excellent anti-clogging and good dispersion stability, even after the device has been stopped for a long time. An aqueous pigment dispersion suitable for ink, an ink jet recording ink using the pigment dispersion, and a recording method and a printing method using the ink are provided.
[0012] 本発明者らは、インクジェットヘッドにおけるノズルの目詰まりの起こしにくい信頼性 の優れた顔料インク組成物について、インクが乾燥した後でも同一組成のインクをカロ えたときに容易に再分散する再分散性の良 、インク組成物を得るために、顔料の分 散剤について検討した結果、特定の高分子分散剤及び特定の中和剤を選択するこ とで前記目的を達成することができることを見出し、本発明に至ったものである。 課題を解決するための手段  [0012] The present inventors easily redisperse a highly reliable pigment ink composition that is less likely to cause nozzle clogging in an inkjet head when the ink having the same composition is calorie even after the ink has dried. As a result of studying pigment dispersants in order to obtain an ink composition having good redispersibility, it was found that the object can be achieved by selecting a specific polymer dispersant and a specific neutralizer. This is the headline and the present invention. Means for solving the problem
[0013] 前記課題を解決するため、本発明の水性顔料分散体は、水、顔料、高分子分散剤 を含有し、前記高分子分散剤の含有量が、顔料に対して 30〜100重量％であり、顔 料が高分子分散剤で分散された水性顔料分散体にぉ ヽて、前記高分子分散剤が、 酸価が 160〜300mgKOHZg、重量平均分子量が 8, 000〜20, 000のスチレン （メタ)アクリル酸系共重合体をアルカリ金属水酸化物で中和して得られた高分子 分散剤であることを特徴とする。 [0014] また、本発明のインクジェット記録用インクは、上記記載のインクジェット記録用水性 顔料分散体を用いたことを特徴とする。 [0013] In order to solve the above problems, the aqueous pigment dispersion of the present invention contains water, a pigment, and a polymer dispersant, and the content of the polymer dispersant is 30 to 100% by weight with respect to the pigment. In the case of an aqueous pigment dispersion in which a pigment is dispersed with a polymer dispersant, the polymer dispersant contains styrene having an acid value of 160 to 300 mg KOHZg and a weight average molecular weight of 8,000 to 20,000. It is a polymer dispersant obtained by neutralizing a (meth) acrylic acid copolymer with an alkali metal hydroxide. [0014] Further, the ink for inkjet recording of the present invention is characterized by using the above-described aqueous pigment dispersion for inkjet recording.
[0015] また、本発明のインクジェット記録方法は、前記本発明のインクジェット記録用インク を使用して紙製品に印刷することを特徴とする。 [0015] Further, the ink jet recording method of the present invention is characterized by printing on a paper product using the ink for ink jet recording of the present invention.
[0016] また、本発明のインクジェット捺染方法は、前記本発明のインクジェット記録用インク を使用して繊維製品に印刷することを特徴とする。 [0016] Further, the ink jet textile printing method of the present invention is characterized by printing on a textile product using the ink for ink jet recording of the present invention.
発明の効果  The invention's effect
[0017] 本発明の水性顔料分散体を用いたインクジェット記録用インクは、本来要求される 保存安定性、高品位な記録画像等の性能を維持しつつ、再分散性の良いインクが 得られ、ノズルの目詰まり防止性に優れ、長時間の連続運転時においても装置の運 転を長時間休止した後でも通常のクリーニングで安定した吐出が得られるという効果 を有する。  [0017] An ink for ink jet recording using the aqueous pigment dispersion of the present invention provides an ink with good redispersibility while maintaining the performance of originally required storage stability, high quality recorded images, and the like. It is excellent in preventing clogging of the nozzles, and has an effect that stable discharge can be obtained by normal cleaning even when the operation of the apparatus is stopped for a long time even during a long continuous operation.
[0018] また、本発明の水性顔料分散体は、前記インクに有用であり、インク調整時に各種 添加剤及び水を必要に応じて添加して、使用用途に適した顔料濃度に調整されたィ ンクを得るために好適であり、インク調整までの保存安定性も良好である。また、得ら れたインクの再分散性が向上するので、得られたインクによるノズルの目詰まり防止 性に優れ、長時間のインクジェット記録プロッターの連続運転時にぉ 、ても装置の運 転を長時間休止した後でも通常のクリーニングで安定した吐出が得られ有用である。  [0018] Further, the aqueous pigment dispersion of the present invention is useful for the ink, and various additives and water are added as necessary at the time of ink adjustment to adjust the pigment concentration to be suitable for the intended use. The ink is suitable for obtaining ink and has good storage stability until ink adjustment. In addition, since the redispersibility of the obtained ink is improved, it is excellent in preventing clogging of the nozzle by the obtained ink, and the operation of the apparatus is prolonged even during continuous operation of the ink jet recording plotter for a long time. Even after a pause, the stable cleaning can be obtained by normal cleaning, which is useful.
[0019] したがって、前記本発明のインクジェット記録用インクを使用したインクジェット記録 方法並びにインクジェット捺染方法にぉ 、ては、高品位な記録画像等の性能を維持 しつつ、ノズルの目詰まりの防止性に優れ、長時間の連続運転時においても装置の 運転を長時間休止した後でも通常のクリーニングで安定した吐出が得られる。  Therefore, the ink jet recording method and the ink jet printing method using the ink for ink jet recording of the present invention can prevent nozzle clogging while maintaining the performance of a high-quality recorded image or the like. It is excellent, and even during continuous operation for a long time, stable discharge can be obtained by normal cleaning even after the operation of the device is stopped for a long time.
発明の詳細な開示  Detailed Disclosure of the Invention
[0020] 前記本発明の水性顔料分散体においては、前記高分子分散剤に用いられるスチ レン—（メタ）アクリル酸系共重合体の酸価が 200〜250mgKOHZgであるのが好ま しい。  In the aqueous pigment dispersion of the present invention, it is preferable that the styrene- (meth) acrylic acid copolymer used for the polymer dispersant has an acid value of 200 to 250 mgKOHZg.
[0021] また、前記本発明の水性顔料分散体においては、前記高分子分散剤に用いられる スチレン （メタ）アクリル酸系共重合体の重量平均分子量が、 10, 000〜18, 000 であるのが好ましい。 In the aqueous pigment dispersion of the present invention, the styrene (meth) acrylic acid copolymer used for the polymer dispersant has a weight average molecular weight of 10,000 to 18,000. Is preferred.
[0022] また、前記スチレン—（メタ)アクリル酸系共重合体は、連続塊状重合法で製造され た共重合榭脂であるのが好まし 、。  [0022] The styrene- (meth) acrylic acid copolymer is preferably a copolymerized resin manufactured by a continuous bulk polymerization method.
[0023] また、前記本発明の水性顔料分散体においては、さらに表面調整剤としてシリコン 系ノ-オン界面活性剤、アルコールアルコキシレート系ノ-オン界面活性剤、ァセチ レングリコール系ノ-オン界面活性剤、フッ素系ノ-オン界面活性剤力 選ばれる少 なくとも 1種を含有するのが好ましい。  [0023] Further, in the aqueous pigment dispersion of the present invention, as a surface conditioner, a silicon-based nonionic surfactant, an alcohol alkoxylate-based nonionic surfactant, and an acetylene glycol-based nonionic surfactant are used. And at least one selected from the group consisting of an agent and a fluorine-based nonionic surfactant.
[0024] また、前記本発明の水性顔料分散体にお!、ては、前記表面調整剤が、前記シリコ ン系ノユオン界面活性剤の一種であるポリエーテル変性ポリジメチルシロキサンであ るのが好ましい。 [0024] Further, in the aqueous pigment dispersion of the present invention, it is preferable that the surface conditioner is a polyether-modified polydimethylsiloxane which is a kind of the silicone-based noion surfactant. .
[0025] また、前記本発明の水性顔料分散体にお!ヽては、水溶性有機溶剤としてグリセリン を含有するのが好ましい。  [0025] The aqueous pigment dispersion of the present invention preferably contains glycerin as a water-soluble organic solvent.
[0026] また、前記本発明の水性顔料分散体においては、ポリエーテル変性ポリジメチルシ ロキサン及びグリセリンを含有して 、ることが好ましぐ前記ポリエーテル変性ポリジメ チルシロキサンの含有量力 水性顔料分散体全量に対して 0. 5〜3重量％であり、 グリセリンの含有量が水性顔料分散体全量に対して 10〜30重量％であるのが好ま しい。  [0026] The water-based pigment dispersion of the present invention preferably contains polyether-modified polydimethylsiloxane and glycerin, and the content power of the polyether-modified polydimethylsiloxane is preferably the total amount of the aqueous pigment dispersion. The content of glycerin is preferably 10 to 30% by weight relative to the total amount of the aqueous pigment dispersion.
[0027] また、前記本発明のインクジェット記録用インクにおいては、前記スチレン一（メタ） アクリル酸系共重合体の含有量が、インク全量に対して 1〜6重量％であるのが好ま しい。尚、ここで本発明の水性顔料分散体や、インクジェット記録用インクにおいては 、前記スチレン （メタ）アクリル酸系共重合体は、これをアルカリ金属水酸化物で中 和して得られた前記共重合体を用いるが、上記、スチレン （メタ)アクリル酸系共重 合体の含有量は、アルカリ金属水酸化物で中和する前の状態に換算した場合の含 有量である。スチレン （メタ）アクリル酸系共重合体の含有量とか、高分子分散剤の 含有量とは、このことを意味する。  In the inkjet recording ink of the present invention, it is preferable that the content of the styrene mono (meth) acrylic acid copolymer is 1 to 6% by weight with respect to the total amount of the ink. Here, in the aqueous pigment dispersion of the present invention and the ink for inkjet recording, the styrene (meth) acrylic acid copolymer is obtained by neutralizing the copolymer with an alkali metal hydroxide. Although a polymer is used, the content of the styrene (meth) acrylic acid copolymer is a content when converted to a state before neutralization with an alkali metal hydroxide. The content of styrene (meth) acrylic acid copolymer and the content of polymer dispersant mean this.
[0028] なお、前記本発明のインクジェット記録用インクにぉ 、ては、前記高分子分散剤の 含有量は、本発明の水性顔料分散体における割合である顔料に対して 30〜： LOO重 量％か、更に高分子分散剤を追加してインクを調整する場合には、前記割合より多く なる。しかし、上述したように、前記本発明のインクジェット記録用インクにおいては、 前記スチレン （メタ）アクリル酸系共重合体の含有量が、インク全量に対して 1〜6 重量％の範囲であるのが好まし 、。 [0028] Incidentally, in the ink for ink jet recording of the present invention, the content of the polymer dispersant is 30 to: LOO weight relative to the pigment which is a ratio in the aqueous pigment dispersion of the present invention. % Or more than the above ratio when adjusting the ink by adding a polymer dispersant. Become. However, as described above, in the inkjet recording ink of the present invention, the content of the styrene (meth) acrylic acid copolymer is in the range of 1 to 6% by weight with respect to the total amount of the ink. I like it.
