US20110223529A1 - Aqueous pigment dispersion and applications thereof - Google Patents

Aqueous pigment dispersion and applications thereof Download PDF

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Publication number
US20110223529A1
US20110223529A1 US12/737,568 US73756809A US2011223529A1 US 20110223529 A1 US20110223529 A1 US 20110223529A1 US 73756809 A US73756809 A US 73756809A US 2011223529 A1 US2011223529 A1 US 2011223529A1
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Prior art keywords
pigment
polymer
block
compound
molecular dispersant
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Inventor
Hiroyuki Shimanaka
Taiyo Aoyagi
Yoshikazu Murakami
Sachio Yoshikawa
Naoyuki Sakai
Atsushi Goto
Yoshinobu Tsujii
Takeshi Fukuda
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Dainichiseika Color and Chemicals Mfg Co Ltd
Kyoto University
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Dainichiseika Color and Chemicals Mfg Co Ltd
Kyoto University
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Assigned to DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD., KYOTO UNIVERSITY reassignment DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AOYAGI, TAIYO, MURAKAMI, YOSHIKAZU, SAKAI, NAOYUKI, SHIMANAKA, HIROYUKI, YOSHIKAWA, SACHIO
Assigned to DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD., KYOTO UNIVERSITY reassignment DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUKUDA, TAKESHI, GOTO, ATSUSHI, TSUJII, YOSHINOBU
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • 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
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • This invention relates to an aqueous pigment dispersion, which contains a pigment highly microdispersed therein, has good storage stability and gives printed images and characters of good quality.
  • This invention is also concerned with a treated pigment, paint, ink, coating formulation, toner, stationery, and the like.
  • living radical polymerization As a polymerization process that can control a polymer structure upon synthesis of a high-molecular dispersant by radical polymerization that makes use of an addition-polymerizable monomer, living radical polymerization has been invented.
  • This living radical polymerization process is a novel and precise polymerization process that initiates polymerization from the initiating compound.
  • its end radical is stabilized with a stable group, the stable end group is caused to dissociate under the action of heat or a catalyst to form a polymer having a radical end.
  • the monomer undergoes a polymerization reaction so that the stable group is immediately bonded to stabilize the radical end.
  • This process prevents a bimolecular termination reaction or disproportionation reaction as a side reaction of radical polymerization and does not deactivate the radical as a reactive end, in other words, is a “living” radical polymerization process.
  • the polymerization proceeds as time goes on, and based on the amount of polymerization initiating compound at the initiation of the reaction, the molecular weight of a resulting polymer is determined, and the molecular weight distribution of the resulting polymer can be controlled very narrow (molecular weight distribution, PDI: to 1.3).
  • PDI molecular weight distribution
  • the polymerization is initiated to enable block polymerization to afford a block copolymer although such block copolymerization can be hardly conducted by the conventional radical polymerization.
  • the selection of an appropriate initiating compound makes it possible to obtain polymers of various higher structures, such as graft copolymers and star polymers.
  • Non-patent Document 1 the nitroxide mediated polymerization (NMP) process that makes use of dissociation and bonding of amine oxide radicals
  • Non-patent Document 2 the atom transfer radical polymerization (ATRP) process that conducts polymerization in the presence of a halogen compound as an initiating compound by using a heavy metal such as copper, ruthenium, nickel or iron and a ligand capable of forming a complex with the heavy metal
  • Patent Document 1 Patent Document 2, and Non-patent Document 2
  • RAFT reversible addition-fragmentation transfer
  • Patent Document 3 the macromolecular design via interchange of xanthate (MADIX) process
  • Patent Document 4 the degenerative mediated polymerization
  • a high-molecular dispersant which is obtained by polymerizing addition-polymerizable monomers such as styrene and a (meth)acrylic monomer and has conventionally been used to disperse a pigment in a pigment dispersion, is a random copolymer making use of the addition-polymerizable monomers.
  • a block polymer was developed. This block copolymer can be obtained by polymerizing addition-polymerizable monomers in accordance with a conventionally-known anionic polymerization or cationic polymerization, and is controlled in structure.
  • the high-molecular dispersant obtained by the living radical polymerization is accompanied by the following problems resulted from the living radical polymerization.
  • tetramethylpiperidine oxide radicals are used as a polymerization initiator.
  • an elevated temperature of 100° C. or higher is needed.
  • a monomer needs to be singly subjected to polymerization without using any polymerization solvent, thereby requiring stricter polymerization conditions.
  • the polymerization of a methacrylate monomer hardly proceeds in general.
  • a special nitroxide compound is needed. As the special nitroxide compound is expensive, the resulting polymer becomes costly.
  • the use of a heavy metal is needed for polymerization, and therefore, the heavy metal is contained in the resulting polymer. Accordingly, it is necessary to remove the heavy metal from the polymer.
  • effluent water and/or waste solvent occurred as a result of the purification contains the heavy metal that places a high load on the environment, and therefore, the removal of the heavy metal from the effluent water and/or waste solvent is needed.
  • oxygen needs to be eliminated from the polymerization atmosphere. If oxygen is contained, cuprous copper is oxidized into cupric copper so that the catalyst is deactivated.
  • the catalyst is oxidized, there is a method that adds a stannic compound, ascorbic acid or the like as a reducing agent to convert the copper back into the original monovalent copper. Even with this method, there is a potential problem that the polymerization may terminate halfway. It is, therefore, essential to fully eliminate oxygen from the polymerization atmosphere.
  • the RAFT process or MADIX process requires to synthesize a special compound such as a dithiocarboxylate ester or xanthate compound, and therefore, is costly.
  • a special compound such as a dithiocarboxylate ester or xanthate compound
  • this process uses the sulfur-containing compound, an unpleasant sulfur smell remains in the resulting polymer.
  • the polymer is colored. It is, therefore, necessary to eliminate these smell and color from the polymer.
  • the DT process makes use of a heavy metal like the ATRP process, and the heavy metal needs to be eliminated from the resulting polymer. Similar to the foregoing, there is, accordingly, a problem of effluent water when the heavy metal is eliminated. Moreover, the synthesis of an organometal compound for use in the process is irksome, and requires high cost.
  • An object of the present invention is, therefore, to provide an aqueous pigment dispersion with a pigment dispersed therein by a high-molecular dispersant, which is free of such problems as described above, has been obtained by a simple living radical polymerization process, is precisely controlled in molecular structure.
  • the present invention provides an aqueous pigment dispersion comprising at least a pigment, water, a high-molecular dispersant, and an alkali, wherein the high-molecular dispersant is a diblock polymer having a formula (1) of A-B or a triblock polymer having a formula (2) of A-B-C, and the diblock or triblock polymer is a diblock or triblock polymer obtained by polymerizing addition-polymerizable monomers with a radical generator while using an organic iodide as a polymerization initiating compound and an organic phosphorus compound, organic nitrogen compound or organic oxygen compound as a catalyst; and in the formulas (1) and (2), A, B and C each represent a polymer block of at least one of the addition-polymerizable monomers, the A and C blocks maybe the same or different, the A and C blocks are each a polymer block which is formed from at least one mono
  • the organic phosphorus compound is an iodine-containing phosphorus halide, phosphite compound or phosphinate compound
  • the organic nitrogen compound is an imide compound or hydantoin compound
  • the organic oxygen compound is a phenolic compound, iodoxyphenyl compound or vitamin
  • the diblock or triblock polymer has an overall acid value of from 20 to 250 mgKOH/g, and a content of the A block or a total content of the A and C blocks in the diblock or triblock polymer amounts to at least 20 wt % of the entire diblock or triblock polymer.
  • the diblock or triblock polymer has a number average molecular weight of from 1,000 to 20,000, and the B block in the diblock or triblock polymer has a number average molecular weight of not greater than 80% of the overall number average molecular weight of the corresponding block polymer; and that the monomer having the acid group is (meth)acrylic acid, and the hydrophobic monomer comprises benzyl(meth)acrylate or cyclohexyl(meth)acrylate.
