Classifications

• • 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
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

• the present invention relates to a pigment dispersion suitably usable for various ink compositions including use for ink jet printing, and an ink for ink jet printing.
• a pigment type ink using a pigment as a coloring agent has an advantage of being excellent in light resistance and water resistance as compared with a dye type ink using a dye as a coloring agent.
• a pigment is generally insoluble in water, it is necessary to be mixed with a resin called as a dispersant for being stably dispersed in water.
• a pigment type ink as a dispersion is poor in stability as a lapse of time since a pigment settles.
• a pigment type ink generally has a disadvantage of being poor in transparency and coloring. Particularly, when recording on a transmission manuscript represented as an OHP film processed for an aqueous recording liquid, transparency is lowered and coloring is remarkably dull due to light scattering by pigment particles.
• a pigment and a resin are kneaded to prepare a solid colored compound, and the compound is dispersed in a dispersing medium to improve transparency and coloring (JP-A-11-80,633); a storage stability of a dispersion is improved by using a pigment coated with a cured polymer having a polar group insoluble in a dispersion medium (JP-A-5-247,370); a pigment is coated with a resin swellable in a dispersion medium to prevent clogging or bleeding (JP-A-3-240,586); and an aqueous solution containing a resin, an amine and water are stirred to fully dissolve the resin, and a premixed pigment is subjected to dispersion treatment to stabilize injecting by controlling a non-adsorbed resin amount to at most 2% (JP-A-2-255,875).
• the present inventors have intensive studied to solve these problems. As a result of the study, it has been found that an excellent ink for ink jet and an excellent pigment dispersion for ink jet having a satisfactory dispersion stability can be obtained without spoiling other performances by using a dispersion having a combination of specific plural resins contained, particularly in the preparation of an ink having a high permeability.
• a pigment dispersion for ink jet having a pigment dispersed, characterized by containing a water-soluble resin and a resin having a urethane bond and/or an amide bond;
• an ink composition for ink jet having a pigment dispersed, characterized by containing a water-soluble resin and a resin having a urethane bond and/or an amide bond;
• an ink composition for ink jet which is obtained by adding an organic solvent to the pigment dispersion as defined in any one of the above features (1) to (3);
• an ink jet recording method which comprises printing by discharging the ink composition for ink jet as defined in any one of the above features (5) to (8) from a nozzle of an ink jet printer;
• the pigment dispersion of the present invention comprises at least a pigment and specific two kinds of resins.
• the pigment used in an aqueous ink composition for ink jet of the present invention is not specifically limited, and any of an organic pigment and an inorganic pigment can be used.
• Examples of the organic pigment include an azo pigment such as an azolake, an insoluble monoazo pigment, an insoluble disazo pigment, a condensed azo pigment, a chelate azo pigment or the like; a polycyclic pigment such as a phthalocyanine pigment, a perylene pigment, a perynone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxazine pigment, a thioindigo pigment, an isoindolinone pigment, a quinophthalone pigment or the like; a dye chelate such as a basic dye type chelate, an acidic dye type chelate or the like; a nitro pigment; a nitroso pigment; and the like.
• an azo pigment such as an azolake, an insoluble monoazo pigment, an insoluble disazo pigment, a condensed azo pigment, a chelate azo pigment or the like
• a polycyclic pigment such as a phthalocyanine pigment,
• examples of the inorganic pigment include titanium oxide, iron oxide, rouge, chromium oxide, Prussian blue, ultramarine blue, molybdate orange, black iron oxide, chrome yellow, carbon black, and the like, and they can be used respectively alone or in a mixture of two or more.
• an isoindolinone type pigment, a quinacridone type pigment, a condensed azo type pigment, a phthalocyanine type pigment, a quinophthalone type pigment, an anthraquinone type pigment or carbon black is preferably usable.
• pigment•yellow 1 color index (hereinafter referred to as “C.I.”) 11680
• pigment•yellow 3 C.I. 11710
• pigment•yellow 14 C.I. 21095
• pigment•yellow 17 C.I. 21105
• pigment•yellow 42 C.I. 77492
• pigment•yellow 74 C.I. 11741
• pigment•yellow 83 C.I. 21108
• pigment•yellow 93 C.I. 20710
• pigment•yellow 98 C.I. 11727
• pigment•yellow 109 C.I. 56284)
• pigment•yellow 110 C.I.
• pigment•yellow 128 C.I. 20037
• pigment•yellow 138 C.I. 56300
• pigment•yellow 139 C.I. 56298
• pigment•yellow 147 C.I. 60645
• pigment•yellow 154 C.I. 11781
• pigment•yellow 155 pigment•yellow 180
• pigment•yellow 185 pigment•orange 5 (C.I. 12075), pigment•orange 13 (C.I. 21110), pigment•orange 16 (C.I. 21160), pigment•orange 34 (C.I. 21160), pigment•orange 43 (C.I. 71105), pigment•orange 61 (C.I.
• pigment•orange 71 (C.I. 561200), pigment•red 5 (C.I. 12490), pigment•red 8 (C.I. 12335), pigment•red 17 (C.I. 12390), pigment•red 22 (C.I. 12315), pigment•red 48:2 (C.I. 15865:2), pigment•red 112 (C.I. 12370), pigment•red 122 (C.I. 73915), pigment•red 177 (C.I. 65300), pigment•red 178 (C.I. 71155), pigment•red 202 (C.I. 73907), pigment•red 254 (C.I. 56110), pigment•red 19 (C.I. 46500), pigment•violet 23 (C.I.