[0029] また、前記本発明のインクジェット記録用インクにぉ 、ては、インクジェット記録用ィ ンクがグリセリンを含有するインクジェット記録用インクであり、前記グリセリンの含有量 力 Sインク全量に対して 5〜50重量％であるのが好ましい。 [0029] In addition, the ink for ink jet recording of the present invention is an ink for ink jet recording in which the ink for ink jet recording contains glycerin. It is preferably 50% by weight.
[0030] また、前記本発明のインクジェット記録用インクにぉ 、ては、前記インクジェット記録 用インクが表面調整剤を含有するインクジェット記録用インクであり、前記表面調整剤 の含有量がインク全量に対して 0. 05〜2重量％であることが好まし 、。 [0030] Further, the ink for ink jet recording of the present invention is an ink for ink jet recording in which the ink for ink jet recording contains a surface conditioner, and the content of the surface conditioner is based on the total amount of the ink. Preferable to be 0.05 to 2% by weight.
[0031] また、前記本発明のインクジェット記録用インクにぉ 、ては、前記表面調整剤が、ポ リエーテル変性ポリジメチルシロキサンであることが好ましい。 [0031] In addition, in the inkjet recording ink of the present invention, it is preferable that the surface conditioner is a polyether-modified polydimethylsiloxane.
[0032] また、前記本発明のインクジェット記録用インクにおいては、更に榭脂ェマルジヨン を含有するのが好ましい。  [0032] The ink for inkjet recording of the present invention preferably further contains a resin emulsion.
[0033] 以下に本発明をさらに詳細に説明する。本発明で使用する高分子分散剤は、顔料 を水性媒体中に分散させるものであり、酸価が 160〜300mgKOHZg、重量平均 分子量が 8, 000〜20, 000のスチレン （メタ）アクリル酸系共重合体をアルカリ金 属水酸ィ匕物で中和して得られた高分子分散剤であることを特徴とする。  [0033] The present invention is described in further detail below. The polymer dispersant used in the present invention is for dispersing a pigment in an aqueous medium. The styrene (meth) acrylic acid copolymer having an acid value of 160 to 300 mgKOHZg and a weight average molecular weight of 8,000 to 20,000 is used. It is a polymer dispersant obtained by neutralizing a polymer with an alkali metal hydroxide.
[0034] 尚、本発明において、 " · · ·（メタ)アクリル酸' · · "とは、 " · · 'アクリル酸' · · "及び Z 又は " · · 'メタクリル酸' · · "を意味する。  [0034] In the present invention, "(meth) acrylic acid" means "..." acrylic acid "... and Z or" ... "methacrylic acid" ... To do.
[0035] 前記スチレン （メタ）アクリル酸系共重合体としては、例えば、スチレン アクリル 酸共重合体、スチレン アクリル酸 アクリル酸エステル共重合体、スチレンーメタク リル酸共重合体、スチレンーメタクリル酸 アクリル酸エステル共重合体、スチレン αメチルスチレン アクリル酸共重合体、スチレン αメチルスチレンーメタクリル酸 共重合体等を挙げることができる。  [0035] Examples of the styrene (meth) acrylic acid copolymer include styrene acrylic acid copolymer, styrene acrylic acid acrylic ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid acrylic ester. Examples include copolymers, styrene α-methylstyrene acrylic acid copolymers, and styrene α-methylstyrene-methacrylic acid copolymers.
[0036] 本発明で用いる前記スチレン—（メタ）アクリル酸系共重合体は、その酸価が 160〜 300mgKOHZgであり、 200〜250mgKOH/gの範囲にあるものが好ましい。酸 価が 160未満の場合、アルカリ金属水酸化物で中和しても水に対する榭脂の溶解性 が悪くなる傾向にあり、酸価が 300を越えると、水性媒体との親和性が強くなり、印字 後の印字の耐水性が悪くなる傾向にある。前記スチレン （メタ)アクリル酸系共重合 体榭脂の酸価は、榭脂 lgを中和するのに要する KOHの mg数を表し、 JIS— K305 4に従って測定する。 [0036] The styrene- (meth) acrylic acid-based copolymer used in the present invention has an acid value of 160 to 300 mgKOHZg, preferably 200 to 250 mgKOH / g. When the acid value is less than 160, the solubility of the resin in water tends to deteriorate even when neutralized with an alkali metal hydroxide. When the acid value exceeds 300, the affinity with an aqueous medium increases. , Printing The water resistance of later printing tends to be poor. The acid value of the styrene (meth) acrylic acid-based copolymer rosin represents the number of mg of KOH required to neutralize the coconut lg, and is measured according to JIS-K3054.
[0037] また、前記スチレン （メタ）アクリル酸系共重合体の重量平均分子量は、 8000〜2 0000であり、 10000〜18000のもの力好ましい。分子量力 8000よりも/ J、さくなると、 再分散性が低下し、 20000より大きくなると、顔料を分散する能力が低下して好ましく ない。前記スチレン （メタ）アクリル酸系共重合体の重量平均分子量は、 GPC (ゲル パーミッションクロマトグラフ）法で測定する。  [0037] The styrene (meth) acrylic acid copolymer has a weight average molecular weight of 8000 to 20000, preferably 10,000 to 18,000. When the molecular weight force is less than 8000 / J, the redispersibility decreases, and when it exceeds 20000, the ability to disperse the pigment decreases, which is not preferable. The weight average molecular weight of the styrene (meth) acrylic acid copolymer is measured by a GPC (gel permeation chromatograph) method.
[0038] 前記スチレン （メタ)アクリル酸系共重合体は、連続塊状重合法で製造された共 重合榭脂であることが好ましい。連続塊状重合法で製造することにより、共重合体の 組成比が正確で一定した榭脂が得られるため、酸基のないモノマー成分を多く含む 水不溶性榭脂の生成を抑えることができ、品質が安定するので好適である。  [0038] The styrene (meth) acrylic acid copolymer is preferably a copolymerized resin manufactured by a continuous bulk polymerization method. Manufacture by a continuous bulk polymerization method provides a coagulant with an accurate and constant composition ratio of the copolymer, so it is possible to suppress the production of water-insoluble coagulant containing a large amount of monomer components without acid groups. Is preferable because it is stable.
[0039] 前記スチレン （メタ）アクリル酸系共重合体の具体例としては、ジョンソンポリマー 社製の、商品名"ジョンクリル 67" (分子量 = 12500、酸価 = 213)、 "ジョンクリル 678 ，，（分子量 =8500、酸価 = 215)、 "ジョンクリル 683" (分子量 =8000、酸価 = 160) 、 "ジョンクリル 690" (分子量 = 16500 ;酸価 = 240)、 "HPD— 671" (分子量 = 172 50 ;酸価 = 214)が挙げられる。特に、インクの再分散性向上の観点から"ジョンタリ ル 67"、 "ジョンクリル 690"、 "HPD— 671"が好ましい。  [0039] As specific examples of the styrene (meth) acrylic acid copolymer, trade names "Johncrill 67" (molecular weight = 12500, acid value = 213) manufactured by Johnson Polymer Co., Ltd., "Johncrill 678, (Molecular weight = 8500, Acid number = 215), "Johncrill 683" (Molecular weight = 8000, Acid number = 160), "Joncrill 690" (Molecular weight = 16500; Acid number = 240), "HPD—671" (Molecular weight = 172 50; acid value = 214) In particular, "John Tall 67", "John Krill 690", and "HPD-671" are preferable from the viewpoint of improving the redispersibility of the ink.
[0040] 前記スチレン （メタ）アクリル酸系共重合体を溶解するために中和剤を使用して中 和する。中和時の PHは、前記スチレン （メタ)アクリル酸系共重合体の溶解性の観 点から 8. 0〜10に調整するのが好ましぐより好ましくは 8. 5〜9. 0である。前記中 和剤としては、アルカリ金属水酸化物を使用する。アルカリ金属水酸化物としては、 水酸化リチウム、水酸化ナトリウム及び水酸化カリウムが好ましい。アルカリ金属水酸 化物を中和剤として使用することにより、インクの再分散性が向上できる。アルカリ源 としてアミン類等の有機塩基やアンモニアを用いたのでは、インクの再分散性、連続 吐出安定性並びに長時間放置後の吐出性の優れたインクを得ることができなくなる。  [0040] In order to dissolve the styrene (meth) acrylic acid copolymer, neutralization is performed using a neutralizing agent. The pH during neutralization is preferably adjusted to 8.5 to 10 and more preferably 8.5 to 9.0 from the viewpoint of solubility of the styrene (meth) acrylic acid copolymer. . As the neutralizing agent, an alkali metal hydroxide is used. As the alkali metal hydroxide, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable. By using alkali metal hydroxide as a neutralizing agent, the redispersibility of the ink can be improved. When an organic base such as amines or ammonia is used as the alkali source, it becomes impossible to obtain an ink having excellent ink redispersibility, continuous ejection stability, and ejection properties after standing for a long time.
[0041] また、前記アルカリ金属水酸ィ匕物で PHを調整するには、前記スチレン （メタ）ァク リル酸系共重合体のほぼ中和当量の前記アルカリ金属水酸化物の 15〜25重量％ 水溶液を加え、最終の PHが 8〜10、好ましくは 8. 5〜9. 0の範囲になるように調整 する。 [0041] Further, in order to adjust PH with the alkali metal hydroxide, 15 to 25 of the alkali metal hydroxide having an almost neutralization equivalent of the styrene (meth) acrylic acid copolymer is used. weight% Add aqueous solution and adjust so that the final PH is in the range of 8-10, preferably 8.5-9.0.
[0042] また、前記スチレン （メタ)アクリル酸系共重合体は、顔料分散時及びインク濃度 調整時の作業性の点から、予め固形榭脂をアルカリ金属水酸ィ匕物で中和して 20〜3 0重量％程度の榭脂水溶液としたのち使用することが好ましい。  [0042] Further, the styrene (meth) acrylic acid copolymer is obtained by neutralizing a solid resin with an alkali metal hydroxide in advance from the viewpoint of workability at the time of pigment dispersion and ink concentration adjustment. It is preferable to use after preparing a 20 to 30% by weight aqueous solution of rosin.