  • the present invention provides a process for treating a pigment by mixing at least the pigment, water, an organic solvent, an alkali and a high-molecular dispersant to disperse the pigment in the water and then adding an acid to the resulting liquid mixture such that the high-molecular dispersant dissolved in the liquid mixture is caused to precipitate to coat the pigment with the high-molecular dispersant or by kneading at least the pigment and the high-molecular dispersant and then adding the resulting kneaded mixture to a poor solvent for the high-molecular dispersant such that the pigment is coated with the high-molecular dispersant, wherein the high-molecular dispersant is the diblock polymer having the formula (1) of A-B or the triblock polymer having the formula (2) of A-B-C; and also a treated pigment obtained by the process and having a pigment content of from 20 to 95 wt %.
  • the present invention also provides a method for producing an aqueous pigment dispersion, which comprises dispersing the treated pigment in an alkaline aqueous medium; and also a paint, ink, coating formulation, toner or stationery comprising the aqueous pigment dispersion.
  • the high-molecular dispersant for use in the present invention has a diblock or triblock structure formed of one or two water-soluble polymer blocks and a water-insoluble polymer block.
  • the water-insoluble polymer block or blocks coat pigment particles or deposit on pigment particles. Even in an aqueous medium, the high-molecular dispersant is not dissolved and remains coating the pigment to form a pigment-resin capsule structure.
  • the water-soluble polymer block or blocks have hydrophilicity, thereby dispersing the encapsulated pigment in the aqueous medium and providing the pigment with high dispersion stability and high microdispersibility.
  • the hydrophilic polymer block is readily dissolved in water.
  • the pigment is hence allowed to readily disperse in water.
  • the use of the aqueous pigment dispersion according to the present invention for the coloration of a product or article can afford a colored product or article having high vividness, a highly-developed color and a high gloss.
  • the process that obtains the high-molecular dispersant for use in the present invention is a novel living radical polymerization process, which is neither the conventional radical polymerization nor the above-described living radical polymerization process and is free of the problem of the heavy metal, smell, coloration, cost and the like in the above-described living, radical polymerization.
  • the aqueous pigment dispersion according to the present invention is an aqueous pigment dispersion which can be obtained by treating a pigment with the above-described high-molecular dispersant and then dispersing the thus-treated pigment, and the aqueous pigment dispersion is very useful as a coloring agent for a water-based paint, gravure ink, stationery color, water-based inkjet ink, wet toner, chemical toner, water-based coating formulation, and the like.
  • the process that obtains the high-molecular dispersant for use in the present invention has the following merits:
  • FIG. 1 shows dried films (left—Example, right—Comparative Example 2).
  • FIG. 2 shows the films after addition of water (left—Example, right—Comparative Example 2).
  • FIG. 3 shows micrographs of the films after addition of water (left—Example, right—Comparative Example 2).
  • FIG. 4 shows printed pigment particles
  • organic pigments include phthlocyanine, azo, azomethineazo, azomethine, anthraquinone, perinone and perylene, indigo and thioindigo, dioxazine, quinacridone, isoindoline, isoindolinone, diketopyrrolopyrrole, quinophthalone, and indathrene pigments, carbon black pigment, and the like.
  • inorganic pigments include extender pigments, titanium oxide pigments, iron oxide pigments, spinel pigments, and the like.
  • pigmentgists mayeachbeusedin combination with the pigment in a similar manner as in the conventionally-known process.
  • Such synergists include sulfonated derivative, aminated derivatives and the like of azo and phthalocyanine pigments.
  • selection may desirably be made as to the kind and particle size of the pigment and the manner of treatment.
  • a microparticulated pigment is desired except where hiding power is needed for an article or produced to be colored.
  • the high-molecular dispersant for use in the present invention is a diblock polymer having a formula (1) of A-B or a triblock polymer having a formula (2) of A-B-C.
  • A, B and C each represent a polymer block of at least one addition-polymerizable monomer
  • the A and C blocks may be the same or different
  • the A and C blocks are each a polymer block which is formed from at least one monomer having an acid group and has an acid value of from 40 to 300 mgKOH/g
  • the B block is a polymer block of a hydrophobic monomer.
  • the diblock or triblock polymer may preferably have an overall acid value of from 20 to 250 mgKOH/g, and the content of A block or the total content of A and C blocks may preferably amount to at least 20 wt % of the entire high-molecular dispersant (diblock or triblock polymer). More preferably, the high-molecular dispersant may have a number average molecular weight of from 1,000 to 20,000, and the B block in the high-molecular dispersant may have a total number average molecular weight of not greater than 80% of the overall number average molecular weight of the dorresponding block polymer.
  • the high-molecular dispersant for use in the present invention is the block polymer formed of the A block and B block or the A block, B block and C block.
  • the A block or the A block and C block are each a polymer block of a monomer having an acid group. By neutralizing such acid groups, the block polymers are rendered soluble in water.
  • the B block is a polymer block formed primarily from a water-insoluble hydrophobic monomer, although the B block may have acid groups. Therefore, the high-molecular dispersant for use in the present invention is an amphiphilic block polymer.
  • B block is insoluble in water, and therefore, is adsorbed on particles of the pigment or are allowed to deposit on the particles of the pigment.
  • the pigment is, therefore, brought into a form that it is encapsulated with the B block.
  • the A block or the A and C blocks are neutralized and ionized with the alkali in the aqueous medium, and therefore, are allowed to dissolve in water.
  • the high-molecular dispersant disperses the pigment in the form of microparticles in the aqueous medium, and provides the resulting aqueous pigment dispersion with improved dispersion stability and storage stability.
  • the encapsulation of the pigment with the high-molecular dispersant makes it possible to reduce the penetration of the pigment into paper and to increase the color development of the pigment when characters or images are printed on the paper with an aqueous pigment dispersion (for example, an ink).
  • an aqueous pigment dispersion for example, an ink.
  • the A block or C block acts as a binder component for the pigment to form coatings, and moreover, shows compatibility with another binder component so that the coatings present a good external appearance.
  • the pigment dispersion according to the present invention is used as a water-based inkjet ink, the ejection stability is good and no nozzle clogging takes place.
  • the A block and the C block may be the same or different, and these blocks are each a polymer block polymerized from a monomer, which contains an acid group, as at least one component.
  • the A block or the A and C blocks are rendered soluble in water.
  • the acid group of such a monomer a conventionally-known, carboxyl, sulfonic or phosphoric group can be mentioned, with a carboxyl group being particularly preferred. Because, in the present invention, the high-molecular dispersant is rendered insoluble to precipitate with an acid after the pigment is dispersed with the high-molecular dispersant, and this precipitation is facilitated when the acid group is a carboxyl group.
  • carboxyl-containing monomers include acrylic acid, acrylic acid dimer, methacrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid, and monomers obtained by reacting maleic anhydride, succinic anhydride or phthalic anhydride with hydroxyalkyl(meth)acrylates such as 2-hydroxyethyl(meth)acrylate and 4-hydroxybutyl(meth)acrylate.
  • Illustrative sulfonic-containing monomers include styrenesulfonic acid, dimethylpropylsulfonic acid (meth)acrylamide, ethylsulfonate(meth)acrylate, ethylsulfonate(meth)acrylamide, vinyl sulfonic acid, and the like.
  • Illustrative phosphoric-containing monomers include methacryloyloxyethyl phosphates.
  • carboxyl-containing monomers are particularly preferred in the present invention. More preferred is acrylic acid or methacrylic acid, because this monomer is low in molecular weight so that its proportion can be increased in a monomer composition to be polymerized and the resulting high-molecular dispersant can hence be provided with a higher acid value. Moreover, these monomers are also high in polymerization degree in the polymerization process to be employed in the present invention.
  • each monomer having an acid group can be used as it is. If necessary, however, the acid group may be protected, and after obtaining a block polymer, the protecting group for each acid group is removed to regenerate the acid group.
  • a conventionally-known monomer can be used in this process.
  • each unit of, for example, a hemiacetal(meth)acrylate such as methyl(meth)acrylate, t-butyl(meth)acrylate, benzyl(meth)acrylate or 1-n-propoxyethyl(meth)acrylate can be deprotected into a unit of (meth)acrylic acid.