• pigment•blue 15:1 C.I. 74160
• pigment•blue 15:3 C.I. 74160
• pigment•blue 15:4 C.I. 74160
• pigment•blue 60 C.I. 69800
• pigment•green 7 C.I. 74260
• pigment•green 36 C.I. 74265
• pigment•yellow 42 (C.I. 77492), pigment-white 6 (C.I. 77891), pigment•blue 27 (C.I. 77510), pigment•blue 29 (C.I. 77007), pigment•black 7 (C.I. 77266), and the like.
• Preferable examples include pigment•yellow 74 (C.I. 11741), pigment•yellow 109 (C.I. 56284), pigment•yellow 110 (C.I. 56280), pigment•yellow 128 (C.I. 20037), pigment•yellow 155, pigment•yellow 180 (C.I. 21290), pigment•red 122 (C.I. 73915), pigment•red 202 (C.I. 73907), pigment•violet 19 (C.I. 46500), pigment•blue 15:1 (C.I. 74160), pigment•blue 15:3 (C.I. 74160), pigment•blue 15:4 (C.I. 74160), pigment•blue 60 (C.I. 69800), pigment•black 7 (C.I. 77266), and the like.
• an organic pigment in view of stability since its particle size easily becomes small and its specific gravity is also small. Further, when considering dispersibility, a primary particle size of a pigment is preferably at most about 0.1 ⁇ m.
• the present invention is characterized by including at least two kinds of resins.
• First resin is a water-soluble resin including various resins usable as a dispersant which is adsorbed on a pigment and works for improving dispersibility of the pigment.
• a water-soluble resin having a hydrophobic group and a hydrophilic group is desirable since it is excellent in dispersing a pigment.
• Typical examples include a copolymer of a hydrophobic monomer and a hydrophilic monomer, and such a copolymer is particularly excellent in dispersing a pigment.
• hydrophobic monomer means a monomer having a hydrophobic group and the term “hydrophilic monomer” means a monomer having a hydrophilic group, which are copolymerizable.
• hydrophobic monomer examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, 2-ethylhexyl acrylate, 2-methylhexyl methacrylate, dec
• a hydrophobic group contained in a hydrophobic monomer is not specially limited, examples of which include an organic group having an aromatic ring such as a phenyl group, a benzyl group or the like, which may be substituted, and an alkyl group which may be substituted, but a ring having an aromatic ring is particularly preferable.
• hydrophilic monomer examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like.
• a ratio of a hydrophilic monomer and a hydrophobic monomer is not specially limited, but it is particularly preferable that a hydrophilic monomer: hydrophobic monomer weight ratio is in a range of from 5:95 to 40:60.
• a copolymer can be obtained by copolymerizing these hydrophobic monomers and hydrophilic monomers. Polymerization can be carried out by a known method, but it is preferable that copolymerization is carried out by a random copolymerization method since a copolymer obtained by random copolymerization provides an excellent stability as a lapse of time when a dispersion is prepared by using the copolymer thus obtained as a dispersant.
• an alkali-soluble resin obtained by neutralizing the above-mentioned copolymer of a hydrophobic monomer and a hydrophilic monomer with an alkaline material is particularly preferable to use an alkali-soluble resin obtained by neutralizing the above-mentioned copolymer of a hydrophobic monomer and a hydrophilic monomer with an alkaline material as a neutralizer to have the polymer solubilized in an aqueous medium.
• Examples of the neutralizer include an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like, monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, morpholine, ammonia, and the like.
• alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like
• monoethanolamine diethanolamine
• triethanolamine monoethylamine
• diethylamine diethylamine
• triethylamine morpholine
• ammonia and the like.
• the water-soluble resin having a hydrophilic group and a hydrophobic group include a styrene-acrylic acid copolymer, a styrene-methylstyrene-acrylic acid copolymer, a styrene-acrylic acid-(meth)acrylic acid ester (a lower alkyl ester of about C 1 C 4 , hereinafter the same) copolymer, a methacrylic acid-(meth)acrylic acid ester copolymer, an acrylic acid-(meth)acrylic acid ester copolymer, a styrene-methacrylic acid copolymer, a styrene-maleic acid copolymer, a styrene-methylstyrene-maleic acid copolymer, a styrene-(meth)acrylic acid ester-maleic acid copolymer, a styrene-(meth)acrylic acid este
• particularly preferable examples include a styrene-acrylic acid copolymer, a styrene-methylstyrene-acrylic acid copolymer, a styrene-maleic acid copolymer, a methacrylic acid-(meth)acrylic acid ester copolymer, and the like.
• a pigment dispersion having particularly excellent dispersibility can be obtained.
• a high molecular dispersant can also be used.
• a polyvinyl alcohol type dispersant, a polyacrylamide type dispersant, a polyester type dispersant, a polyacrylic acid type dispersant or the like is known, and they may be selected from commercially available products.
• a glass transition point of the water-soluble resin is not specially limited, but a preferable glass transition point is at least 30° C., more preferably at least 50° C.
• a dispersion and an ink composition become poor in stability as a lapse of time.
• a pigment having a function partially as a dispersant does not work when a temperature is raised, and consequently the stability as a lapse of time becomes poor.
• the glass transition point indicates a temperature zone wherein physical properties rapidly vary by partial crystallization or hydrogen bonding in the inside of a non-crystalline solid such as a plastic when a temperature is lowered, and can be measured by a thermally analyzing apparatus such as “DSC7” of Perkin Elmer Co. It is general to carry out the thermal analysis at a temperature gradient of 5 to 10° C./min.