[0043] また、水性顔料分散体製造時の前記スチレン （メタ)アクリル酸系共重合体の使 用量は、顔料 100重量部に対し 30〜： LOO重量部が好ましい。より好ましくは 30〜80 重量部であり、さらに好ましくは 30〜60重量部である。 30重量部以上にすることで、 顔料の分散を十分に行うことができ、 100重量部以下にすることで、顔料分散時の粘 度上昇を防止できる。ここで使用量は、前記スチレン （メタ)アクリル酸系共重合体 の含有量で定義したと同様であり、前記スチレン （メタ)アクリル酸系共重合体は、 上述の如くこれをアルカリ金属水酸ィヒ物で中和して得られた前記共重合体を用いる 力 上記、スチレン （メタ)アクリル酸系共重合体の使用量は、アルカリ金属水酸ィ匕 物で中和する前の状態に換算した場合の使用量である。  [0043] The amount of the styrene (meth) acrylic acid copolymer used in the production of the aqueous pigment dispersion is preferably 30 to LOO parts by weight with respect to 100 parts by weight of the pigment. More preferably, it is 30-80 weight part, More preferably, it is 30-60 weight part. When the amount is 30 parts by weight or more, the pigment can be sufficiently dispersed, and when the amount is 100 parts by weight or less, an increase in viscosity at the time of pigment dispersion can be prevented. The amount used here is the same as defined by the content of the styrene (meth) acrylic acid copolymer, and the styrene (meth) acrylic acid copolymer is an alkali metal hydroxide as described above. The above-mentioned copolymer obtained by neutralization with an ionic compound is used. The amount of the styrene (meth) acrylic acid copolymer used above is the same as that before neutralization with an alkali metal hydroxide. This is the amount used when converted.
[0044] 本発明に使用される顔料は特に限定されるものではなぐカーボンブラック、有機顔 料が挙げられる。  [0044] The pigment used in the present invention is not particularly limited, and examples thereof include carbon black and organic pigments.
[0045] カーボンブラックの例としては、ファーネスブラック及びチャンネルブラック等が挙げ られる。これらのカーボンブラックは 1種類を使用しても良ぐまた複数種類のカーボ ンブラックを併用しても良 、。  [0045] Examples of carbon black include furnace black and channel black. These carbon blacks can be used alone or in combination with multiple types of carbon black.
[0046] 有機顔料の例としては、溶性ァゾ顔料、不溶性ァゾ顔料、不溶性ジスァゾ顔料、縮 合ァゾ顔料、フタロシアニン顔料、キナクリドン顔料、イソインドリノン顔料、ジォキサジ ン顔料、ペリレン顔料、ペリノン顔料、チォインジゴ顔料、アンスラキノン顔料及びキノ フタロン顔料等が挙げられる。これらの有機顔料は 1種類を使用しても良ぐまた複数 種類の有機顔料を併用しても良い。前記顔料の使用量は、水性顔料分散体の全重 量に対して、 5〜30重量％が好ましい。より好ましくは 10〜25重量％である。前記顔 料を顔料分散体製造時にこの範囲で使用することにより、インク調整時に各種添カロ 剤及び水を添加してインクを調整する場合にお!ヽても十分な顔料濃度が得られ、顔 料分散体製造時の粘度が上がりすぎることもなぐ顔料の分散性の観点からも好適で ある。 [0046] Examples of organic pigments include soluble azo pigments, insoluble azo pigments, insoluble bisazo pigments, condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments. Thioindigo pigments, anthraquinone pigments and quinophthalone pigments. One kind of these organic pigments may be used, or a plurality of kinds of organic pigments may be used in combination. The amount of the pigment used is preferably 5 to 30% by weight based on the total weight of the aqueous pigment dispersion. More preferably, it is 10 to 25% by weight. By using the above-mentioned pigment in this range when producing the pigment dispersion, a sufficient pigment concentration can be obtained even when adjusting the ink by adding various additives and water during ink preparation. From the viewpoint of the dispersibility of the pigment, which does not increase the viscosity at the time of the preparation of the pigment dispersion. is there.
[0047] 本発明にお ヽて、水性顔料分散体製造時に表面調整剤を添加しておくことが好ま しい。前記表面調整剤としては、シリコン系ノニオン界面活性剤、アルコールアルコキ シレート系ノ-オン界面活性剤、アセチレングリコール系ノ-オン界面活性剤、フッ素 系ノニオン界面活性剤が好ましぐ特にシリコン系ノニオン界面活性剤であるポリエー テル変性ポリジメチルシロキサンが好ましい。前記表面調整剤の使用量は、水性顔 料分散体の全重量に対して、 0. 5〜3重量％が好ましい。より好ましくは 1. 0〜2. 5 重量％である。前記表面調整剤を顔料分散体製造時にこの範囲で添加すると顔料 の濡れ性が向上してよりスムーズに分散が行えるので好適である。  [0047] In the present invention, it is preferable to add a surface conditioner during the production of the aqueous pigment dispersion. Examples of the surface conditioner include silicon-based nonionic surfactants, alcohol alkoxylate-based nonionic surfactants, acetylene glycol-based nonionic surfactants, and fluorine-based nonionic surfactants. Polyether-modified polydimethylsiloxane which is a surfactant is preferred. The amount of the surface conditioner used is preferably 0.5 to 3% by weight based on the total weight of the aqueous pigment dispersion. More preferably, it is 1.0 to 2.5% by weight. It is preferable to add the surface conditioner in this range during the production of the pigment dispersion because the wettability of the pigment is improved and the dispersion can be performed more smoothly.
[0048] 本発明にお ヽて、水性顔料分散体製造時に、水溶性有機溶剤を使用することが好 ましい。使用される水溶性有機溶剤としては、グリセリン、ジエチレングリコール、トリエ チレングリコール、ポリエチレングリコール 200、ポリエチレングリコール 300、ポリェチ レンダリコール 400、プロピレングリコール等が好ましい。特に、グリセリンを添加して おくと、水性顔料分散体製造時の分散液表面の乾燥を防止でき好適である。  [0048] In the present invention, it is preferable to use a water-soluble organic solvent when producing the aqueous pigment dispersion. As the water-soluble organic solvent to be used, glycerin, diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, propylene glycol and the like are preferable. In particular, it is preferable to add glycerin to prevent drying of the surface of the dispersion during production of the aqueous pigment dispersion.
[0049] また、水性顔料分散体製造時の水溶性有機溶剤の使用量は、顔料分散体製造時 の分散液表面の乾燥を防止し、インク化するまでの顔料分散体の保存性を向上させ るという観点から、水性顔料分散体の全重量に対して、 10〜30重量％が好ましい。 さらに好ましくは 15〜25重量％である。  [0049] The amount of the water-soluble organic solvent used in the production of the aqueous pigment dispersion prevents the surface of the dispersion from drying during the production of the pigment dispersion, and improves the storage stability of the pigment dispersion until it is converted into an ink. From the viewpoint of reducing the weight, the content is preferably 10 to 30% by weight based on the total weight of the aqueous pigment dispersion. More preferably, it is 15 to 25% by weight.
[0050] 本発明の水性顔料分散体は、インク調整時に各種添加剤及び水を添加して、使用 用途に適した顔料濃度に調整するために好適であり、インク調整までの保存安定性 も良好である。また、得られたインクの再分散性が向上するので、得られたインクによ るノズルの目詰まりの防止性に優れ、長時間のインクジェット記録プロッターの連続運 転時においても装置の運転を長時間休止した後でもインクジェット記録プロッターに 指示されている所定の通常のクリーニングで安定した吐出が得られ有用である。  [0050] The aqueous pigment dispersion of the present invention is suitable for adjusting the pigment concentration suitable for the intended use by adding various additives and water at the time of ink adjustment, and also has good storage stability until ink adjustment. It is. In addition, since the redispersibility of the obtained ink is improved, it is excellent in preventing nozzle clogging by the obtained ink, and the operation of the apparatus is prolonged even during continuous operation of an ink jet recording plotter for a long time. Even after a period of time pause, stable ejection can be obtained by a predetermined normal cleaning designated by the ink jet recording plotter, which is useful.
[0051] 次に本発明のインクジェット記録用インクは、前記水性顔料分散体を使用して調整 される。本発明のインクジェット記録用インクにおいて、スチレン （メタ)アクリル酸系 共重合体の含有量は、顔料の分散性及び保存安定性を良好に保つ目的から、イン クの全重量に対して 0. 5〜8重量％が好ましい。より好ましくは 1〜6重量％であり、 特に好ましくは 2〜4重量％である。 [0051] Next, the ink for inkjet recording of the present invention is prepared using the aqueous pigment dispersion. In the ink for inkjet recording of the present invention, the content of the styrene (meth) acrylic acid copolymer is 0.5 with respect to the total weight of the ink for the purpose of maintaining good dispersibility and storage stability of the pigment. ~ 8 wt% is preferred. More preferably 1 to 6% by weight, Particularly preferred is 2 to 4% by weight.
[0052] 本発明の顔料の含有量は、一般的に、分散安定性を保ち、且つ必要な印字濃度 が得られることから、インクの全重量に対して 0. 5〜8重量％が好ましい。より好ましく は 0. 5〜6重量％である。  [0052] The content of the pigment of the present invention is generally preferably 0.5 to 8% by weight based on the total weight of the ink, since dispersion stability is maintained and a necessary printing density is obtained. More preferably, it is 0.5 to 6% by weight.
[0053] 本発明のインクジェット記録用インクにおいて、使用される水溶性有機溶剤としては 、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラ エチレングリコーノレ、ポリエチレングリコール、プロピレングリコール、ポリプロピレング リコール、ブチレングリコール、へキシレングリコール、チォジグリコール、グリセリン等 の多価アルコール類、エチレングリコールモノメチルエーテル、エチレングリコールモ ノエチノレエーテノレ、エチレングリコーノレモノブチノレエーテノレ、ジエチレングリコーノレモ ノメチルエーテル、ジエチレングリコールモノェチルエーテル、ジエチレングリコーノレ モノブチノレエーテノレ、プロピレングリコーノレモノメチノレエーテノレ等のグリコーノレエーテ ル類、メタノール、エタノール、 n—プロピルアルコール、イソプロピルアルコール等の アルコール類が挙げられる。 [0053] In the inkjet recording ink of the present invention, examples of the water-soluble organic solvent used include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and butylene glycol. , Polyhydric alcohols such as hexylene glycol, thiodiglycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl etherenole, ethylene glycol monobutino enoate, diethylene glycol monomethyl ether, diethylene glycol mono Glycolols such as ethyl ether, diethyleneglycolone monobutinoleethenole, propyleneglycololemonomethinoleethenore Over Te le include methanol, ethanol, n - propyl alcohol, and isopropyl alcohol.