  • the contents of acid groups in these blocks are important.
  • the acid values are from 40 to 300 mgKOH/g, preferably from 60 to 250 mgKOH/g. If these acid values are lower than 40 mgKOH/g, the high-molecular dispersant for use in the present invention is not soluble in water. If these acid values exceed 300 mgKOH/g, on the other hand, the acid values are so high that, when the aqueous pigment dispersion is used for the coloration of an article, the resulting color coating is provided with reduced waterproofness.
  • the A block or the A and C blocks affect even the B block in the high-molecular dispersant so that, even when a pigment is coated with the high-molecular dispersant, the B block may separate from the pigment due to the high water solubility of the high-molecular dispersant and capsules may hence be destructed.
  • a further copolymerizable monomer may also be used.
  • other properties can be imparted including, for example, an adjustment to the acid value for the dissolution in water, adhesiveness to a surface to be coated, compatibility with a binder when mixed with a paint or the like, thermal stability and softness/hardness property to the A block or the A and C blocks, and the like.
  • the copolymerizable monomer a conventionally-known monomer can be mentioned.
  • examples include vinyl monomers such as styrene, vinyltoluene, vinylhydroxybenzene, chloromethylstyrene, vinylnaphthalene, vinylbiphenyl, vinylethylbenzene, vinyldimethylbenzene, ⁇ -methylstyrene, ethylene, propylene, isoprene, butene, butadiene, 1-hexene, cyclohexene, cyclodecene, dichloroethylene, chloroethylene, fluoroethylene, tetrafluoroethylene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, isocyanatodimethylmethane isopropenyl benzene, phenylmaleimide, cyclohexylmaleimide, and hydroxymethylstyrene;
  • aliphatic, alicyclic and aromatic alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate, 2-methylpropane(meth)acrylate, t-butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate, tetradecyl(meth)acrylate, octadecyl(meth)acrylate, behenyl(meth)acrylate, isostearyl(meth)acrylate, cyclohex
  • alkylene glycol mono(meth)acrylates such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, and cyclohexanediol mono(meth)acrylate;
  • polyalkylene glycol mono(meth)acrylates such as poly(n ⁇ 2)ethylene glycol mono(meth)acrylate, poly(n ⁇ 2)propylene glycol mono(meth)acrylate, poly(n ⁇ 2)tetramethylene glycol mono(meth)acrylate, the mono(meth)acrylate of a mono- or poly (n ⁇ 2) ethylene glycol-mono- or poly(n ⁇ 2)propylene glycol random copolymer, and the mono(meth)acrylate of a mono- or poly(n ⁇ 2)ethylene glycol-mono- or poly(n ⁇ 2)propylene glycol block copolymer; further, the mono(meth)acrylates of (polyalkylene)glycol monoalkyl, alkylene and alkyne ethers or esters, such as (poly)ethylene glycol monomethyl ether(meth)acrylate, (poly)ethylene glycol monooctyl ether(meth)acrylate, (poly)
  • monomers with a primary amino group contained therein include vinylamine, allylamine, aminostyrene, 2-aminoethyl(meth)acrylate, 2-aminopropyl(meth)acrylamide, and the like
  • monomers with a secondary amino group contained therein include vinylmethylamine, allylmethylamine, methylaminostyrene, t-butylaminoethyl(meth)acrylate, tetramethylpiperidyl(meth)acrylate, t-butylaminopropyl(meth)acrylamide, and the like;
  • Monomers with a tertiary amino group contained therein include dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, pentamethylpiperidyl(meth)acrylate, N-ethylmorpholine(meth)acrylate, dimethylpropyl(meth)acrylamide, vinylpyridine, vinylimidazole, vinylbenzotriazole, vinylcarbazole, dimethylaminostyrene, diallylmethylamine, and the like.
  • Monomers with a quaternary amino group contained therein include trimethyl ammonium styrene chloride, dimethyl lauryl aminostyrene chloride, vinyl methyl pyridinyl iodide, chlorotrimethylaminoethyl(meth)acrylate, chlorodiethylmethylaminoethyl(meth)acrylate, chlorobenzyldimethylaminoethyl(meth)acrylate, trimethylaminoethyl(meth)acrylate methyl sulfate, diallyldimethylammonium chloride, and the like. Further included are those which can be obtained by reacting primary or secondary amines with glycidyl-containing monomers such as glycidyl(meth)acrylate.
  • Oxygen-containing monomers include tetrahydrofurfuryl(meth)acrylate, morpholine(meth)acrylate, methylmorpholine(meth)acrylate, methylmorpholinoethyl(meth)acrylate, and the like.
  • Nitrogen-containing monomers include (meth)acryloyloxyethyl isocyanate, (meth)acryloyloxyethoxyethyl isocyanate, blocked isocyanate-containing (meth)acrylates obtained by blocking these isocyanates with caprolactone or the like; and amide monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methylol(meth)acrylamide and N-butoxymethyl(meth)acrylamide.
  • polyester-type mono(meth)acrylate esters obtained by subjecting lactones such as ⁇ -caprolactone and ⁇ -butyrolactone to ring-opening polymerization while using, as initiators, the above-described (poly)alkylene glycol mono(meth)acrylate esters such as (meth)acryloyloxyethyl mono- or poly (n ⁇ 2)caplolactone; ester-type (meth)acrylates obtained by reacting dibasic acids to the above-described (poly)alkylene glycol mono(meth)acrylate esters such as 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate and 2-(meth)acryloyloxyethyl-2-hydroxyethyl succinate to half-esterify the dibasic acids and then reacting alcohols or alkylene glycols to the other carboxyl groups;
  • the mono(meth)acrylates of polyfunctional hydroxyl compounds having 3 or more hydroxyl groups such as glycerol mono(meth)acrylate and dimethylolpropane mono(methacrylate); halogen-containing (meth)acrylates such as 3-chloro-2-hydroxypropyl(meth)acrylate, octafluorooctyl(meth)acrylate and tetrafluoroethyl(meth)acrylate; UV-absorbing monomers such as 2-(4-benzoxy-3-hydroxyphenoxy)ethyl(meth)acrylate and 2-(2′-hydroxy-5-(meth)acryloyloxyethylphenyl)-2H-benzotriazole, said UV-absorbing monomers being preferably copolymerized especially to provide pigments with improved light resistance; and ⁇ -hydroxymethyl-substituted acrylates such as ethyl- ⁇ -hydroxymethyl acrylate.
  • a monomer which has a reactive group such as an addition-polymerizable group may be reacted to provide the side chains of the polymer with addition-polymerizable groups.
  • methacrylic groups can be introduced, for example, into a block polymer, which has been obtained by polymerizing (meth)acrylic acid as a copolymerization component and includes the A block, by reacting glycidyl methacrylate to the block polymer, and acrylic groups can be introduced, for example, into a block polymer, which has been obtained by polymerizing 2-hydroxyethyl(meth)acrylate as a copolymerization monomer component and has hydroxyl groups, by reacting acryloyloxyethyl isocyanate to the block polymer.
  • These high-molecular dispersants with the above-described addition-polymerizable groups contained on side chains thereof can be used as polymers to be subjected to ultraviolet curing or electron beam curing.
  • the A block and C block in the high-molecular dispersant may be the same or different. Therefore, they may have the same acid value or different acid values, and further, they may have the same monomer composition or different monomer compositions. It is, however, necessary for each of them to have such a composition as giving such an acid value as described above.
  • the B block in the high-molecular dispersant is a water-insoluble polymer block.
  • monomers usable for forming the B block the above-described monomers can be mentioned.
  • hydrophobic monomers including (meth)acrylates having an aromatic ring, for example, benzyl(meth)acrylate and (meth)acrylates having an alicyclic alkyl group, for example, cyclohexyl(meth)acrylate.
  • the B block is the water-insoluble polymer block, and therefore, the proportion of units of such a monomer contained in the B block may preferably be 50 wt % or higher. Owing to this monomer composition, the solubility of the B block in water is reduced so that, even when used in an aqueous solvent, B blocks do not separate from the pigment.