• a copolymer comprising a hydrophobic monomer such as styrene or (meth)acrylic acid ester and a hydrophilic monomer such as (meth)acrylic acid, and having a glass transition point of at least 30° C., more preferably at least 50° C., is particularly excellent in dispersion stability.
• a molecular weight of a water-soluble resin is not specially limited, but a preferable molecular weight is 2,000 to 30,000, more preferably 2,000 to 20,000, as a weight average molecular weight measured by GPC (gel permeation chromatography).
• an acid value of a water-soluble resin is preferably from 50 to 320, more preferably from 55 to 270.
• the acid value is an mg amount of KOH necessary for neutralizing 1 g of a resin.
• a water-soluble resin is added in an amount of from 5 to 100 parts by weight, more preferably from 10 to 80 parts by weight, to 100 parts by weight of a pigment. If the amount of a water-soluble resin is less than 5 parts by weight to 100 parts by weight of a pigment, dispersibility of a pigment becomes insufficient and a deposit is formed or a stability as a lapse of time becomes poor. On the other hand, if the amount of a water-soluble resin exceeds 100 parts by weight, a dispersion or an ink prepared therefrom becomes highly viscous, and an injecting performance is lowered.
• the present invention further employs a resin having an amide bond and/or a urethane bond as a second resin in addition to the above-mentioned water-soluble resins.
• a resin having an amide bond and/or a urethane bond as a second resin in addition to the above-mentioned water-soluble resins.
• Their examples include a homopolymer obtained by polymerizing (meth)acrylamide, vinylpyrrolidone or the like, a copolymer of the above illustrated homopolymers with other vinyl monomers, a polyurethane resin, and the like.
• a polyurethane resin is particularly preferable.
• the polyurethane resin is not specially limited, and a water-soluble or water-dispersible polyurethane resin obtained by reacting a diisocyanate compound and a diol compound is usable.
• diisocyanate compound examples include an alicyclic diisocyanate compound such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate or the like, an arylaliphatic diisocyanate compound such as xylylene diisocyanate, tetramethylxylylene diisocyanate or the like, an aromatic diisocyanate compound such as toluilene diisocyanate, phenylmethane diisocyanate or the like, a modified material of the above illustrated diisocyanates (such as carbodiimide, uretodion or uretoimine-containing modified materials), and the like.
• an alicyclic diisocyanate compound such as hexamethylene diisocyanate, 2,2,4-trimethylhe
• diol compound examples include a diol compound obtained by (co)polymerizing an alkylene oxide such as ethylene oxide or propylene oxide, and a heterocyclic ether such as tetrahydrofuran or the like.
• the diol compound include a polyether diol such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol or the like, a polyester diol such as polyethylene adipate, polybutylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyethylene/butylene adipate, polyneopentyl/hexyl adipate or the like, a polylactone diol such as polycaprolactone diol or the like, polycarbonate diol, and the like.
• a polyether diol such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol or the like
• a polyester diol such as polyethylene adipate, polybutylene adipate, polyneopentyl adipate, poly-3-methylpent
• diol compounds having an acidic group such as a carboxylic acid group, a sulfonic acid group or the like are usable, examples of which include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutyric acid and the like. Among them, dimethylolpropionic acid is preferable.
• These diol compounds may be used in a combination of two or more kinds.
• a polyhydroxy compound having a low molecular weight may be added.
• the polyhydroxy compound having a low molecular weight includes a material usable as a starting material for polyester diol, such as glycol, an alkylene oxide low mol adduct, a trihydric alcohol such as glycerin, trimethylolethane or trimethylolpropane, and their alkylene oxide low mol adducts.
• a chain can be extended after neutralizing or during neutralizing an acid group derived from dimethylolalkanoic acid or a chain can be extended with di(tri)amine.
• a polyamine used in the extension of chain include hexamethylenediamine, isophoronediamine, hydrazine, piperazine or the like, and they may be used in a combination of two or more.
• the form of a urethane resin is not limited. Typical forms include an emulsion type such as self-emulsified emulsion or self-stabilized type. Particularly, among the above compounds, a diol having an acidic group such as a carboxylic acid group, a sulfonic acid group or the like is preferably usable, or a polyhydroxy compound having a low molecular weight may be added, or a urethane resin having an acidic group introduced, particularly one having a carboxyl group, is desirable. Further, it is preferable for improving gloss or friction resistance to crosslink these functional groups such as a carboxyl group with the following crosslinking treatment.
• a diol having an acidic group such as a carboxylic acid group, a sulfonic acid group or the like is preferably usable, or a polyhydroxy compound having a low molecular weight may be added, or a urethane resin having an acidic group introduced, particularly one having a carboxyl group, is desirable
• a base used for neutralization examples include an alkyl amine such as butyl amine or trimethyl amine, an alkanol amine such as monoethanol amine, diethanol amine or triethanol amine, morpholine, ammonia, and an inorganic base such as sodium hydroxide or the like.
• Examples of a high molecular material having an amide bond and/or a urethane bond include a polyether type polyurethane resin, a polyester type polyurethane resin or a polycarbonate type polyurethane resin, which are obtained by using a polyether type diol, a polyester type diol or a polycarbonate type diol.
• an acid value of the high molecular compound having an amide bond and/or a urethane bond is not specially limited, but is preferably from 5 to 100, more preferably from 10 to 80.