[0054] 上記水溶性有機溶剤のうち、グリセリン、ジエチレングリコール、トリエチレングリコー ル、ポリエチレングリコール 200、ポリエチレングリコール 300、ポリエチレングリコーノレ 400、プロピレングリコールが好ましい。特に、グリセリンは保湿剤として好ましい。  Of the water-soluble organic solvents, glycerin, diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, and propylene glycol are preferable. In particular, glycerin is preferred as a humectant.
[0055] これらは、単独でも 2種以上混合して使用してもかまわない。  [0055] These may be used alone or in combination of two or more.
[0056] これら水溶性有機溶剤の含有量は、インクの粘度調整、保湿効果による目詰まり防 止の点から、インクの全重量に対して 5〜50重量％が好ましい。より好ましくは 10〜4 5重量％で、 15〜40重量％が特に好ましい。  [0056] The content of these water-soluble organic solvents is preferably 5 to 50% by weight with respect to the total weight of the ink from the viewpoint of adjusting the viscosity of the ink and preventing clogging due to the moisturizing effect. More preferably, it is 10 to 45% by weight, and particularly preferably 15 to 40% by weight.
[0057] また、本発明のインクジヱット記録用インクを使用して、各種紙製品及び繊維製品に インクジェット記録方法で印刷する場合には、被印刷物への浸透性を高めるために、 さらに浸透剤を使用するのが好ましい。本発明のインクに用いる浸透剤としては、ァ セチレングリコール系、アセチレンアルコール系、シリコン系、ポリオキシエチレンアル キルエーテル系等のノ-オン性界面活性剤、アルキル硫酸ナトリウム、アルキルベン ゼンスルホン酸ナトリウム、ォレイン酸ナトリウム，ジォクチルスルホコハク酸ナトリウム 等のァ-オン性界面活性剤、アルキレングリコールモノアルキルエーテル、アルキレ ングリコール、一価アルコール類等の水溶性有機溶剤等が好適である。前記浸透剤 の添カ卩量は、インク全重量に対して 0. 05〜2重量％、好ましくは、 0. 1〜1重量％の 範囲で使用される。 0. 05重量％未満では、効果が少なくなり、 2重量％を越えて使 用してもほとんど効果は上がらない。これらをこの範囲で添加することにより印刷物の 乾燥性が向上し、連続して印刷しても前の印刷部分が次の印刷媒体の裏面に転写 されることがなくなるため、特にインクジェット印刷方法にあっては高速印刷が可能と なる。 [0057] Further, when printing on various paper products and textile products by the ink jet recording method using the ink jet recording ink of the present invention, a penetrating agent is further used in order to increase the permeability to the printing material. It is preferable to do this. Examples of penetrants used in the ink of the present invention include nonionic surfactants such as acetylene glycol, acetylene alcohol, silicon, and polyoxyethylene alkyl ether, sodium alkyl sulfate, and sodium alkylbenzene sulfonate. , Surfactants such as sodium oleate and sodium dioctylsulfosuccinate, alkylene glycol monoalkyl ether, alkyle Water-soluble organic solvents such as ethylene glycol and monohydric alcohols are preferred. The amount of the penetrating agent added is in the range of 0.05 to 2% by weight, preferably 0.1 to 1% by weight, based on the total weight of the ink. If it is less than 0.05% by weight, the effect is reduced, and if it exceeds 2% by weight, the effect is hardly improved. By adding these within this range, the dryness of the printed matter is improved, and even if continuous printing is performed, the previous printed portion is not transferred to the back side of the next print medium, and thus is particularly suitable for the inkjet printing method. High-speed printing is possible.
[0058] また、本発明のインクジヱット記録用インクを使用して、各種紙製品及び繊維製品に インクジェット記録方法で印刷する場合には、被印刷物の耐擦過性を高めるために、 さらに榭脂ェマルジヨンを含有するのが好まし 、。  [0058] Further, when printing on various paper products and textile products by the ink jet recording method using the ink jet recording ink of the present invention, a resin emulsion is further added in order to increase the scratch resistance of the substrate. It is preferable to contain.
[0059] 本発明のインクジェット記録用インクは、特に各種繊維製品にインクジェット捺染方 法で染色する場合に、バインダーとして榭脂ェマルジヨンを使用すると、顔料をより強 固に種々の繊維製品に固着でき、耐摩擦性、耐洗濯性等の諸堅牢度が向上して好 適である。前記榭脂ェマルジヨンの含有量は、インク全重量に対して 0. 5〜20重量 %、好ましくは、 1〜15重量％の範囲で使用される。前記榭脂ェマルジヨンの含有量 が 0. 5重量％以上であることにより目的とする堅牢度が得られ、 20重量％以下にす ることにより、粘度が高すぎることもなぐインクの吐出安定性に悪影響を及ぼさない。  [0059] The ink for inkjet recording of the present invention can fix the pigment more strongly to various textiles by using a resin emulsion as a binder, particularly when dyeing various textiles by the inkjet printing method. Various fastnesses such as abrasion resistance and washing resistance are improved, which is preferable. The content of the resin emulsion is in the range of 0.5 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the ink. When the content of the resin emulsion is 0.5% by weight or more, the intended fastness can be obtained, and by setting it to 20% by weight or less, the viscosity of the ink can be prevented from being too high. No adverse effect.
[0060] このような榭脂ェマルジヨンの榭脂成分としては、アクリル系榭脂、スチレン一アタリ ル系榭脂、酢酸ビニル系榭脂、スチレン ブタジエン系榭脂、塩ィ匕ビ二ル系榭脂、 ブタジエン系榭脂、スチレン系榭脂などがあげられる。  [0060] The resin component of such a resin emulsion is an acrylic resin, a styrene one-aryl resin, a vinyl acetate resin, a styrene butadiene resin, or a salt vinyl resin. Butadiene-based resin, styrene-based resin, and the like.
[0061] また、市販の榭脂ェマルジヨンとしては、例えばジョンソンポリマー社製スチレンーァ クリル系榭脂の、商品名"ジョンクリル 537"、 "ジョンクリル 775"、 "ジョンクリル 7610" 等があげられる。  [0061] Commercially available rosin emulsions include, for example, trade names "John Crill 537", "Jon Crill 775", "John Crill 7610", etc., made of styrene-acrylic resin manufactured by Johnson Polymer Co., Ltd.
[0062] 本発明のインクジェット記録用インクは、下記化学式 (I)で示される化合物（式中、 R は炭素数 25〜50のアルキル基を表し、 nは 10〜： LOOを表す。）を使用することができ る。 Rは、好ましくは炭素数 30〜50のアルキル基であり、特に炭素数 30〜35のアル キル基が好ましい。 nは、好ましくは 20〜： LOOであり、特に好ましくは 30〜： LOOである 。また、アルキル基は直鎖であっても分岐鎖であってもよいが、直鎖状アルキル基が 好ましい。 [0062] The ink for inkjet recording of the present invention uses a compound represented by the following chemical formula (I) (wherein R represents an alkyl group having 25 to 50 carbon atoms, and n represents 10 to LOO). can do. R is preferably an alkyl group having 30 to 50 carbon atoms, and particularly preferably an alkyl group having 30 to 35 carbon atoms. n is preferably 20 to: LOO, particularly preferably 30 to: LOO. The alkyl group may be linear or branched, but the linear alkyl group is preferable.
[0063] この化合物の HLBは、水への溶解性の点から 10以上、好ましくは 14〜18である。  [0063] The HLB of this compound is 10 or more, preferably 14-18, from the viewpoint of solubility in water.
[0064] R— O—（CH CH O) — H (I) [0064] R—O— (CH 2 CH 2 O) —H (I)
2 2 η  2 2 η
化学式 (I)の化合物の含有量は、インクの全量に対して 0. 1〜1. 5重量％使用さ れるのが好ましぐより好ましくは 0. 1〜1. 0重量％が好ましい。 0. 1〜1. 5重量％ の範囲で用いることにより、添加量が多すぎてインクの粘度が高くなりすぎる問題もな ぐより再分散性を向上する効果も発揮でき好ましい。  The content of the compound of formula (I) is preferably 0.1 to 1.5% by weight, more preferably 0.1 to 1.0% by weight, based on the total amount of the ink. The use in the range of 0.1 to 1.5% by weight is preferable because the added amount is too large and the viscosity of the ink becomes too high, and the effect of improving the redispersibility is exhibited.
[0065] 上記化学式 (I)の化合物の例としては、米国ペトロライト社製の "ュ-トツタス 450" ( Rは炭素数 30の直鎖状アルキル基、 ηは約 10、 HLB= 10)、 "ュ-トツタス 480" (R は炭素数 30の直鎖状アルキル基、 nは約 40、 HLB= 16)、 "ュ-トツタス 490" (Rは 炭素数 30の直鎖状アルキル基、 nは約 94、 HLB= 18)、 "ュ-トツタス 550" (Rは炭 素数 40の直鎖状アルキル基、 n力約 12、 HLB= 10)、 "ュ-トツタス 750" (Rは炭素 数 50の直鎖状アルキル基、 n力約 16、 HLB= 10)などが挙げられる。この中でも、 特に、 "ュ-トツタス 480"及び"ュ-トツタス 490"が好ましい。  [0065] As an example of the compound of the above chemical formula (I), "Toottus 450" (R is a linear alkyl group having 30 carbon atoms, η is about 10, HLB = 10) manufactured by Petrolite, USA, "Ututus 480" (R is a linear alkyl group with 30 carbon atoms, n is about 40, HLB = 16), "Ututus 490" (R is a linear alkyl group with 30 carbon atoms, n is Approx. 94, HLB = 18), "Touttus 550" (R is a straight-chain alkyl group with 40 carbon atoms, n-force is about 12, HLB = 10), "Touttus 750" (R is 50 carbon atoms) Linear alkyl group, n force of about 16, HLB = 10) and the like. Of these, “autotutus 480” and “autotutus 490” are particularly preferable.
[0066] また、前記化学式 (I)の化合物を添加する場合、作業性の点から、あらかじめ作成 した 5〜15重量％程度の水溶液を使用するのが好ましい。  [0066] When the compound of the above formula (I) is added, it is preferable to use an aqueous solution of about 5 to 15% by weight prepared in advance from the viewpoint of workability.
[0067] 本発明のインクには、その他各種添加剤を本発明の目的の達成を妨げない範囲に おいて、必要に応じて添加することができる。例えば、表面調整剤、ヒドロトロープ剤、 PH調整剤、粘度調整剤、防腐剤、防かび剤、光安定剤、キレート化剤、消泡剤等で ある。  [0067] Various other additives may be added to the ink of the present invention as needed within a range not impeding the achievement of the object of the present invention. For example, surface modifiers, hydrotropes, PH modifiers, viscosity modifiers, preservatives, fungicides, light stabilizers, chelating agents, antifoaming agents and the like.