  • the B block it is also possible to use a monomer having an aliphatic, aromatic or alicyclic alkyl group which is preferably non-functional, or a monomer having an acid group, amino group or hydroxyl group. It is, however, to be noted that the monomer may have an acid group but the B block should not become soluble in water upon neutralization of such acid groups and that the monomer may have an amino group or a quaternary ammonium base group but the B block should not be rendered soluble in water with an acid or should not be soluble in water for the existence of such quaternary ammonium base groups.
  • the combined use of a monomer having an amino group is preferred as the resulting high-molecular dispersant is provided with improved coatability for a pigment, which has been treated with a synergist having an acid group such as a sulfonic group, through ionic bonding with surfaces of the pigment, and the combined use of a monomer having a hydroxyl group is also preferred as the resulting high-molecular dispersant is provided with improved coatability for a pigment through hydrogen bonding with surfaces of the pigment.
  • a monomer having two or more addition-polymerizable groups may also be used insofar as it is such a hydrophobic monomer as described above.
  • the use of a bifunctional or higher functionality monomer forms bonding between two types of functional groups themselves in the resulting polymer.
  • the B block is polymerized in a branched form, thereby providing a multi-branched, star block polymer in which block polymers A are grafted on the B block.
  • the bifunctional or higher functional monomer to be used examples include divinylbenzene; the (meth)acrylates of diols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol and cyclohexanedimethanol; polyester polyol (meth)acrylates; the (meth)acrylates of polyhydroxy compounds such as trimethylolpropane and pentaerythritol; products obtained by reacting acid groups of monomers having the acid groups with glycidyl groups of monomers having the glycidyl groups; and products obtained by reacting hydroxyl-containing monomers with isocyanato-containing monomers.
  • divinylbenzene the (meth)acrylates of diols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol and cyclohexanedimethanol
  • polyester polyol (meth)acrylates the (meth)acrylates of polyhydroxy compounds such as trimethylolprop
  • the monomer having the acid group may be used in an amount such that the B block is provided with an acid value of preferably smaller than 20 mgKOH/g, more preferably 10 mgKOH/g or smaller.
  • the monomer having the amino group may be used in an amount such that the B block is provided with an amine value of preferably 100 mgKOH/g or smaller, more preferably 50 mgKOH/g or smaller.
  • a monomer having nonionic hydrophilic groups like polyethylene glycol may also be used, the inclusion of many nonionic hydrophilic groups in the resulting B block is not preferred because the resulting high-molecular dispersant is dissolved in water.
  • the high-molecular dispersant for use in the present invention is such an A-B diblock polymer or A-B-C triblock polymer as described above.
  • a description will now be made about the quantitative relationship between the A block or the A and C blocks (“the A block” and “the C block” will hereinafter be called “the hydrophilic blocks”) and the B block in the high-molecular dispersant.
  • the overall acid value of the high-molecular dispersant, said acid value being originated from the hydrophilic block or blocks may preferably range from 20 to 250 mgKOH/g, and within this range, the weight ratio of the hydrophilic block or blocks to the B block and the acid value are adjusted.
  • the high-molecular dispersant does not have compatibility with water and cannot: be brought into a state that it is dissolved or dispersed in water. If the acid value exceeds 250 mgKOH/g, on the other hand, the high-molecular dispersant itself is provided with unduly high hydrophilicity so that, when a pigment is treated with the high-molecular dispersant, the B block separates from the pigment and the high-molecular dispersant is dissolved in water. Even when the resulting aqueous pigment dispersion is used for the coloration of an article, the resulting color coating is provided with inferior waterproofness because of the high acid value.
  • the overall acid value of the high-molecular dispersant may be preferably from 30 to 200 mgKOH/g, more preferably from 40 to 180 mgKOH/g.
  • the molecular weight of the high-molecular dispersant for use in the present invention may be preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, still more preferably from 5,000 to 10,000 as a styrene-equivalent number average molecular weight measured by gel permeation chromatography (hereinafter abbreviated as “GPC”).
  • GPC gel permeation chromatography
  • a molecular weight lower than 1,000 does not allow the resulting high-molecular dispersant to exhibit steric hindrance after its adsorption on a pigment so that the high-molecular dispersant is provided with reduced pigment dispersibility.
  • a molecular weight higher than 20,000 results in an aqueous pigment dispersion having a higher viscosity, and therefore, the dispersion of a pigment does not proceed well.
  • a single molecule of the high-molecular dispersant may adsorb on plural pigment particles, thereby possibly causing coagulation of the pigment.
  • PDI polydispersity index
  • excessively broad PDI means that the high-molecular dispersant includes from a polymer of high molecular weight to a polymer of low molecular weight, and therefore, a phenomenon other than that occurs within the above-described molecular weight range may take place. Such excessively broad PDI is not preferred accordingly.
  • PDI may be preferably 1.7 or smaller, more preferably 1.6 or smaller.
  • the hydrophilic block or blocks may preferably amount to 20 wt % or more of the entire high-molecular dispersant.
  • the molecular weight of the B block in the whole high-molecular dispersant may preferably amount to less than 80%.
  • the addition of the high-molecular dispersant to water may result in coagulation of B blocks themselves due to the strong hydrophobicity of the B block despite the existence of the hydrophilic block or blocks in the high-molecular dispersant so that the high-molecular dispersant may become insoluble as a whole in water even when neutralized with an alkali.
  • the content of the hydrophilic block or blocks in the high-molecular dispersant may be 30 wt % or higher.
  • the molecular weight of the B block may be preferably 80% or lower, more preferably 70% or lower of the overall molecular weight of the high-molecular dispersant. In such a range, the dissolution of the high-molecular dispersant in water results in very fine dispersion of B blocks owing to the inclusion of hydrophilic blocks, thereby making it possible to afford an aqueous solution which is clear to the eye.
  • This polymerization process is not the conventional radical polymerization or living radical polymerization, but is novel living radical polymerization.
  • this living radical polymerization uses neither a metal compound nor a ligand, and does not need using a special compound such as a nitroxide compound, dithiocarboxylate ester or xanthate compound.
  • This living radical polymerization can be readily conducted by simply using an organoiodide compound as an initiating compound and a catalyst in combination in the conventional radical polymerization that uses addition-polymerizable monomers and a radical generator as a polymerization initiator.
  • the above-described polymerization process proceeds through a reaction mechanism represented by the following reaction formula (1), and is a reversible activation reaction of a dormant species, Polymer-X (P-X), into a propagating radical.
  • reaction formula (1) is a reversible activation reaction of a dormant species, Polymer-X (P-X), into a propagating radical.
  • a free radical generated from the polymerization initiator in the presence of the initiating compound with iodine (X) bonded thereto extracts an active hydrogen or active halogen atom from the catalyst to form a catalyst radical A•
  • This A• then extracts X from the initiating compound to form XA.
  • the initiating compound therefore, becomes a radical, to which a monomer polymerizes so that X is immediately extracted from XA to prevent any termination reaction.
  • A• extracts X from the end X to form XA and an end radical. To this end radical, the monomer reacts so that X is immediately given to the end radical to stabilize the end radical.
  • the polymerization proceeds to permit control of the molecular weight and structure. It is, however, to be noted that the above-described polymerization process may be accompanied by a bimolecular termination reaction or disproportionation in some instances.