• Preferable examples of the high molecular compound having an amide bond and/or a urethane bond include NeORez R-960 (manufactured by Zeneca), NeORez R-989 (manufactured by Zeneca), NeORez-9320 (manufactured by Zeneca), NeORad NR-440 (manufactured by Zeneca), Hydran AP-30 (manufactured by Dainippon Ink and Chemicals, Incorporated), Hydran APX-601 (manufactured by Dainippon Ink and Chemicals, Incorporated), Hydran SP-510 (manufactured by Dainippon Ink and Chemicals, Incorporated), Hydran SP-97 (manufactured by Dainippon Ink and Chemicals, Incorporated),
• the resin having a urethane bond and/or an amide bond is added in an amount of from 5 to 100 parts by weight, preferably from 10 to 80 parts by weight, to 100 parts by weight of a pigment. If the amount of the resin is less than 5 parts by weight to 100 parts by weight of a pigment, friction resistance of a recorded material becomes poor, and stability as a lapse of time also becomes poor. On the other hand, if the amount of the resin exceeds 100 parts by weight, a dispersion and an ink composition become highly viscous, and an injecting performance becomes lowered, thereby lowering gloss.
• the present invention is characterized by using a combination of the above-mentioned water-soluble resin and the resin having an amide bond and/or a urethane bond.
• An adding method is not limited, but preferably the water-soluble resin is first added to a pigment. Thereafter, the mixture is subjected to the following kneading step to form a dispersion having the pigment dispersed therein, and then it is preferable to add the resin having an amide bond and/or a urethane bond to the dispersion. It is preferable to carry out the following crosslinking treatment before or after adding the resin having an amide bond and/or a urethane bond.
• the crosslinking treatment after adding the resin having an amide bond and/or a urethane bond. It has been found that dispersion stability and gloss are remarkably improved by adding the resins in this manner. This is probably because the water-soluble resin is firmly fixed onto the pigment surface in the kneading step to achieve a desired dispersion state, and the water-soluble resin and the resin having an amide bond and/or a urethane bond forms a film coated on the pigment surface by the crosslinking reaction, and the film is more firmly fixed and stabilized.
• an amount of a free resin not adsorbed on the pigment can be reduced, and the added resin can effectively disperse the pigment, thereby achieving quite satisfactory dispersion stability.
• a urethane resin having an acidic group introduced as the resin having an amide bond and/or a urethane bond, particularly one having a carboxyl group these carboxyl groups are crosslinked with a functional group such as a carboxyl group contained in the previously added water-soluble resin by a crosslinking agent in the crosslinking step, thus more firmly bonding to the pigment.
• the crosslinking treatment may be carried out after adding the water-soluble resin and the crosslinked water-soluble resin is firmly fixed on the pigment to improve stability.
• the method for measuring an amount of an unadsorbed resin comprises precipitating a pigment and a resin content adsorbed on the pigment by an ultra-centrifugal machine, and then measuring an amount of a remaining resin contained in the supernatant liquid by TOC (total organic carbon meter) or gravimetric method (method comprising evaporating the supernatant liquid to solid and measuring a resin amount) (JP-A-2-255,875).
• a particularly suitable method in the present invention comprises subjecting a liquid to an ultra-high speed cooling centrifugal machine (Beckman-made) at 55,000 rpm for 5 hours to precipitate a pigment content and a resin content adsorbed on the pigment, thereafter taking a predetermined amount of the supernatant liquid or taking only a resin not adsorbed by a membrane-separating method such as an ultrafiltration method, and then drying to solid by a vacuum dryer (60° C., 24 hours). This resin amount is calculated by percentage as a remaining resin concentration to the charged ink.
• a satisfactory dispersion can be achieved by dispersing a pigment at a stage of adding a water-soluble resin, and then a resin having an amide bond and/or a urethane bond is added to carry out crosslinking treatment, thereby firmly fixing the both resins to the pigment. Further, when a solvent having a high permeability is added thereto, stability is improved and agglomeration of pigments at the time of drying is hardly caused, and smoothness of a paper surface is improved, thus improving gloss also.
• a pigment and the above-mentioned water-soluble resin it is preferable to first knead a pigment and the above-mentioned water-soluble resin.
• the kneading step is not specially limited and a well known step may be employed so long as the pigment and the water-soluble resin are kneaded in contact with each other.
• a solid content ratio (weight) of pigment: water-soluble resin is preferably 95:5-65:35, more preferably 90:10-70:30.
• a system of being mixed with water may be employed, and in such a case, an ordinary stirrer may be satisfactorily used.
• a pigment may be wetted with a water-soluble resin.
• a resin and a water-soluble resin, and an organic resin added optionally as desired are charged into a kneading apparatus, and are kneaded therein.
• the organic solvent used is not specially limited, but it is preferable to use a solvent having such a high boiling point as not being volatilized in the kneading step in order to prevent the pigment from splashing during the step, and it is preferable to have the resin dissolved by using a solvent having a lower boiling point in combination.
• Examples of the solvent having a high boiling point include polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol or glycerin, pyrrolidones such as N-methyl-2-pyrrolidone or 2-pyrrolidone, and the like.
• An amount of the solvent used is selected depending on a combination of a pigment and a resin in such a manner as to apply an appropriate shear to a mixture of a pigment and a resin during the kneading operation, and the solvent is generally added in an amount of from 20 to 100 parts by weight, preferably from 30 to 80 parts by weight, to 100 parts by weight of a pigment.
• Examples of the organic solvent having a low boiling point used at the time of kneading include alcohols such as methanol, ethanol or isopropyl alcohol, and ketones such as acetone or methyl ethyl ketone.
• a kneading apparatus employed is not specially limited so long as it provides an appropriate shear to a mixture of a pigment and a resin in contact with each other at the time of kneading, and may be selected from general kneading apparatuses. Typical examples include two-roll or three-roll rollers or kneaders.