[0068] 上記添加剤のうち、表面調整剤としては、シリコン系ノ-オン界面活性剤、アルコー ルアルコキシレート系ノニオン界面活性剤、アセチレングリコール系ノニオン界面活 性剤、フッ素系ノ-オン界面活性剤が好ましぐ特にシリコン系ノ-オン界面活性剤 であるポリエーテル変性ポリジメチルシロキサンが好まし 、。これらの表面調整剤は、 インクの表面張力を調整し、インクをインク流路系材料に濡れ易くするのに有効であ る。これらの表面調整剤の含有量は、インク全重量に対して 0. 05〜2重量％、好まし くは、 0. 1〜1重量％の範囲で使用される。 0. 05重量％未満では、効果が少なくな り、 2重量％を越えて使用してもほとんど効果は上がらない。 [0069] 次に、前記水性顔料分散体の製造方法及びそれを用いたインクの調整方法につ いて説明する。 [0068] Among the above-mentioned additives, as the surface conditioner, a silicon-based nonionic surfactant, an alcohol alkoxylate-based nonionic surfactant, an acetylene glycol-based nonionic surfactant, a fluorine-based nonionic surfactant In particular, polyether-modified polydimethylsiloxane, which is a silicone-based nonionic surfactant, is preferred. These surface conditioners are effective in adjusting the surface tension of the ink and making the ink easy to get wet with the ink flow path system material. The content of these surface conditioners is 0.05 to 2% by weight, preferably 0.1 to 1% by weight, based on the total weight of the ink. If the amount is less than 0.05% by weight, the effect is reduced, and if it exceeds 2% by weight, the effect is hardly improved. [0069] Next, a method for producing the aqueous pigment dispersion and a method for adjusting ink using the same will be described.
(1)水に、スチレン—（メタ)アクリル酸系共重合体を加え、撹拌しながら中和剤である アルカリ金属水酸化物の 15〜25重量％水溶液を添カ卩し、 PHを 8〜10、好ましくは 8 . 5〜9. 0に調整しながら 60〜90°C程度に加熱して完全に溶解させた後常温まで 冷却し、中和されたスチレン （メタ)アクリル酸系共重合体榭脂水溶液を作成する。 (1) Add styrene- (meth) acrylic acid copolymer to water, add a 15 to 25% by weight aqueous solution of alkali metal hydroxide as a neutralizing agent while stirring, and adjust pH to 8 to 10. Styrene (meth) acrylic acid copolymer neutralized by heating to about 60-90 ° C and completely dissolving it while adjusting to 8.5-9.0, then cooling to room temperature Create an aqueous solution of rosin.
(2)水に、顔料、前記榭脂水溶液、必要に応じて表面調整剤、水溶性有機溶剤、前 記化学式 (I)の化合物や前記添加剤を混合し、ディゾルバーを用いてプレミキシング を約 30分間行う。次いで、 (2) In water, a pigment, the aqueous solution of rosin, if necessary, a surface conditioner, a water-soluble organic solvent, the compound of the formula (I) and the additive are mixed, and premixing is performed using a dissolver. Do for 30 minutes. Then
(3)該プレミキシング液をサンドミル等の湿式媒体ミルで、前記顔料を微細に分散さ せ、水性顔料分散体を得る。  (3) The premixing liquid is finely dispersed in a wet medium mill such as a sand mill to obtain an aqueous pigment dispersion.
(4)該水性顔料分散体に、水、必要に応じて榭脂ェマルジヨン、浸透剤、水溶性有 機溶剤、前記化学式 (I)の化合物、等の前記添加剤を加え濃度調整した後、濾紙等 でろ過してからインクジェット記録用インクとして使用する。  (4) To the aqueous pigment dispersion, water, if necessary, a resin emulsion, a penetrant, a water-soluble organic solvent, the compound of the above chemical formula (I), and the like are added to adjust the concentration, and then the filter paper. Use it as an ink for ink jet recording after being filtered by etc.
[0070] 上記方法において、スチレン （メタ)アクリル酸系共重合体から得られた前記高分 子分散剤は、顔料の再分散性を向上させるために、濃度調整時にさらに添加しても よい。  [0070] In the above method, the high molecular dispersant obtained from the styrene (meth) acrylic acid copolymer may be further added during the concentration adjustment in order to improve the redispersibility of the pigment.
[0071] 上記方法で得られた顔料の平均粒子径は 200nm以下が好ましぐより好ましくは 5 0〜150nmである。  [0071] The average particle size of the pigment obtained by the above method is preferably 200 nm or less, more preferably 50 to 150 nm.
[0072] 以上、顔料、スチレン （メタ)アクリル酸系共重合体、中和剤、水溶性有機溶媒、 榭脂ェマルジヨン、浸透剤、その他の成分について例示した力 本発明はこの例に 限定されるものではない。  [0072] As described above, the power exemplified for the pigment, the styrene (meth) acrylic acid copolymer, the neutralizer, the water-soluble organic solvent, the resin emulsion, the penetrant, and other components. The present invention is limited to this example. It is not a thing.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0073] 以下に、実施例を挙げて本発明を更に具体的に説明するが、本発明の態様はこれ らに限定されるものではない。尚、下記実施例において"部"は特に断らない限り"重 量部"を、また"％ "は特に断らない限り"重量％ "を示す。 [0073] Hereinafter, the present invention will be described more specifically with reference to examples, but the embodiments of the present invention are not limited thereto. In the following examples, “part” represents “weight part” unless otherwise specified, and “%” represents “weight%” unless otherwise specified.
実施例 1  Example 1
[0074] [顔料分散体 1] 水 1100部中にスチレン—（メタ）アクリル酸系共重合体として" HPD— 671 " (ジョン ソンポリマー社製、分子量 = 17250、酸価 = 214) 600部を添加し、撹拌しながらほ ぼ中和当量の 20%濃度の水酸ィ匕カリウム水溶液をカ卩え、 PHを 8. 5〜9. 0に調整し ながら 80°Cに加熱して完全に溶解後常温まで冷却し、水を追加して合計量を 2400 部とすることにより、スチレン—（メタ)アクリル酸系共重合体中和物の 25%榭脂水溶 液 Aを得た。前記 25%榭脂水溶液 Aの PHは 8. 7であった。次に、前記 25%榭脂水 溶液 Aを 30部、ブラック顔料 (カーボンブラック、デグサ 'ヒュルス社製、商品名" COL OR BLACK S160") 15部、水溶性有機溶剤としてグリセリン 20部、表面調整剤 としてポリエーテル変性ポリジメチルシロキサン（ビックケミー ·ジャパン (株)製" BYK - 348") 1. 5部及び水を添カ卩し全量を 100部とし、ディゾルバーを用いて 30分間プ レミキシングを行う。次に、該プレミキシング液を直径 0. 4mmのジルコンビーズ 220 部を使用して、サンドミルにて 15時間分散して顔料分散体 1を得た。顔料の平均粒 径は 80nmであった。 [0074] [Pigment dispersion 1] Add "HPD-671" (manufactured by Johnson Polymer Co., Ltd., molecular weight = 17250, acid value = 214) as a styrene- (meth) acrylic acid-based copolymer in 1100 parts of water. Add a 20% aqueous solution of potassium hydroxide and water equivalent to the equivalent amount, adjust the pH to 8.5 to 9.0, heat to 80 ° C, dissolve completely, cool to room temperature, and add water. Thus, by making the total amount 2400 parts, 25% aqueous solution A of styrene- (meth) acrylic acid copolymer neutralized product was obtained. The pH of the 25% aqueous rosin solution A was 8.7. Next, 30 parts of the 25% aqueous solution A, 15 parts of black pigment (carbon black, manufactured by Degussa Huls, trade name “COL OR BLACK S160”), 20 parts of glycerin as a water-soluble organic solvent, surface conditioning Polyether-modified polydimethylsiloxane as an agent ("BYK-348" manufactured by Big Chemie Japan Co., Ltd.) 1. Add 5 parts and water to make a total of 100 parts, and premix for 30 minutes using a dissolver . Next, the premixing liquid was dispersed in a sand mill for 15 hours using 220 parts of zircon beads having a diameter of 0.4 mm to obtain pigment dispersion 1. The average particle size of the pigment was 80 nm.
[0075] [インク 1] [0075] [Ink 1]
前記顔料分散体 1を 25部、榭脂ェマルジヨンとして"ジョンクリル 537" (ジョンソンポリ マー社製、スチレン—アクリル系榭脂、酸価 40、榭脂固形分 46%)を 16部、浸透剤 として" BYK— DYNWET800" (ビックケミ^ ~ ·ジャパン（株）製、アルコールアルコキ シレート系界面活性剤）を 0. 5部、水溶性有機溶剤としてグリセリン 15部、表面調整 剤としてポリエーテル変性ポリジメチルシロキサン（ビックケミー ·ジャパン (株)製" BY K- 348") 0. 3部、さらに水をカ卩ぇ全量を 100部とし、顔料濃度を 3. 75%に調整し たインクを作成した。  25 parts of Pigment Dispersion 1 and 16 parts of “Jonkrill 537” (made by Johnson Polymer Co., Ltd., styrene-acrylic resin, acid value 40, 46% solids of resin) as penetrant. "BYK—DYNWET800" (produced by Big Chemi ~ Japan Co., Ltd., alcohol alkoxylate surfactant) 0.5 parts, 15 parts glycerin as water-soluble organic solvent, polyether-modified polydimethylsiloxane as surface conditioner ("BY K-348" manufactured by Big Chemie Japan Co., Ltd.) An ink was prepared by adjusting the pigment concentration to 0.35% by adding 0.3 parts of water, 100 parts of the total amount of water.
実施例 2  Example 2
[0076] [顔料分散体 2] [0076] [Pigment dispersion 2]
実施例 1の前記ブラック顔料に代えて、イェロー顔料（C. I. Pigment Yellow 74) Instead of the black pigment of Example 1, yellow pigment (C. I. Pigment Yellow 74)
15部を使用する以外は実施例 1と同様に分散して顔料分散体 2を得た。顔料の平均 粒径は 93nmであった。 A pigment dispersion 2 was obtained by dispersing in the same manner as in Example 1 except that 15 parts were used. The average particle size of the pigment was 93 nm.