  • the initiating compound which is used in the present invention to initiate living radical polymerization, is a conventionally-known organoiodide compound, and is not specifically limited. Specific examples include alkyl iodides such as methyl iodide, ethyl iodide, propyl iodide, isopropyl iodide, butyl iodide, t-butyl iodide, iodophenylmethane, iododiphenylmethane, iodotriphenylmethane, 2-iodo-1-phenylethane, 1-iodo-1-phenylethane, 1-iodo-1,1-diphenylethane and diiodomethane; iodine-containing organohalide compounds such as iododichloromethane, iodochloromethane, iodotrichloromethane and iodod
  • iodoalcohols such as 1-iodoethanol, 1-iodopropanol, 2-iodopropanol, 2-iodo-2-propanol, 2-iodo-2-methylpropanol, 2-phenyl-1-iodoethanol and 2-phenyl-2-iodoethanol; ester compounds of these iodoalcohols with carboxylic compounds such as acetic acid, butyric acid and fumaric acid; iodocarboxylic acids such as iodoacetic acid, ⁇ -iodopropionic acid, ⁇ -iodobutyric acid, ⁇ -iodoisobutyric acid, ⁇ -iodovaleric acid, ⁇ -iodoisovaleric acid, ⁇ -iodocaproic acid, ⁇ -iodophenylacetic acid, ⁇ -iododiphenylacetic acid, ⁇ -iodo- ⁇ -phenyl
  • bifunctional initiating compounds having two iodine atoms including, for example, 1,2-diiodoethane, 1,2-diiodotetrafluoroethane, 1,2-diiodotetrachloroethane, 1,2-diiodo-1-phenylethane, and reaction products of the above-described iodocarboxylic acids such as ⁇ -iodoisobutyric acid with diols such as ethylene glycol or diamines such as hexamethylenediamine.
  • Organoiodide compounds for use in the present invention can be obtained, for example, through reactions of azo compounds such as azobisisobutyronitrile with iodine, or by subjecting organohalide compounds, which are similar to the above-described organoiodide compounds except for the substitution of their iodine atoms with other halogen atoms such as bromine or chlorine atoms, to halogen exchange reactions with iodide salts such as quaternary ammonium iodide and sodium iodide. It is to be noted that no particular limitation is imposed on their production processes.
  • the catalyst for use in the present invention is an organic phosphorus compound, organic nitrogen compound or organic oxygen compound, which extracts an iodine atom from the above-described initiating compound to form a radical, and may preferably be one or more compounds selected from iodine-containing phosphorus halides, phosphite compounds and phosphinate compounds as organic phosphorus compounds, imide compounds and hydantoin compounds as organic nitrogen compounds, and phenolic compounds, iodoxyphenyl compounds and vitamins as organic oxygen compounds.
  • phosphorus compounds iodine-containing phosphorus halides, phosphite compounds and phosphinate compounds
  • phosphorus triiodide dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diperfluoroethyl phosphinate, diphenyl phosphite, dibenzyl phosphite, bis(2-ethylhexyl)phosphite, bis(2,2,2-trifluoroethyl)phosphite, diallyl phosphite, ethylene phosphite, ethoxyphenyl phosphinate, phenylphenoxy phosphinate, ethoxymethyl phosphinate, phenoxymethyl phosphinate, phenoxymethyl phosphinate, phenoxymethyl phosphinate, phenoxymethyl phosphinate, phenoxymethyl phosphinate,
  • imide compounds and hydantoin compounds can be mentioned including, for example, succinimide, 2,2-dimethylsuccinimide, ⁇ , ⁇ -dimethyl- ⁇ -methylsuccinimide, 3-ethyl-3-methyl-2,5-pyrrolidinedione, cis-1,2,3,6-tetrahydrophthalimide, ⁇ -methyl- ⁇ -propylsuccinimide, 5-methylhexahydroisoindol-1,3-dione, 2-phenylsuccinimide, ⁇ -methyl- ⁇ -phenylsuccinimide, 2,3-diacetoxysuccinimide, maleimide, phthalimide, 4-methylphthalimide, N-chlorophthalimide, N-bromophthalimide, N-bromophthalimide, 4-nitrophthalimide, 2,3-naphthalenecarboximide, pyromellitic diimide, 5-bromoisoindol-1,3-
  • phenolic compounds each having a phenolic hydroxyl group which is a hydroxyl group bonded to an aromatic ring
  • iodoxyphenyl compounds as iodides of such phenolic hydroxyl groups
  • vitamins can be mentioned.
  • the phenolic compounds include phenol, hydroquinone, methoxyhydroquinone, t-butylphenol, t-butylmethylphenol, catechol, resorcinol, di-t-butylhydroxytoluene, dimethylphenol, trimethylphenol, di-t-butylmethoxyphenol, polymer obtained by polymerizing hydroxystyrene, and hydroxyphenyl-carrying microparticles of the polymer.
  • the iodoxyphenyl compounds include thymol iodide and the like, and the vitamins include vitamin C, vitamin E and the like.
  • the amount of the catalyst may preferably be smaller than the number of moles of the polymerization initiator. If the number of moles of the catalyst is excessively large, the polymerization is controlled so much that it does not proceed.
  • the polymerization initiator for use in the present invention conventionally-known one is usable. No particular limitation is imposed on it, and commonly-employed organic peroxides and azo compounds can be used. Specific examples include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyl-3,3-isopropylhydroperoxide, t-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis(4
  • the polymerization initiator can be used as much as preferably from 0.001 to 0.1 molar times, more preferably from 0.002 to 0.05 molar times the number of moles of the monomer, because an unduly small use amount of the initiator results in insufficient polymerization while an excessively large use amount of the initiator has a potential problem that a polymer of the addition-polymerizable monomer alone may be formed.
  • the high-molecular dispersant for use in the present invention can be obtained.
  • the polymerization may be conducted in bulk without using any organic solvent, but solution polymerization that uses a solvent is preferred. No particular limitation is imposed on the organic solvent to be used. Examples include hydrocarbon solvents such as hexane, octane, decane, isodecane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, and cumene;
  • alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, benzyl alcohol and cyclohexanol; glycol solvents such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, diglyme, triglyme,
  • ether solvents such as diethyl ether, dipropyl ether, methyl cyclopropyl ether, tetrahydrofuran, dioxane, and anisole;
  • ketone solvents such as methyl ethyl ketone, diethyl ketone, isobutyl methyl ketone, cyclohexanone, isophorone, and acetophenones
  • ester solvents such as methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, caprolactone, methyl lactate, and ethyl lactate
  • halogenated solvents such as chloroform and dichloroethane
  • amide solvents such as dimethylformamide, dimethylacetamide, pyrrolidone, N-methylpyrrolidone, and caprolactam
  • the above-described block polymer is used as a high-molecular dispersant in an aqueous pigment dispersion. It is, therefore, particularly preferred to neutralize a polymerization mixture with an aqueous alkaline solution upon neutralization of the A block or the A and C blocks in the high-molecular dispersant after its solution polymerization, and then to use the thus-neutralized polymerization mixture for the dispersion treatment of the pigment as it is.
  • the organic solvent for use in the polymerization may preferably be an organic solvent which is soluble in water. Examples of particularly preferred organic solvents, therefore, include alcohol solvents and glycol solvents.
  • the solid content (monomer concentration) in the polymerization mixture may be from 5 to 80 wt %, with from 20 to 60 wt % being preferred, although no particular limitation is imposed thereon. If the solid content is lower than 5 wt %, the monomer concentration is so low that the polymerization may not be brought to completion. On the other hand, 80 wt % to bulk polymerization leads to a polymerization mixture having unduly high viscosity, and hence, to a potential problem that stirring may become difficult or the polymerization degree may be reduced.
  • the polymerization temperature is not particularly limited, and may be preferably from 0° C. to 150° C., more preferably from 30° C. to 120° C.
  • the polymerization temperature should be adjusted depending on the half-life of each polymerization initiator.
  • the polymerization time is not particularly limited and may be, for example, from 0.5 hour to 48 hours, and as a practical time, preferably from 1 hour to 24 hours, more preferably from 2 hours to 12 hours.
  • the atmosphere is not particularly limited, and the polymerization may be conducted in air.
  • oxygen may exist in a usual range in the system, or if necessary, the polymerization may be conducted under a nitrogen stream to eliminate oxygen.
  • commercial products can be used as they are although impurities may be removed by distillation or with activated carbon, alumina or the like. Further, the polymerization may be conducted under shading, but no problem arises even when the polymerization is conducted in a transparent vessel such as a glass vessel.
  • the diblock polymer or triblock polymer can be obtained as the high-molecular dispersant for use in the present invention.