• the mixture of a pigment and a water-soluble resin in a kneading apparatus is heated by the heat of the apparatus or self-heated by a shear force received from the kneading apparatus, thereby raising a temperature.
• the kneading temperature is adjusted to be from 25 to 200° C., preferably from 100 to 150° C.
• the neutralization may be carried out by adding the pigment kneaded product to a solvent having an alkaline compound added in water, and mixing and stirring.
• the alkaline compound used for neutralization is not specially limited.
• examples of the alkaline compound include organic amines such as ammonia, monomethanol amine, diethanol amine, triethanol amine, morpholine or 2-amino-2-methyl-1-propanol; and alkali metal salts such as sodium hydroxide, potassium hydroxide or ammonium hydroxide.
• an amount of the alkaline compound added is such an amount as to completely neutralize a hydrophilic group in the resin, and accordingly it is preferable to make a neutralization rate of 80 to 150%, particularly 90 to 120%, which is determined by an equivalent amount of the alkaline compound added and an acid equivalent amount of the resin.
• the heating temperature is preferably from 40 to 100° C., more preferably from 60 to 90° C.
• the pigment kneaded product is dispersed by a dispersing machine such as a beads mill as described below.
• a dispersing machine such as a beads mill as described below.
• various additives such as a preservative, a wetting agent and the like may be added in addition to the pigment kneaded product, water and alkali.
• Dispersing means are not specially limited, and typical examples include various mechanical methods conventionally employed in the preparation of a pigment fine particle dispersion, e.g. a mechanical method such as a grinding method using a ball mill and a pulverizing method by vibration such as an ultrasonic dispersing machine. Further, it is well known to employ a method of using a dispersing machine called as a sand mill, a basket mill or a pearl mill for an apparatus of obtaining finer particles.
• the dispersing medium and a dispersing machine used herein are not specially limited, and conventionally well known various materials may be used.
• the dispersing medium is not specially limited, but its preferable examples include ceramics; hard glass such as soda glass beads or alkali-free beads; hard plastic beads such as polymethyl methacrylate beads; metals such as chrome beads or stainless steel beads; or metal compounds such as zirconia. Zirconia is particularly preferable since it can produce satisfactorily fine particles.
• an amount of a dispersing medium loaded into a dispersing machine is at least 65%, preferably at least 70%, and a mixing ratio of a dispersing medium and an aqueous pigment composition (dispersing medium/aqueous pigment composition (volume ratio)) is at least 1/30, preferably at least 1/25, and when considering a practical operation efficiency, the mixing ratio is preferably at most 1/1, more preferably at most 1/2.
• a wet system pulverizing apparatus having the above-mentioned dispersing machine at a peripheral velocity of at least 5 m/s, preferably at least 7 m/s, in respect of making fine particles of a pigment.
• the time of operating the wet system pulverizing apparatus is not specially limited, but may be from about 2 to 150 minutes as a residence time of dispersion.
• a particle size is at least 5 nm and at most 200 nm after dispersing a pigment. Further, it is preferable to finally make a pigment having a particle size in a range of from 5 to 100 nm by removing coarse particles by centrifugal treatment. If the particle size exceeds 100 nm, separation or settling of pigments tends to occur. On the other hand, if the particle size is smaller than 5 nm, control or light resistance performances of particles become poor. A particularly preferable particle size is in a range of from 5 to 80 nm.
• This particle size is a dispersed particle size (volume 50% particle size) of pigment particles actually forming a dispersion, and Microtrac UPA (LEEDS & NORTHRUP Co.) is used as a measuring device.
• a pigment is finely pulverized in a kneading step and a dispersing step, and it is preferable to crosslink a resin in a dispersion state before or after adding a resin having a urethane bond and/or an amide bond.
• a crosslinking agent crosslinkable at a low temperature of about 0 to 100° C.
• This crosslinking reaction is a reaction of producing a new chemical bond bonding high molecular materials having a chain-like structure to newly develop a tridimensional net-like structure, and includes a case of further crosslinking high molecular materials already having a partially crosslinked structure and also a case of precipitating a higher molecular material from a dissolved resin.
• a curing reaction is also included in the crosslinking reaction.
• Examples of the crosslinking agent include a carboxyl group-reactive type such as a polycarbodiimide type having a carbodiimide group in a molecule, an oxazoline type having an oxazoline group in a molecule or an aziridine type. Further examples include a hydroxyl group-reactive type such as a melamine resin type of butyrated melamine or full-etherified melamine, or an isocyanate type represented as an aqueous block isocyanate. Still further examples include a carbonyl group-reactive type such as a dihydrazide type.
• an ethyleneimine type having an active amino group such as polyethyleneimine, aminoethyl-modified ethyleneimine or aziridinyl-modified ethyleneimine, an aliphatic amine such as polymethylene diamine, an aromatic amine such as diaminodiphenylmethane, an epoxy resin type having a glycidyl ether structure, and an aqueous oligomer such as an acryl oligomer having a (meth)acryloyl group.
• the aqueous oligomer include an oligoester (meth)acrylate mainly having an ester bond, an epoxy (meth)acrylate having an epoxy resin as a main structure, and the like.
• a carboxyl group-reactive type is particularly preferable since it is excellent in dispersibility in a pigment dispersion.
• a blending ratio of a crosslinking agent to a resin is preferably 1/100-50/100 at a weight ratio (crosslinking agent/resin (effective solid content weight ratio)). If the weight ratio is smaller than 1/100, a crosslinking effect becomes poor and stability of a dispersion or an ink becomes poor, and if the weight ratio is larger than 50/100, agglomeration of pigments tends to occur and a viscosity of the liquid becomes high.