[0077] [インク 2] [0077] [Ink 2]
実施例 1の前記顔料分散体 1に代えて、前記顔料分散体 2を 20部、水溶性有機溶 剤としてグリセリンを 17. 5部及び榭脂ェマルジヨンとしで'ジョンクリル 775" (ジョンソ ンポリマー社製、スチレン アクリル系榭脂、酸価 55、榭脂固形分 45%)を 13部使 用する以外は実施例 1と同様にして顔料濃度を 3. 0%に調整したインクを作成した。 実施例 3 Instead of the pigment dispersion 1 of Example 1, 20 parts of the pigment dispersion 2 in a water-soluble organic solution Except for using 17.5 parts of glycerin and 13 parts of “Jonkrill 775” (Johnson Polymer Co., Ltd., styrene acrylic resin, acid value 55, 45% solids). An ink with a pigment concentration adjusted to 3.0% was prepared in the same manner as in Example 1. Example 3
[0078] [顔料分散体 3] [0078] [Pigment dispersion 3]
実施例 1の前記ブラック顔料に代えて、マゼンタ顔料（C. I. Pigment Red 122) 1 Instead of the black pigment of Example 1, a magenta pigment (C. I. Pigment Red 122) 1
5部を使用する以外は実施例 1と同様に分散して顔料分散体 3を得た。顔料の平均 粒径は 86nmであった。 A pigment dispersion 3 was obtained by dispersing in the same manner as in Example 1 except that 5 parts were used. The average particle size of the pigment was 86 nm.
[0079] [インク 3] [0079] [Ink 3]
実施例 1の前記顔料分散体 1に代えて、前記顔料分散体 3を 20部、水溶性有機溶 剤としてグリセリンを 17. 5部及び榭脂ェマルジヨンとしで'ジョンクリル 775" (ジョンソ ンポリマー社製、スチレン アクリル系榭脂、酸価 55、榭脂固形分 45%)を 13部使 用する以外は実施例 1と同様にして顔料濃度を 3. 0%に調整したインクを作成した。 実施例 4  Instead of the pigment dispersion 1 of Example 1, 20 parts of the pigment dispersion 3, 17.5 parts of glycerin as a water-soluble organic solvent, and “Joncrill 775” (manufactured by John Son Polymer Co., Ltd.) Ink was prepared by adjusting the pigment concentration to 3.0% in the same manner as in Example 1, except that 13 parts of styrene-acrylic resin, acid value 55, and 45% solid content of resin were used. Four
[0080] [顔料分散体 4]  [0080] [Pigment dispersion 4]
スチレン （メタ）アクリル酸系共重合体として"ジョンクリル 67" (ジョンソンポリマー 社製、分子量 = 12500、酸価 = 213) 600部を使用する以外は実施例 1と同様に、 P Hを 8. 7に調整したスチレン—（メタ)アクリル酸系共重合体中和物の 25%榭脂水溶 液 Bを得た。次に、実施例 1の前記榭脂水溶液 A及び前記ブラック顔料に代えて、前 記 25%榭脂水溶液 Bを 30部及びシアン顔料（C. I. Pigment Blue 15 : 3) 15部を 使用する以外は実施例 1と同様に分散して顔料分散体 4を得た。顔料の平均粒径は 82nmであった。  As in Example 1, except that 600 parts of "Johncrill 67" (manufactured by Johnson Polymer Co., Ltd., molecular weight = 12500, acid value = 213) is used as the styrene (meth) acrylic acid copolymer, the pH is set to 8.7. A 25% aqueous resin solution B of a neutralized styrene- (meth) acrylic acid copolymer prepared in the above was obtained. Next, in place of the aqueous resin solution A and the black pigment in Example 1, 30 parts of the aqueous 25% aqueous resin solution B and 15 parts of cyan pigment (CI Pigment Blue 15: 3) were used. Dispersion was carried out in the same manner as in Example 1 to obtain Pigment Dispersion 4. The average particle size of the pigment was 82 nm.
[0081] [インク 4]  [0081] [Ink 4]
実施例 1の前記顔料分散体 1に代えて、前記顔料分散体 4を 15部、水溶性有機溶 剤としてグリセリンを 17. 5部及び榭脂ェマルジヨンとしで'ジョンクリル 775" (ジョンソ ンポリマー社製、スチレン アクリル系榭脂、酸価 55、榭脂固形分 45%)を 9部使用 する以外は実施例 1と同様にして顔料濃度を 2. 25%に調整したインクを作成した。 実施例 5 [0082] [顔料分散体 5] Instead of the pigment dispersion 1 of Example 1, 15 parts of the pigment dispersion 4, 17.5 parts of glycerin as a water-soluble organic solvent, and “Joncrill 775” (manufactured by John Son Polymer Co., Ltd.) Ink was prepared by adjusting the pigment concentration to 2.25% in the same manner as in Example 1 except that 9 parts of styrene-acrylic resin, acid value 55, and 50% solid content of resin were used. [0082] [Pigment dispersion 5]
中和剤としてほぼ中和当量の 20%濃度の水酸ィ匕ナトリウム水溶液をカ卩える以外は 実施例 1と同様に、 PHを 8. 7に調整したスチレン—（メタ)アクリル酸系共重合体中 和物の 25%榭脂水溶液 Cを得た。次に、前記実施例 1の榭脂水溶液 Aに代えて、 2 5%榭脂水溶液 Cを用いる以外は実施例 1と同様に分散して顔料分散体 5を得た。顔 料の平均粒径は 80nmであった。  A styrene- (meth) acrylic acid copolymer having a pH adjusted to 8.7, as in Example 1, except that a neutralized equivalent of 20% sodium hydroxide aqueous solution having a neutralization equivalent was covered. A 25% aqueous solution of coconut resin C was obtained. Next, pigment dispersion 5 was obtained by dispersing in the same manner as in Example 1 except that 25% aqueous solution of rosin C was used instead of aqueous solution of rosin A in Example 1. The average particle size of the pigment was 80 nm.
[0083] [インク 5]  [0083] [Ink 5]
実施例 1の前記顔料分散体 1に代えて、前記顔料分散体 5を 25部使用する以外は 実施例 1と同様にして顔料濃度を 3. 75%に調整したインクを作成した。  An ink having a pigment concentration adjusted to 3.75% was prepared in the same manner as in Example 1 except that 25 parts of the pigment dispersion 5 was used in place of the pigment dispersion 1 of Example 1.
実施例 6  Example 6
[0084] [顔料分散体 6]  [0084] [Pigment dispersion 6]
中和剤としてほぼ中和当量の 20%濃度の水酸化リチウム水溶液を使用する以外 は実施例 1と同様に、 PHを 8. 7に調整したスチレン—（メタ）アクリル酸系共重合体 中和物の 25%榭脂水溶液 Dを得た。次に、実施例 1の前記榭脂水溶液 Aに代えて、 上記 25%榭脂水溶液 Dを用いる以外は実施例 1と同様に分散して顔料分散体 6を 得た。顔料の平均粒径は 80nmであった。  A styrene- (meth) acrylic acid copolymer with a pH adjusted to 8.7 as in Example 1, except that a 20% aqueous lithium hydroxide solution having a neutralization equivalent of approximately 20% was used as a neutralizing agent. A 25% aqueous solution of rosin oil D was obtained. Next, a pigment dispersion 6 was obtained by dispersing in the same manner as in Example 1 except that the above 25% aqueous solution of resin A was used in place of the aqueous solution of resin A in Example 1. The average particle size of the pigment was 80 nm.
[0085] [インク 6]  [0085] [Ink 6]
実施例 1の前記顔料分散体 1に代えて、前記顔料分散体 6を 25部使用する以外は 実施例 1と同様にして顔料濃度を 3. 75%に調整したインクを作成した。  An ink having a pigment concentration adjusted to 3.75% was prepared in the same manner as in Example 1 except that 25 parts of Pigment Dispersion 6 was used instead of Pigment Dispersion 1 of Example 1.
比較例  Comparative example
[0086] [顔料分散体 7] [0086] [Pigment dispersion 7]
中和剤として 25%濃度のアンモニア水を使用する以外は実施例 1と同様に、 PHを 8. 7に調整したスチレン—（メタ)アクリル酸系共重合体中和物の 25%榭脂水溶液 E を得た。次に、実施例 1の前記榭脂水溶液 Aに代えて、 25%榭脂水溶液 Eを用いる 以外は実施例 1と同様に分散して顔料分散体 7を得た。顔料の平均粒径は 80nmで めつに。  25% aqueous solution of styrene- (meth) acrylic acid copolymer neutralized with pH adjusted to 8.7, as in Example 1, except that 25% aqueous ammonia was used as the neutralizing agent. I got E. Next, pigment dispersion 7 was obtained by dispersing in the same manner as in Example 1 except that 25% aqueous solution of rosin E was used in place of aqueous solution of rosin A in Example 1. The average particle size of the pigment is 80nm.
[0087] [顔料分散体 8] [0087] [Pigment Dispersion 8]
中和剤としてモノエタノールァミン (希釈せず)を使用する以外は実施例 1と同様に 、 PHを 8. 7に調整したスチレン—（メタ)アクリル酸系共重合体中和物の 25%榭脂水 溶液 Fを得た。次に、実施例 1の前記榭脂水溶液 Aに代えて、 25%榭脂水溶液 Fを 用いる以外は実施例 1と同様に分散して顔料分散体 8を得た。顔料の平均粒径は 80 nmであつ 7こ。 Similar to Example 1 except that monoethanolamine (undiluted) is used as the neutralizing agent. A 25% aqueous solution F of a styrene- (meth) acrylic acid copolymer neutralized product having a pH adjusted to 8.7 was obtained. Next, a pigment dispersion 8 was obtained by dispersing in the same manner as in Example 1 except that the 25% aqueous solution of resin F was used in place of the aqueous solution of resin A in Example 1. The average particle size of the pigment is 80 nm.
[0088] [顔料分散体 9]  [0088] [Pigment dispersion 9]
中和剤としてジエタノールァミン (希釈せず)を使用する以外は実施例 1と同様に、 P Hを 8. 7に調整したスチレン—（メタ)アクリル酸系共重合体中和物の 25%榭脂水溶 液 Gを得た。次に、実施例 1の前記榭脂水溶液 Aに代えて、 25%榭脂水溶液 Gを用 いる以外は実施例 1と同様に分散して顔料分散体 9を得た。顔料の平均粒径は 80η mであった。  25% of a neutralized styrene- (meth) acrylic acid copolymer having a pH adjusted to 8.7, as in Example 1, except that diethanolamine (not diluted) was used as a neutralizing agent. Aqueous fat solution G was obtained. Next, pigment dispersion 9 was obtained by dispersing in the same manner as in Example 1 except that 25% aqueous solution of rosin G was used in place of aqueous solution of rosin A in Example 1. The average particle size of the pigment was 80 ηm.