  • the diblock polymer a addition-polymerizable monomer having at least an acid group is polymerized in the presence of a monofunctional organoiodide as an initiating compound by the above-described process to obtain a polymer block (which will be designated as “the A block”).
  • This polymer has been substituted at an end thereof with an iodine atom, and therefore, has been stabilized.
  • the monomer is added further, and by dissociating the iodine atom under heat or the like, polymerization can be initiated again.
  • This A block is collected and purified, and is dissolved again in an organic solvent.
  • the A block as an initiating compound and preferably adding the catalyst and polymerization initiator further, the next monomer is added and polymerized.
  • the end iodine atom of the polymer block is dissociated to initiate polymerization again, so that a diblock polymer can be obtained with a B block linked to the A block.
  • the diblock polymer can also be obtained by adding the monomer for the B block without collecting the A polymer block after the formation of the A block, preferably adding the catalyst and polymerization initiator further, and then conducting polymerization.
  • the monomer for the A block does not require complete polymerization insofar as the A block is provided with the above-described acid value and the B block is not soluble in water. Accordingly, the monomer for the B block may be added and polymerized at the time point that the polymerization degree of the monomer for the A block has reached preferably 50% or higher, more preferably 80% or higher. The addition can be made at once, or can be made dropwise by a dropping device. Dropwise addition makes it possible to impart a gradient to the concentration of the monomer in the block polymer B, that is, to provide a gradient polymer.
  • the A-B diblock polymer may also be obtained likewise by first polymerizing the monomer for the B block as a water-insoluble polymer and then polymerizing a monomer which comprises at least a monomer having an acid group.
  • a diblock polymer is obtained by polymerizing a monomer containing an acid group and then polymerizing a hydrophobic monomer as in the above-described diblock polymer. After the diblock polymer is collected, purified and then dissolved in a solvent or immediately after the block polymer is obtained, a monomer containing at least an acid group is added as a copolymer component, the polymerization initiator and catalyst may preferably be added further, and polymerization is conducted.
  • an A-B-C triblock polymer can be obtained.
  • the B block is insoluble in water and the A and B blocks become soluble in water upon neutralization.
  • polymerization degree of the monomer for the B block is preferably 80% or more, polymerization can be conducted by adding the monomer for the C block.
  • A-B-A triblock polymer makes it possible to obtain an A-B-A triblock polymer
  • polymerization of a C block having a monomer composition different from the monomer for the A block makes it possible to provide a A-B-C triblock polymer.
  • the monomer for the B block is polymerized in a state that the polymerization degree of the monomer for the A block has not reached 100% yet, and further, a monomer of a composition similar to that of the monomer for the A block is added and polymerized, an A-B-C triblock polymer can also be obtained.
  • An A-B-C triblock polymer can also be obtained when the monomer for the C block is added and polymerized in a state that the monomer for the B block has not been completely polymerized yet.
  • an A-B-C(A) triblock copolymer can also be obtained by using a bifunctional initiating compound, polymerizing a hydrophobic monomer, and then polymerizing a monomer containing an acid group.
  • the molecular weight of the resulting polymer can be controlled depending on the amount of the initiating compound.
  • the resulting polymer can be controlled to a desired molecular weight or the magnitude of its molecular weight can be controlled.
  • a preset molecular weight can be calculated by:
  • the polymerization process to be used in the present invention may be accompanied by a side reaction such as bimolecular termination or disproportionation, so that the actual molecular weight may not be controlled to the above-described calculated molecular weight.
  • a side reaction such as bimolecular termination or disproportionation
  • the polymer may have a greater molecular weight as a result of coupling or a smaller molecular weight as a result of termination.
  • the polymerization degree may not be required to be 100%. In such a case, the remaining monomer may be distilled off, or upon precipitation of the resulting block polymer, may be removed, or after the desired block polymer is obtained, the polymerization initiator and catalyst may be added to complete the polymerization.
  • the diblock polymer or triblock polymer for use in the present invention has been formed or contained, no problem arises even if the individual block polymers are separately contained.
  • the high-molecular dispersant may contain the diblock polymer or triblock polymer of the present invention at 50 wt % or higher, with 80 wt % or higher being more preferred.
  • PDI becomes broader when the above-described side reaction is accompanied.
  • no particular limitation is imposed on the PDI of the block polymer. Nonetheless, its PDI maybe preferably 1.7 or smaller, more preferably 1.6 or smaller.
  • the high-molecular dispersant for use in the present invention may be used, as it is, without neutralization.
  • the acid groups in the A block or the acid groups in the A and C blocks maybe neutralized to use the high-molecular dispersant for the preparation of an aqueous pigment dispersion.
  • an alkali may be added to make the block polymer soluble in water.
  • alkali that neutralizes acid groups No particular limitation is imposed on the alkali that neutralizes acid groups, and illustrative are ammonia; amines such as diethanolamine, triethylamine, diethanolamine and triisopropanolamine; terminal amine derivatives of polyalkylene glycols; and alkali metal salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, calcium hydroxide and zinc hydroxide.
  • a diblock polymer or triblock polymer can be obtained as a high-molecular dispersant for use in the present invention.
  • an aqueous solution of the high molecular dispersant can be obtained.
  • the preparation method of the aqueous pigment dispersion according to the present invention which comprises coating the pigment with the high-molecular dispersant and using the coated pigment.
  • the aqueous pigment dispersant according to the present invention is obtained by dispersing the pigment in water while using at least the above-described pigment, water, and the high-molecular dispersant neutralized with the alkali.
  • the preparation method of the aqueous pigment dispersion the following methods are preferred.
  • the high-molecular dispersant may coagulate to make difficult the dispersion of the pigment because the B block is not soluble in water when the high-molecular dispersant neutralized after polymerization is singly added to water. It is, therefore, preferred to add an organic solvent to a solution of the high-molecular dispersant such that the B block is made compatible with water and is dissolved, dispersed or swollen in the water.
  • the organic solvent the above-exemplified organic solvents can be used. Although not particularly limited, the use of an organic solvent having solubility in water is preferred.
  • This organic solvent is compatible with the B block and is also compatible with water, thereby dissolving, dispersing or swelling the B block in an aqueous solvent.
  • the B block is made compatible with water in the aqueous solvent so that the adsorption of the high-molecular dispersant, specifically the B block on the pigment is promoted.
  • the organic solvent may be only in the amount of the solvent used for the polymerization, or may be added further.
  • the organic solvent should be used in an amount such that the B block is prevented from coagulation to avoid the precipitation of the high-molecular dispersant itself.
  • the pigment is dispersed by a conventionally-known method.
  • the pigment concentration in the dispersion may be from 0.5 to 70 wt %, preferably from 5 to 50 wt % based on the dispersion although it varies depending on the kind and application purpose of the pigment.
  • the use amount of the high-molecular dispersant may desirably be from 5 to 500 parts by weight per 100 parts by weight of the pigment.
  • the coated pigment which is coated with the high-molecular dispersant may preferably contain the pigment as much as from 20 to 95%.
  • the dispersion method of the pigment is a conventionally-known method, and is not specifically limited.
  • the pigment, the alkali-neutralized high-molecular dispersant, the water and the organic solvent are combined and stirred, and by a conventionally-known disperser, the pigment is dispersed.
  • a conventionally-known disperser it is possible to use, for example, a kneader, an attritor, a ball mill, a sand mill or medium-containing, horizontal disperser making use of a glass or zircon medium, a colloid mill or the like.
  • bead mill bead media of 1 ⁇ m or smaller are preferred as its medium.
  • aqueous pigment dispersion may be provided as it is, or by a centrifuge, ultracentrifuge or filter, coarse particles which may exist slightly may be removed.
  • the aqueous pigment dispersion obtained in this dispersion step will be called “the aqueous pigment pre-dispersion”.
  • This aqueous pigment pre-dispersion may be applied to an article as it is.
  • the B block in the high-molecular dispersant is in a state that it is compatible with water owing to the existence of the organic solvent that is compatible with the B block. Therefore, B blocks separate from the pigment, and the aqueous pigment pre-dispersion is similar to conventional aqueous pigment dispersions.