• the weight ratio should be at least 1/100, preferably at least 2/100, and in order to prevent qualities of an aqueous pigment dispersion from lowering due to an excess amount of a crosslinking agent, the weight ratio is at most 50/100, preferably at most 45/100, and any further improvement of the crosslinking effect can not be expected if the weight ratio is still larger.
• crosslinking without a crosslinking agent.
• a combination of at least two kinds of crosslinkable functional groups must be contained in a molecule.
• Examples of a self-crosslinkable functional group include a radical-polymerizable unsaturated functional group and a hydrolyzable alkoxysilane group.
• Examples of a combination of such radical-polyemerizable unsaturated functional groups include preferably a combination of a carboxyl group and an epoxy group, a combination of a carboxyl group and a 1,3-dioxolan-2-on-4-yl group, a combination of a hydroxyl group and a blocked isocyanate group, a combination of a hydroxyl group and a N-alkoxymethylamide group, a combination of a hydroxyl group and a hydrolyzable alkoxysilane group or a combination of an amino group and an epoxy group, and a self-crosslinkable functional group may be introduced when copolymerizing the above-mentioned hydrophobic monomer and hydrophilic monomer.
• Temperature and time for crosslinking a resin are not specially limited, and may be adjusted depending on kinds of a resin and a crosslinking agent employed.
• pH at the time of finishing the crosslinking reaction may be in a range of from 7.0 to 10.0, and if pH is at most 7.0, there is a possibility that a water-soluble resin dissolved by naturalization tends to precipitate, and stability as a lapse of time becomes poor.
• the crosslinking treatment achieves remarkable effects of not causing agglomeration and adsorption among pigment particles in water, maintaining a function of a resin itself as a dispersant, curing and stabilizing. Accordingly, it is preferable to maintain a functional group, e.g. a polar group such as a carboxyl group, necessary for maintaining a resin itself in a dissolved state without completely reacting the functional group in a resin, even after crosslinking
• a functional group e.g. a polar group such as a carboxyl group
• a crosslinking rate of a resin in a dispersion i.e. so-called a gel fraction
• a gel fraction is preferably from 20 to 100%.
• the gel fraction is preferably at least 30%, more preferably at least 35%.
• the upper limit of the gel fraction is 100%, and a higher gel fraction is more preferable.
• the gel fraction is generally considered as a measure of a crosslinking degree of a resin, but the gel fraction in the present invention is calculated from a numerical value determined by measuring an elution amount of a resin by drying an aqueous pigment dispersion to powder and using tetrahydrofuran as a solvent.
• an aqueous pigment dispersion is freeze-dried and 10 g of the obtained powder is placed in 100 ml of tetrahydrofuran and is stirred at 60° C. for 1 hour.
• a gel fraction is calculated by measuring a solid content of a resin amount eluted in tetrahydrofuran and making an elution amount at the time of not crosslinking as “blank”.
• a weight average molecular weight of a crosslinked resin is preferably at least 30,000, more preferably at least 200,000, in respect of fully improving properties of an aimed aqueous pigment dispersion. A larger weight average molecular weight is more preferable.
• a divalent metal ion content in an aqueous pigment dispersion it is preferable to adjust a divalent metal ion content in an aqueous pigment dispersion to at most 100 ppm by treating with an ion exchange resin or the like. It is more preferable to adjust to 50 ppm.
• a metal ion content can be measured by an atomic absorption photometer Z-8230 (Hitachi, Ltd.) or an ICP analyzing apparatus SPQ9000 (Seiko Denshi Corporation), and the numerical values in the present invention were measured by these apparatuses.
• a multi-valent ion content in a recording ink is preferably at most 100 ppm, more preferably at most 80 ppm.
• One of methods of removing multi-valent metal ions is to treat a dispersion or a recording ink with a cation exchange resin.
• the cation exchange resin (weak acidic cation exchange resin, strong acidic cation exchange resin) used is not specially limited so long as it removes a multi-valent metal ion, and a commercially available cation exchange resin may be appropriately selected.
• Examples of the commercially available cation exchange resin include ⁇ DIAION WK 10 ⁇ , ⁇ DIAION WK 11 ⁇ , ⁇ DIAION WK 20 ⁇ , ⁇ DIAION PA 406 ⁇ , ⁇ DIAION PA 408 ⁇ , ⁇ DIAION PA 412 ⁇ , ⁇ DIAION PA 416 ⁇ , ⁇ DIAION PA 418 ⁇ , ⁇ DIAION PK 208 ⁇ , ⁇ DIAION PK 212 ⁇ , ⁇ DIAION PK 216 ⁇ , ⁇ DIAION PK 220 ⁇ and ⁇ DIAION PK 228 ⁇ (manufactured by Mitsubishi Chemical Corporation), ⁇ Amberlite IR-118H ⁇ , ⁇ Amberlite IR-120B ⁇ , ⁇ Amberlite IR-122 ⁇ , ⁇ Amberlite IR-124 ⁇ , ⁇ Amberlite 252 ⁇ , ⁇ Amberlite 201CT ⁇ , ⁇ Amberlite 200C ⁇ , ⁇ Amberlite IRC-50 ⁇ and ⁇ Amberlite IRC-84 ⁇ (manufactured by Organo Corporation).
• the treatment may be carried out in combination with an anion exchange resin (weak basic anion exchange resin, medium basic anion exchange resin or strong basic anion exchange resin) treatment.