[0089] [顔料分散体 10]  [0089] [Pigment dispersion 10]
中和剤としてトリエタノールァミン (希釈せず)を使用する以外は実施例 1と同様に、 PHを 8. 7に調整したスチレン—（メタ)アクリル酸系共重合体中和物の 25%榭脂水 溶液 Hを得た。次に、実施例 1の前記榭脂水溶液 Aに代えて、 25%榭脂水溶液 Hを 用いる以外は実施例 1と同様に分散して顔料分散体 10を得た。顔料の平均粒径は 8 Onmであった。  25% of the neutralized styrene- (meth) acrylic acid copolymer having a pH adjusted to 8.7, as in Example 1, except that triethanolamine (not diluted) was used as a neutralizing agent. A water-absorbent solution H was obtained. Next, pigment dispersion 10 was obtained by dispersing in the same manner as in Example 1 except that 25% aqueous solution of rosin H was used instead of aqueous solution of rosin A in Example 1. The average particle size of the pigment was 8 Onm.
[0090] [顔料分散体 11]  [0090] [Pigment dispersion 11]
中和剤としてジェチルエタノールァミン (希釈せず)を使用する以外は実施例 1と同 様に、 PHを 8. 7に調整したスチレン—（メタ)アクリル酸系共重合体中和物の 25%榭 脂水溶液 Iを得た。次に、実施例 1の前記榭脂水溶液 Aに代えて、 25%榭脂水溶液 I を用いる以外は実施例 1と同様に分散して顔料分散体 11を得た。顔料の平均粒径 は 80nmであった。  A neutralized styrene- (meth) acrylic acid copolymer having a pH adjusted to 8.7 was prepared in the same manner as in Example 1 except that jetylethanolamine (not diluted) was used as a neutralizing agent. A 25% aqueous resin solution I was obtained. Next, a pigment dispersion 11 was obtained by dispersing in the same manner as in Example 1, except that 25% aqueous solution of resin I was used instead of the aqueous solution of resin A in Example 1. The average particle size of the pigment was 80 nm.
[0091] [顔料分散体 12]  [0091] [Pigment dispersion 12]
スチレン （メタ）アクリル酸系共重合体として"ジョンクリル 680" (ジョンソンポリマ 一社製、分子量 =4900、酸価 = 215) 600部を使用する以外は実施例 1と同様に、 PHを 8. 7に調整したスチレン—（メタ)アクリル酸系共重合体中和物の 25%榭脂水 溶！ ¾ [を得た。次に、実施例 1の前記榭脂水溶液 Aに代えて、前記 25%榭脂水溶! ¾ を使用する以外は実施例 1と同様に分散して顔料分散体 12を得た。顔料の平均粒 径は 80nmであった。 As in Example 1, except that 600 parts of “Johncrill 680” (manufactured by Johnson Polymer Co., Ltd., molecular weight = 4900, acid value = 215) is used as the styrene (meth) acrylic acid copolymer, the pH is 8. 25% aqueous solution of styrene- (meth) acrylic acid copolymer neutralized to 7% water soluble! ¾ [We got. Next, a pigment dispersion 12 was obtained by dispersing in the same manner as in Example 1 except that the 25% aqueous solution of rosin water was used instead of the aqueous rosin solution A in Example 1. Average particle size of pigment The diameter was 80 nm.
[0092] [顔料分散体 13] [0092] [Pigment dispersion 13]
実施例 1で用いた前記 25%榭脂水溶液 Aを 12部に変更する以外は実施例 1と同 様に分散して顔料分散体 12を得た。顔料の平均粒径は 80nmであった。  A pigment dispersion 12 was obtained by dispersing in the same manner as in Example 1, except that the 25% aqueous solution of rosin A used in Example 1 was changed to 12 parts. The average particle size of the pigment was 80 nm.
[0093] [インク 7〜13] [0093] [Ink 7-13]
実施例 1の前記顔料分散体 1に代えて、顔料分散体 7〜13を 25部使用する以外 は実施例 1と同様にして顔料濃度を 3. 75%に調整したブラックインクを作成した。  A black ink having a pigment concentration adjusted to 3.75% was prepared in the same manner as in Example 1 except that 25 parts of Pigment Dispersions 7 to 13 were used in place of Pigment Dispersion 1 of Example 1.
[0094] 上記実施例 1〜6および比較例 7〜13の分散剤として使用したスチレン （メタ)ァ クリル酸系榭脂及びアルカリ中和剤の種類にっ 、て、表 1に示した。 [0094] Table 1 shows the types of styrene (meth) acrylic acid-based resins and alkali neutralizers used as dispersants in Examples 1 to 6 and Comparative Examples 7 to 13 described above.
[0095] 上記実施例のインク 1〜6および比較例のインク 7〜13のインク糸且成について、水 以外の成分の割合を表 2に示した。 [0095] Table 2 shows the ratio of components other than water for the ink yarns of Inks 1 to 6 in the above Examples and Inks 7 to 13 in Comparative Examples.
[0096] [表 1] [0096] [Table 1]
スチレン— （メタ） アクリル酸系共重合樹脂中和物水溶液に使用した樹脂及び中和剤の種類について Types of resins and neutralizers used in aqueous solutions of styrene- (meth) acrylic acid copolymer resin neutralized products
Figure imgf000020_0001
Figure imgf000020_0001
(注） 〇印は使用した樹脂及び中和剤を表す。 (Note) 〇 indicates the resin and neutralizer used.
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実施例及ぴ比較例のィンク組成 （w t %) Ink composition of Examples and Comparative Examples (w t%)
Figure imgf000021_0002
Figure imgf000021_0002
ここで、 「Y— 74」 はイェロー顔料 （C.I. Pigment Yellow 74)、 「R— 122」 はレッド顔料 （C.I. Pigment Red 122). 「B_15 3」 はブルー顔料 （ I. Pigment Blue 15:3) を表す。  Here, “Y-74” is yellow pigment (CI Pigment Yellow 74), “R-122” is red pigment (CI Pigment Red 122). “B_15 3” is blue pigment (I. Pigment Blue 15: 3). To express.
スチレン— （メタ） アクリル酸系共重合体の中和剤は [表 1] 記載の通りである。  The neutralizing agents for styrene (meth) acrylic acid copolymers are as described in [Table 1].
また、 "ジョンクリル 537"、 "ジョンクリル 775"及び "ジョンクリル 7610"は、 固形分換算の値である。
Figure imgf000021_0001
“John Crill 537”, “John Crill 775” and “John Crill 7610” are values in terms of solid content.
Figure imgf000021_0001
[0099] (1)再分散性試験 [0099] (1) Redispersibility test
インク組成物 0. 5gをガラス製時計皿（ φ 90mm)表面に薄く塗り広げた状態にして カゝら 30°Cの恒温槽に入れ放置する。 15時間後、時計皿を恒温槽から取り出し、イン クが乾燥状態になった周辺部分の外側から少量の水で静かに洗い流した時の状態 を観察する。  Apply 0.5 g of the ink composition to the surface of a glass watch glass (φ 90 mm) thinly and place it in a thermostatic chamber at 30 ° C. After 15 hours, remove the watch glass from the thermostat and observe the condition when the ink is gently washed with a small amount of water from the outside of the surrounding area where the ink has become dry.
評価基準：（〇)凝集することなく速やかに再分散する。（△)一部小さな薄膜状の凝 集物が認められるが、ガラス表面には付着しない。 （X )かなり凝集物が認められ、ガ ラス表面にインク乾燥物が付着したまま残る。  Evaluation criteria: (◯) Redispersed promptly without agglomeration. (△) Some thin film aggregates are observed, but do not adhere to the glass surface. (X) A considerable amount of agglomerate is observed, and the dried ink remains on the glass surface.
[0100] (2)連続吐出安定性試験 [0100] (2) Continuous discharge stability test
市販の大判インクジェット用プロッタ一として (株)ミマキエンジニアリング製" JV2— 1 30" (ピエゾ方式)を使用して、印字解像度 720 X 720dpi、単色'塗りつぶし印刷、 印字幅 1200mmの条件で、ドット抜け等の印字不良が認められるまで連続印字を行 つた o  Using "JV2-130" (piezo method) manufactured by Mimaki Engineering Co., Ltd. as a commercially available large-format inkjet plotter, dot missing, etc. under the conditions of print resolution 720 X 720dpi, single color 'filled printing, print width 1200mm O Continuous printing was performed until printing failure was detected o
[0101] 評価基準：（〇） 5時間以上目詰まりなし。（△) 30分〜 1時間で目詰まりを生じた。 (  [0101] Evaluation criteria: (○) No clogging for 5 hours or more. (△) Clogging occurred in 30 minutes to 1 hour. (
X ) 30分以内に目詰まりを生じた。  X) Clogging occurred within 30 minutes.
[0102] (3)長時間放置後の吐出性  [0102] (3) Dischargeability after standing for a long time
上記印字条件にて 30分連続運転後、そのまま 48時間放置し、通常のクリーニング の後、同条件にて正常に印字ができるか再度印字テストを行った。  After 30 minutes of continuous operation under the above printing conditions, the sample was left as it was for 48 hours, and after normal cleaning, a printing test was performed again to check whether printing was possible under the same conditions.
評価基準：（〇）上記インクジェット用プロッター所定のヘッドクリーニング 1回で正常 に印刷できた。（△)数回クリーニングが必要。（X )さらにクリーニングしても回復しな い。  Evaluation criteria: (◯) The above-mentioned inkjet plotter was able to print normally after a predetermined head cleaning. (△) Requires several cleanings. (X) Does not recover even after further cleaning.
[0103] [表 3] X X X [0103] [Table 3] XXX
X X X X X X
X X X X X X
X X X X X X
イク Nンo.  Iku N.
σ: X X X  σ: X X X
分散性再  Redistribution
X X X  X X X
X X X X X X
連続吐出安定性  Continuous discharge stability
〇 〇 〇  ○ ○ ○
o 〇 〇時放後性長間置吐出の'  o 〇 〇
〇 〇 〇  ○ ○ ○
遛  遛
〇 〇 〇  ○ ○ ○
〇 〇 〇  ○ ○ ○
〇 o 〇  ○ o ○
これらの試験結果から明らかなように、本発明の実施例のように、特定の酸価、及 び重量平均分子量の範囲内のスチレン （メタ）アクリル酸系共重合体をアルカリ金 属水酸化物で中和した顔料分散体を使用して作成したインク 1 6は、再分散性が 良好で、連続吐出安定性及び長時間放置後の吐出性に優れていたが、中和剤とし てアンモニア及び有機塩基を使用した比較例のインク 7 11は、再分散性が悪く、 連続吐出安定性及び長時間放置後の吐出性も悪力つた。また、比較例のインク 12 のように、低分子量のスチレン （メタ)アクリル酸系共重合体を使用した場合も同様 に再分散性が悪ぐ連続吐出安定性及び長時間放置後の吐出性も悪力 た。また、 比較例のインク 13のように、スチレン （メタ）アクリル酸系共重合体の使用量を 20重 量％にした場合も同様に再分散性が悪ぐ連続吐出安定性及び長時間放置後の吐 出性も悪力つた。 As is clear from these test results, as in the examples of the present invention, a styrene (meth) acrylic acid copolymer within a specific acid value and weight average molecular weight range was converted to an alkali metal hydroxide. Ink 16 prepared using the pigment dispersion neutralized with the above had good redispersibility, excellent continuous ejection stability and ejection properties after standing for a long time, but ammonia and Comparative ink 711 using an organic base was poor in redispersibility, and had a poor continuous discharge stability and dischargeability after standing for a long time. The same applies when a low molecular weight styrene (meth) acrylic acid copolymer is used as in the ink 12 of the comparative example. In addition, continuous discharge stability with poor redispersibility and discharge after standing for a long time were also bad. In addition, as in Comparative Example 13, when the amount of styrene (meth) acrylic acid copolymer used is 20% by weight, the redispersibility is similarly poor, and continuous discharge stability and after standing for a long time. The exhaling ability was also bad.