  • the aqueous pigment pre-dispersion obtained as described above is provided as it is or with its pigment content diluted to 10 wt % or lower with water.
  • the neutralized high-molecular dispersant may be added to give a desired pigment content as needed.
  • the acid groups of the high-molecular dispersant have been neutralized with the alkali, the high-molecular dispersant is ionized and dissolved in water. By adding an acid to the high-molecular dispersant, the high-molecular dispersant can be rendered insoluble in water.
  • the high-molecular dispersant can be caused to deposit or capsulate on the pigment particles.
  • the acid to be used for the deposition or capsulation include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; and organic acids such as acetic acid, propionic acid and toluenesulfonic acid.
  • the acid may be added as it is, but it is preferred to use the acid in the form of an aqueous solution of 10 wt % or lower.
  • the acid While stirring the aqueous pigment pre-dispersion by a conventionally-known method, particularly preferably by using a stirrer, which can be driven at a high speed, such as a dissolver after its dilution with water, the acid is gradually added.
  • the amount of the acid to be added is preferably at least equimolar, more preferably 1.1 molar times or more relative to the alkali with which the A block and C block in the high-molecular dispersant have been neutralized.
  • the resultant precipitate is collected by filtration.
  • the mixture may be heated as needed such that the precipitated particles are caused to coagulate to facilitate the filtration. It is preferred to thoroughly remove the ionic substance and organic solvent, which still adhere on the precipitate, by this filtration.
  • the aqueous pigment paste obtained by the filtration may then be dried and ground for use in the next step. It is, however, preferred to use the aqueous pigment paste as it is, because the use of the aqueous pigment paste as it is can avoid the fusion of the high-molecular dispersant through drying and can hence obviate grinding, and further, the particle size of the pigment remains unchanged from the particle size at the time of the dispersion.
  • the preparation method (2) According to this method, at least the pigment and the high-molecular dispersant are kneaded by a conventional method.
  • the amount of the high-molecular dispersant to be used may desirably be from 5 to 500 parts by weight per 100 parts by weight of the pigment as described above.
  • the high-molecular dispersant may be added beforehand such that a desired pigment content can be achieved upon kneading, or as an alternative, the high-molecular dispersant may be added in an amount of from 20 to 100 wt % based on the pigment, and after kneading, the high-molecular dispersant may be added further to achieve the desired pigment content.
  • the kneading may be performed for from 30 minutes to 60 hours, preferably for from 1 hour to 12 hours either at room temperature or with heating by a conventionally-known kneading machine such as, for example, a kneader, extruder or ball mill. It is also preferred to make combined use of a carbonate, chloride or the like as a fine medium for microparticulating the pigment and also to make combined use of a viscous organic solvent such as ethylene glycol or diethylene glycol to impart lubricity or the like, in the mixture as needed.
  • a viscous organic solvent such as ethylene glycol or diethylene glycol to impart lubricity or the like
  • the carbonate, chloride or the like is used from 1 to 30 times by weight, preferably from 2 to 20 times by weight relative to the pigment.
  • the use amount of the viscous organic solvent is adjusted depending on the viscosity during the kneading of the pigment.
  • the use amount of the high-molecular dispersant relative to the pigment is adjusted beforehand based on the above-described amount.
  • the kneaded mixture is added to an organic solvent in which the high-molecular dispersant is not soluble, preferably to a solvent having low solubility for the high-molecular dispersant, for example, water, methanol, hexane or a mixture thereof to cause the high-molecular dispersant to precipitate such that the high-molecular dispersant is allowed to deposit or capsulate on particles of the pigment.
  • an organic solvent in which the high-molecular dispersant is not soluble
  • a solvent having low solubility for the high-molecular dispersant for example, water, methanol, hexane or a mixture thereof to cause the high-molecular dispersant to precipitate such that the high-molecular dispersant is allowed to deposit or capsulate on particles of the pigment.
  • the kneaded mixture is added to an aqueous solution of an acid such that the high-molecular dispersant is neutralized to deposit or capsulate on the particles of the pigment.
  • the pigment coated as described above is then collected by filtration and thoroughly washed with water. Especially when the kneading was conducted while using the carbonate, chloride or the like, water washing is needed to remove the carbonate, chloride or the like.
  • the aqueous pigment paste may then be dried and ground into powder, although it may preferably be used as it is.
  • the aqueous pigment dispersion according to the present invention can be obtained via the treated pigment which is coated with the high-molecular dispersant.
  • the above-described treated pigment is next added to an aqueous alkaline solution for its dispersion.
  • an alkali the above-exemplified alkalis can be used.
  • an organic solvent can also be added as needed. Usable as this organic solvent is an organic solvent, which does not dissolve the B block and is soluble in water. This organic solvent differs depending on the kind of the polymer of the B block, and therefore, cannot be specified.
  • examples include water-soluble organic solvents containing two or more hydroxyl groups per molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, dipropylene glycol, glycerin and 1,2-hexanediol; and mono or di(C 1 -C 4 lower alkyl) ethers of dimeric and higher oligomeric polyalkylene glycols.
  • the content of the organic solvent may preferably be such that the B block is not dissolved, with less than 100% of the content of the high-molecular dispersant being more preferred, although no limitation is imposed on the content.
  • the aqueous pigment dispersion according to the present invention can be obtained.
  • the A block and C block in the high-molecular dispersant in the treated pigment are neutralized with the alkali to dissolve them in water.
  • the B block is not soluble in water, and therefore, does not separate from the pigment, thereby making it possible to obtain the aqueous pigment dispersion according to the present invention in which the pigment is encapsulated with the high-molecular dispersant.
  • the thus-obtained, aqueous pigment dispersion may be provided as it is. From the standpoint of providing the dispersion with higher reliability, however, it is preferred to remove coarse particles, which may exist slightly, by a centrifuge, ultracentrifuge or filter.
  • the concentration of the pigment may be preferably from 0.5 to 50 wt %, more preferably from 0.5 to 30 wt % based on the dispersion although it depends on the kind of the pigment.
  • the viscosity (25° C.) of the dispersion may be preferably from 1 to 50 mPa ⁇ s, preferably from 2 to 30 mPa ⁇ s.
  • the viscosity of the aqueous pigment dispersion making use of the treated pigment, which is coated with the high-molecular dispersant according to the present invention, has excellent stability with time.
  • Water-based pigment dispersions can be obtained by using high-molecular dispersants as described above. These aqueous pigment dispersions can be used as coloring agents in conventionally-known paints, inks, coating formulations, stationery and toners. Specifically, these aqueous pigment dispersions can be used as coloring agents in water-based paints, oil-based paints, gravure inks, water-based flexographic inks, inkjet inks, inks for stationery, inks for writing instruments, coating formulations, colors for color filters, wet toners, chemical toners, and the like. Their contents vary depending on the pigment concentrations, and therefore, cannot be specified. They can be used at concentrations as much as needed to give desired color densities.
  • a reactor composed of a 1-L separable flask fitted with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, diethylene glycol dimethyl ether (hereinafter called “diglyme”) (241.5 parts), 2-iodo-2-cyanopropane (hereinafter called “CP-1”) (6.2 parts), methyl methacrylate (hereinafter abbreviated as “MMA”) (180 parts), acrylic acid (hereinafter abbreviated as “AA”) (14.4 parts), azobisisobutyronitrile (hereinafter abbreviated as “AIBN”) (5.2 parts), and iodosuccinimide (hereinafter abbreviated as “NIS”) (0.1 parts) were added, followed by stirring while allowing nitrogen to flow. The reaction temperature was raised to 75° C., at which polymerization was conducted for 3 hours.
  • diglyme diethylene glycol dimethyl ether
  • CP-1 2-iodo-2-cyanopropane
  • MMA methyl methacryl
  • the polymerization mixture was sampled, and its solid content was measured. As a result, the solid content was found to be 42.0%, and therefore, the monomers were confirmed to be polymerized substantially in their entirety. Further, the molecular weight was measured by GPC. As a result, the number average molecular weight (hereinafter called “Mn”) was found to be 5,000, and the polydispersity index (hereinafter called “PDI”) was found to be 1.42. A polymer was, therefore, obtained with narrow molecular weight distribution and uniform molecular weight.