• anion exchange resin include ⁇ DIAION WA 10 ⁇ , ⁇ DIAION WA 11 ⁇ , ⁇ DIAION WA 20 ⁇ , ⁇ DIAION WA 21 ⁇ , ⁇ DIAION WA 30 ⁇ , ⁇ DIAION PA 406 ⁇ , ⁇ DIAION PA 408 ⁇ , ⁇ DIAION PA 412 ⁇ , ⁇ DIAION PA 416 ⁇ , ⁇ DIAION PA 418 ⁇ , ⁇ DIAION PA 306 ⁇ , ⁇ DIAION PA 308 ⁇ , ⁇ DIAION PA 312 ⁇ , ⁇ DIAION PA 316 ⁇ , ⁇ DIAION PA 318 ⁇ , ⁇ DIAION SA 10A ⁇ , ⁇ DIAION SA 11A ⁇ , ⁇ DIAION SA 12A ⁇ , ⁇ DIAION SA 20A ⁇ and ⁇ DIAION SA 21A ⁇ (manufactured by Mitsubishi Chemical Corporation), ⁇ Amberlite IRA-400T ⁇ , ⁇ Amberlite IRA-400T ⁇
• an ultrafiltration membrane As a method for removing impurities, an ultrafiltration membrane is used. Generally, this means a treatment with a separating membrane capable of removing each component from compounds having respectively from a low molecular weight to a high molecular weight and ionic materials in a solution by each kind of membranes.
• Examples of impurities include a material remaining at the time of preparing a pigment, an excess component in a dispersion liquid composition, a dispersant not adsorbed on an organic pigment, and a contaminating component.
• a molecular weight of a material separatable by an ultrafiltration membrane varies depending on its fractional molecular weight of the ultrafiltration membrane. For example, when a fractional molecular weight of the ultrafiltration membrane used in the treatment is 1000, only a material having a molecular weight of at most 1000 is separatable from a solvent.
• the pigment dispersion liquid of the present invention contains a dispersion medium in addition to the above-described pigment and specific resins.
• the dispersion medium is not specially limited, and a dispersion medium conventionally used for a pigment dispersion liquid can be selected.
• a dispersion medium conventionally used for a pigment dispersion liquid can be selected.
• water and other aqueous medium are preferable, but other various organic solvents may be contained.
• the aqueous medium used herein means water or a water-soluble solvent compatible with water. It is particularly preferable to use an ion-exchanged water as water, but it is not limited thereto.
• a water-soluble solvent is preferably selected from solvents used in an ink composition described below.
• pigment dispersion liquid is not specially limited and optimally selected so long as they do not adversely affect physical properties of the dispersion or do not adversely affect the preparation of an ink, and may include a solvent selected from an organic solvent used in an ink composition for ink jet described below or an additive such as a mildew-proofing agent to an aqueous ink composition using an aqueous medium.
• the ink composition of the present invention is an ink composition for ink jet having a pigment dispersed, and is an ink composition for ink jet characterized by containing a water-soluble resin and a resin having a urethane bond and/or an amide bond.
• the preparation method of the ink composition of the present invention is not specially limited, but it is preferable to prepare a pigment dispersion liquid by the above-mentioned method and to remove coarse particles contained therein by centrifugal treatment, and thereafter it is preferable to proceed with an ink-producing step by adding an organic solvent such as a water-soluble organic solvent.
• a content of a pigment in the ink composition is preferably at least 0.5 wt %, more preferably at least 2 wt %, in order to satisfactorily achieve a coloring effect, and is preferably at most 25 wt %, more preferably at most 10 wt %, in order to provide an appropriate viscosity for maintaining a satisfactory injecting performance at the viscosity of the ink composition.
• Examples of a preferable water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, diglycerin, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,5-pentanediol, 1,3-dimethyl-2-imidazolidinone and the like, and they may be used respective alone or in a mixture of two or more.
• the water-soluble organic solvent is added in an amount of from 5 to 30 wt %, preferably from 6 to 25 wt %, to an ink liquid, and if the water-soluble organic solvent is added in an amount of higher than the above upper limit, the ink itself becomes highly viscous, and consequently stability and injecting performance of the ink become poor, a blur into a paper becomes large, and a drying speed becomes low.
• the viscosity is at most 20 mPa ⁇ s.
• water-soluble organic solvents examples of which include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, t-butanol, trimethylolpropane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and the like.
• the ink composition of the present invention may contain such additives as a mildew-proofing agent, a defoaming agent, a rust-proofing agent, an antiseptic agent and the like.
• the ink composition of the present invention is excellent particularly as an ink for ink jet.
• the ink composition is applicable to an ink jet recording method characterized in that printing is carried out by injecting the ink composition through a nozzle of an ink jet printer or an ink jet recording method characterized in that recording is carried out by liquid droplets formed by applying heat energy to the ink composition.
• the ink composition of the present invention is applicable to an ink jet recording method characterized in that recording is carried out by liquid droplets formed by applying a mechanical energy to the ink composition.
• the ink composition of the present invention is particularly suitable for being used as an ink jet ink having a high permeability.
• conventionally known various methods can be employed for raising a high permeability.
• JP-A-2001-302,950 illustrates an ink composition having an improved permeability to a recording medium and having an excellent continuous injecting stability by containing a surfactant having an acetylene bond.
• JP-A-2002-3760 illustrates one containing a compound of the following chemical formula (1) having an acetylene bond, 1,5-pentanediol, and a butyl ether type solvent.
• JP-A-2002-30,237 illustrates an ink composition containing an acetylene glycol type surfactant and/or a polysiloxane type surfactant, an alkylether derivative of a polyhydric alcohol, the alkyl carbon number of which is at least 3 (preferably from 3 to 6), as an organic solvent, and/or 1,2-alkanediol, as a satisfactory ink composition having an excellent color reproducibility, a high permeability and a short drying time.