産業上の利用可能性  Industrial applicability
[0105] 本発明の水性顔料分散体は、インクジェット記録用インクの製造に有用であり、イン ク調整時に各種添加剤及び水を必要に応じて添加して、使用用途に適した顔料濃 度に調整されたインクを得るために好適な水性顔料分散体である。インク調整までの 保存安定性も良好である。また、得られたインクの再分散性が向上するので、得られ たインクによるノズルの目詰まり防止性に優れ、長時間のインクジェット記録プロッタ 一の連続運転時においても装置の運転を長時間休止した後でも通常のクリーニング で安定した吐出が得られるインクジェット記録用顔料インクを得ることができる。  [0105] The aqueous pigment dispersion of the present invention is useful in the production of inks for ink jet recording, and various additives and water are added as necessary at the time of ink adjustment to obtain a pigment concentration suitable for the intended use. An aqueous pigment dispersion suitable for obtaining a conditioned ink. Storage stability until ink adjustment is also good. In addition, since the redispersibility of the obtained ink is improved, it is excellent in preventing clogging of the nozzle by the obtained ink, and the operation of the apparatus is stopped for a long time even during continuous operation of a long-time inkjet recording plotter. A pigment ink for ink-jet recording can be obtained, which can be stably discharged even after normal cleaning.
[0106] 本発明の水性顔料分散体を用いたインクジェット記録用インクは、本来要求される 保存安定性、高品位な記録画像等の性能を維持しつつ、再分散性の良いインクが 得られ、ノズルの目詰まり防止性に優れ、長時間の連続運転時においても装置の運 転を長時間休止した後でも通常のクリーニングで安定した吐出が得られるので、イン クジェット記録用顔料インクとして有用である。  [0106] An ink for ink jet recording using the aqueous pigment dispersion of the present invention provides an ink having good redispersibility while maintaining the performance of originally required storage stability, high quality recorded images, and the like. Excellent nozzle clogging prevention, and is useful as a pigment ink for ink jet recording because stable discharge can be obtained by normal cleaning even during long periods of continuous operation even after the operation of the device has been stopped for a long time. .
[0107] 前記本発明のインクジェット記録用インクを使用したインクジェット記録方法並びに インクジェット捺染方法においては、高品位な記録画像等の性能を維持しつつ、ノズ ルの目詰まりの防止性に優れ、長時間の連続運転時においても装置の運転を長時 間休止した後でも通常のクリーニングで安定したインクジェット記録並びにインクジェ ット捺染が行え、インクジェット記録並びにインクジェット捺染に有効に利用できる。  [0107] In the ink jet recording method and the ink jet textile printing method using the ink for ink jet recording of the present invention, while maintaining the performance of a high-quality recorded image and the like, it is excellent in preventing clogging of the nozzle, and for a long time. Even during continuous operation of the apparatus, stable ink jet recording and ink jet printing can be performed by ordinary cleaning even after the operation of the apparatus is stopped for a long time, and can be effectively used for ink jet recording and ink jet printing.

Claims

請求の範囲 The scope of the claims
[1] 水、顔料、高分子分散剤を含有し、顔料が高分子分散剤で分散された水性顔料分 散体において、前記高分子分散剤の含有量が、顔料に対して 30〜： LOO重量％であ り、前記高分子分散剤が、酸価が 160〜300mgKOHZg、重量平均分子量が 8, 0 00〜20, 000のスチレン （メタ）アクリル酸系共重合体をアルカリ金属水酸化物で 中和して得られた高分子分散剤であることを特徴とする水性顔料分散体。  [1] In an aqueous pigment dispersion containing water, a pigment, and a polymer dispersant, and the pigment is dispersed with the polymer dispersant, the content of the polymer dispersant is 30 to: The styrene (meth) acrylic acid copolymer having an acid value of 160 to 300 mgKOHZg and a weight average molecular weight of 8,000 to 20,000 is an alkali metal hydroxide. A water-based pigment dispersion characterized by being a polymer dispersant obtained by neutralization.
[2] 前記スチレン—（メタ）アクリル酸系共重合体の酸価が 160〜250mgKOHZgである 請求項 1に記載の水性顔料分散体。  [2] The aqueous pigment dispersion according to claim 1, wherein the styrene- (meth) acrylic acid copolymer has an acid value of 160 to 250 mg KOHZg.
[3] 前記スチレン （メタ）アクリル酸系共重合体の重量平均分子量が、 10, 000〜18, 000である請求項 1または 2に記載の水性顔料分散体。  [3] The aqueous pigment dispersion according to claim 1 or 2, wherein the styrene (meth) acrylic acid copolymer has a weight average molecular weight of 10,000 to 18,000.
[4] 前記スチレン （メタ)アクリル酸系共重合体が、連続塊状重合法で製造された共重 合榭脂である請求項 1〜3のいずれかに記載の水性顔料分散体。  4. The aqueous pigment dispersion according to any one of claims 1 to 3, wherein the styrene (meth) acrylic acid copolymer is a copolymerized resin manufactured by a continuous bulk polymerization method.
[5] さらに、表面調整剤として、シリコン系ノ-オン界面活性剤、アルコールアルコキシレ 一ト系ノユオン界面活性剤、アセチレングリコール系ノ-オン界面活性剤、フッ素系ノ ユオン界面活性剤、から選ばれる少なくとも 1種を含有する請求項 1〜4のいずれか に記載の水性顔料分散体。  [5] Further, as the surface conditioning agent, a silicon-based surfactant, an alcohol alkoxylate surfactant, an acetylene glycol surfactant, or a fluorine surfactant is selected. The aqueous pigment dispersion according to claim 1, comprising at least one selected from the group consisting of:
[6] 前記表面調整剤が、前記シリコン系ノニオン界面活性剤の一種であるポリエーテル 変性ポリジメチルシロキサンである請求項 5に記載の水性顔料分散体。  6. The aqueous pigment dispersion according to claim 5, wherein the surface conditioner is a polyether-modified polydimethylsiloxane that is a kind of the silicon-based nonionic surfactant.
[7] さらに、水溶性有機溶剤としてグリセリンを含有する請求項 1〜6のいずれかに記載 の水性顔料分散体。  7. The aqueous pigment dispersion according to any one of claims 1 to 6, further comprising glycerin as a water-soluble organic solvent.
[8] さらに、ポリエーテル変性ポリジメチルシロキサン及びグリセリンを含有し、前記ポリェ 一テル変性ポリジメチルシロキサンの含有量力 水性顔料分散体全量に対して 0. 5 〜3重量％であり、グリセリンの含有量が水性顔料分散体全量に対して 10〜30重量 %である請求項 1〜4のいずれかに記載の水性顔料分散体。  [8] Furthermore, it contains polyether-modified polydimethylsiloxane and glycerin, and the content power of the above-mentioned polyether-modified polydimethylsiloxane is 0.5 to 3% by weight based on the total amount of the aqueous pigment dispersion, and the glycerin content. The aqueous pigment dispersion according to any one of claims 1 to 4, wherein is 10 to 30% by weight based on the total amount of the aqueous pigment dispersion.
[9] 請求項 1〜8の 、ずれかに記載の水性顔料分散体を含むインクジェット記録用インク  [9] An ink for inkjet recording comprising the aqueous pigment dispersion according to any one of claims 1 to 8.
[10] 前記スチレン （メタ）アクリル酸系共重合体の含有量力 インク全量に対して 1〜6 重量％である請求項 9に記載のインクジェット記録用インク。 10. The ink for inkjet recording according to claim 9, wherein the content power of the styrene (meth) acrylic acid copolymer is 1 to 6% by weight based on the total amount of the ink.
[11] 前記インクジェット記録用インクがグリセリンを含有するインクジェット記録用インクであ り、前記グリセリンの含有量力 Sインク全量に対して 5〜50重量％である請求項 9または[11] The ink for ink jet recording is an ink for ink jet recording containing glycerin, and the content power of the glycerin is 5 to 50% by weight with respect to the total amount of the ink.
10に記載のインクジェット記録用インク。 The ink for inkjet recording according to 10.
[12] 前記インクジェット記録用インクが表面調整剤を含有するインクジェット記録用インク であり、前記表面調整剤の含有量がインク全量に対して 0. 05〜2重量％である請求 項 9〜： L 1のいずれかに記載のインクジェット記録用インク。 [12] The ink for ink jet recording is an ink for ink jet recording containing a surface conditioner, and the content of the surface conditioner is 0.05 to 2% by weight with respect to the total amount of the ink. 2. The ink for inkjet recording according to any one of 1.
[13] 前記表面調整剤が、ポリエーテル変性ポリジメチルシロキサンである請求項 12に記 載のインクジェット記録用インク。 13. The ink for ink jet recording according to claim 12, wherein the surface conditioner is polyether-modified polydimethylsiloxane.
[14] さらに榭脂ェマルジヨンを含有する請求項 9〜13のいずれかに記載のインクジェット 記録用インク。 [14] The ink for inkjet recording according to any one of [9] to [13], further comprising a resin emulsion.
[15] 請求項 9〜 14のいずれかに記載のインクジェット記録用インクを使用して紙製品に印 刷することを特徴とするインクジェット記録方法。  [15] An inkjet recording method comprising printing on a paper product using the inkjet recording ink according to any one of [9] to [14].
[16] 請求項 14に記載のインクジェット記録用インクを使用して繊維製品に印刷することを 特徴とするインクジェット捺染方法。 [16] An ink jet textile printing method comprising printing on a textile using the ink for ink jet recording according to [14].
PCT/JP2005/021561 2004-12-09 2005-11-24 Aqueous pigment dispersion, ink-jet recording ink, and recording method and textile printing method using the same WO2006061995A1 (en)

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