• examples of an organic solvent include ethylene glycol monobutyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol
• examples of a 1,2-alkanediol include preferably 1,2-C 1 C 8 alkanediol, more preferably 1,2-C 1 C 6 alkanediol, most preferably 1,2-hexanediol.
• the 1,2-alkanediol is added in an amount of from 1 to 15 wt %, preferably 2 to 10 wt %.
• an acetylene glycol type surfactant include various compounds illustrated in JP-A-2002-30237. More particular examples include Surfynol 82, 104, 440, 465, 485, TG (manufactured by Air Products and Chemicals, Inc.), Orfin STG, E1010 (manufactured by Nisshin Kagaku K.K.), and the like.
• the dispersion liquid was adjusted to pH 8.5 with sodium hydroxide, and was subjected to centrifugal treatment at 25000 G for 5 minutes to remove coarse particles. After removing the coarse particles, the dispersion liquid had a solid content of 26.0%, a pH value of 8.3 and a pigment particle size (volume 50% dispersion size) of 75.2 nm.
• the ink composition was allowed to stand in a constant temperature room at 50° C. for 1 month, and presence or absence of separation of pigment, water floating and precipitation as well as changes in viscosity and average particle size of pigment were observed. It was evaluated as “abnormal” when the separation of pigment, water floating and precipitation occurred even at a small degree or the changes in viscosity and average particle size of pigment were caused.
• the paper sheet printed by the above injecting performance test (b) was measured with regard to gloss on 200 mirror surface by using a gloss meter VG2000 (manufactured by Nippon Denshoku Kogyo K.K.).
• Example 1 An ink composition was prepared in the same manner as in Example 1, except that the polyester type polyurethane resin was not added. The same evaluation tests as in Example 1 were carried out, and the results are shown in the following Table 1.
• the dispersion liquid was adjusted to pH 8.5 with sodium hydroxide, and was subjected to centrifugal treatment at 25000 G for 5 minutes to remove coarse particles. After removing the coarse particles, the dispersion liquid had a solid content of 26.8%, a pH value of 8.4 and a pigment particle size (volume 50% dispersion size) of 9.8 nm.
• the dispersion liquid was adjusted to pH 8.5 with sodium hydroxide, and was subjected to centrifugal treatment at 25000 G for 5 minutes to remove coarse particles. After removing the coarse particles, the dispersion liquid had a solid content of 25.9%, a pH value of 8.3 and a pigment particle size (volume 50% dispersion size) of 56.3 nm.
• solid content concentration was adjusted to 20 wt %.
• the dispersion liquid thus prepared is referred to as “blue dispersion”.
• An ink composition was prepared by using the blue dispersion thus obtained and the following components.
• Component Amount (parts) Blue dispersion (solid content 20%) 15.0 Ethylene glycol monoethyl ether 10.0 2-Pyrrolidone 5.0 1,2-Hexanediol 10.0 Surfynol 465 0.5 Antiseptic agent (benzisothiazoline) 0.2 Ion exchanged water 59.3
• the dispersion liquid was adjusted to pH 8.5 with sodium hydroxide, and was subjected to centrifugal treatment at 25000 G for 5 minutes to remove coarse particles. After removing the coarse particles, the dispersion liquid had a solid content of 25.5%, a pH value of 8.4 and a pigment particle size (volume 50% dispersion size) of 81.1 nm.
• Example 1 An ink composition was prepared in the same manner as in Example 4, except that the polycarbonate type polyurethane resin was not added. The same evaluation tests as in Example 1 were carried out, and the results are shown in the following Table 1.
• the dispersion liquid was adjusted to pH 8.5 with sodium hydroxide, and was subjected to centrifugal treatment at 25000 G for 5 minutes to remove coarse particles. After removing the coarse particles, the dispersion liquid had a solid content of 26.0%, a pH value of 8.4 and a pigment particle size (volume 50% dispersion size) of 64.8 nm.
• Example 2 An ink composition was prepared in the same manner as in Example 2, except that the polycarbodiimide type crosslinking agent was not added. The same evaluation tests as in Example 1 were carried out, and the results are shown in the following Table 1.
• Example 3 An ink composition was prepared in the same manner as in Example 3, except that the kneading step was not carried out. The same evaluation tests as in Example 1 were carried out, and the results are shown in the following Table 1.
• Example 1 An ink composition was prepared in the same manner as in Example 5, except that the centrifugal treatment of removing coarse particles was not carried out. The same evaluation tests as in Example 1 were carried out, and the results are shown in the following Table 1.
• TABLE 1 Stability as a Injecting Gloss Friction lapse of time performance value resistance
• Example 1 ⁇ ⁇ 61.1 ⁇
• Example 2 ⁇ ⁇ 78.5 ⁇
• Example 3 ⁇ ⁇ 58.6 ⁇
• Example 4 ⁇ ⁇ 54.3 ⁇
• Example 5 ⁇ ⁇ 63.9 ⁇
• Example 6 X ⁇ 77.9 ⁇
• Example 7 ⁇ ⁇ 41.2 ⁇
• Example 8 ⁇ X 36.8 ⁇ Comp. Ex. 1 X ⁇ 49.6 X Comp. Ex. 2 X ⁇ 47.3 X
• the present invention can provide a pigment dispersion for ink jet and an ink composition for ink jet, which are greatly improved in stability in a highly permeable solvent and have excellent friction resistance and gloss.

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• 2003
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