  • Mn number average molecular weight
  • PDI polydispersity index
  • the polymer showed no UV absorption (when measured at 254 nm wavelength; UV absorption will hereinafter means a measurement value at this wavelength), and no molecular weight was confirmed by a UV detector.
  • the acid value of the polymer was 56.3 mgKOH/g.
  • benzyl methacrylate (hereinafter abbreviated as “BzMA”) (35.2 parts) and AIBN (0.3 parts) was added, followed by polymerization at the same temperature for 3 hours.
  • BzMA benzyl methacrylate
  • AIBN 0.3 parts
  • Mn 5,500
  • PDI 1.43
  • UV absorption by the benzyl group was confirmed, Mn and PDI as determined by UV absorption were 5,400 and 1.44, respectively.
  • the molecular weight determined by GPC in the visible range was substantially the same as that determined in the UV range.
  • the BzMA polymer block As the molecular weight increased as a result of the linkage of the BzMA polymer block to the MMA/AA polymer block, the BzMA polymer block is considered to have block-copolymerized to the above-described MMA/AA polymer block.
  • the solid content was found to be 49.6%, and therefore, the monomer was confirmed to be polymerized substantially in its entirety. Its molecular weight was also measured. Mn was 6,800, and PDI was 2.02. Mn and PDI as determined by UV absorption were 5,000 and 2.48, respectively.
  • the molecular weight is not greater by only the molecular weight of the BzMA polymer block than the molecular weight of the MMA/AA polymer block, the molecular weight determined in the visible range and the molecular weight determined in the UV range are substantially different from each other, clouding took place upon addition of water, and precipitation or settling was observed when diluted with water. It is, therefore, indicated that water-insoluble homopolymer of BzMA existed and the MMA/AA polymer block and BzMA polymer block were not linked together in the form of a block polymer. Accordingly, the usefulness of the living radical polymerization employed in the present invention has been confirmed.
  • the solution of the high-molecular dispersant solution will be called “the solution of comparative high-molecular dispersant-1”. Its solid content and pH were 42.0% and 10.3. The solution was cloudy after neutralization. After left over in a vessel, however, the water-insoluble high-molecular dispersant precipitated out on the bottom wall of the vessel.
  • a solution of the high-molecular dispersant-14 was obtained as described above.
  • the solid content and pH of the solution were 41.2% and 9.5. Even when the solution was placed in a vessel and was left over, no precipitation of the polymer took place and the solution remained clear.
  • the solution of the high-molecular dispersant-14 was diluted with 10-fold water, a blue microdispersion was formed although it was substantially clear.
  • the BzMA polymer block was, therefore, considered to be dispersed as microparticles.
  • the amount of iodine ions in the solution was measured by an ion chromatograph, it was found to be 0.57%. Accordingly, the end iodine atom of the polymer was dissociated in its entirety.
  • the polymer was a triblock polymer of the A-B-C type.
  • MMA 120 parts
  • MAA 25.8 parts
  • V-70 0.74 parts
  • a portion of the polymerization mixture was sampled, and its solid content was measured. The solid content was found to be 48.3%, and therefore, the monomers were confirmed to be polymerized substantially in their entirety.
  • BDG Diethylene glycol monobutyl ether
  • This polymer was an A-B block polymer, which was obtained by polymerizing the A polymer as a water-soluble polymer after polymerization of the hydrophobic B polymer, and further, which used methacrylic acid.
  • This polymer is also an A-B polymer in which the molecular weight of the B polymer was relatively large.
  • composition of the A block in each block polymer was expressed as a composition in terms of weight ratio by calculating the remainder of the monomer or monomers for the corresponding B block from the yield of the B block, and the acid value of the A block was calculated from the composition.
  • copper phthalocyanine blue (“CYANINE BLUE KBM”, product of Dainichi Seika Color & Chemicals Mfg. Co., Ltd.; 1,000 parts
  • deionized water 316 parts was added to the resulting mill base to obtain an aqueous pigment dispersion having a pigment content of 18%.
  • Deionized water 5,000 parts was then poured into the mill base obtained as described above, and with stirring at high speed, 5% hydrochloric acid was added dropwise to cause the high-molecular dispersant to precipitate.
  • the pH was 9.5 at the beginning, and owing to the addition of the acid, was lowered to 2.1.
  • the aqueous pigment dispersion was then filtered, and the resulting filter cake was thoroughly washed with deionized water to obtain a pigment paste having a solid content of 30.5%.
  • a small portion of the aqueous pigment dispersion was next placed in an aluminum cup, and was left over for 3 hours in a vacuum drier controlled at 50° C. to obtain a dried film.
  • a vacuum drier controlled at 50° C. to obtain a dried film.
  • the film was dissolved upon contact with the water.
  • the solution obtained after the dissolution was observed under a microscope, the solution was free of coarse particles, and all particles had been dissolved. Therefore, even when the aqueous pigment dispersion according to the present invention is once dried, its dried product is hence good in re-dispersibility.
  • the high-molecular dispersant is considered to have capsulated on the pigment, and therefore, self-dispersibility is considered to have imparted to the pigment.
  • Example 1 Using the comparative high-molecular dispersants of Comparative Examples 1 and 2, similar experiments were conducted in a similar manner as described above. In addition, the mill base before the precipitation treatment in Example 1 was adjusted to have a similar solid content, and a similar re-dispersibility test was conducted. The results are shown together with the results of Example 1 in Table 8.
  • Comparative Example 1 an MMA/AA copolymer of high acid value existed in the dispersant, and therefore, the dispersion of the pigment proceeded to afford an aqueous pigment dispersion with the pigment being dispersed to a certain degree of fineness. With respect to its re-dispersibility, however, a dried film was observed to separate as it was. When observed under a microscope, coagulated particles and a film-shaped material were observed.
  • the high-molecular dispersant used in Comparative Example 2 had a low acid value, and the dispersion of the pigment was insufficient in the resultant dispersion. Similar to Comparative Example 1, the re-dispersibility was poor. In the mill base of Example 1, the high-molecular dispersant had not capsulated the pigment completely, and the high-molecular dispersant separated from the pigment. Therefore, the performance of the dispersant is not considered to have been fully exhibited.
  • Example 1 As in Example 1, a similar operation was conducted on PY-74 as a yellow pigment, PR-122 as a magenta pigment and carbon black as a black pigment, respectively, whereby an aqueous yellow pigment dispersion, aqueous magenta pigment dispersion and aqueous black pigment dispersion were obtained. Described specifically, for the aqueous yellow pigment dispersion, “SEIKA FAST YELLOW A3” (product of Dainichi Seika Color & Chemicals Mfg.
  • aqueous yellow pigment dispersion-1 As aqueous yellow pigment dispersion-1, aqueous red pigment dispersion-1 and aqueous black pigment dispersion-1, the aqueous pigment dispersions of the respective colors were obtained with good storage stability and very good dried-film re-dispersibility like the aqueous blue pigment dispersion-1.
  • a further experiment was conducted by changing the high-molecular dispersant from the high-molecular dispersant-7 to the high-molecular dispersant-12 in the aqueous red pigment dispersion-1. Similar results were obtained.
  • FIG. 1 shows films after drying
  • FIG. 2 shows the conditions of the respective films when water was added
  • FIG. 3 shows the films as observed under a microscope when water was added.
  • the film obtained by using the high-molecular dispersant according to the present invention has been confirmed to have readily dissolved.
  • these dispersions are used as water-based pigment inks for stationery, the above-described good re-dispersibility is considered to prevent drying of pen points and, even when the pen points become dry, to permit writing again once the pen points are brought into contact with water.
  • the above-described good re-dispersibility is considered to prevent drying of print heads and, even when the print heads become dry, to permit readily cleaning them up again with a washing solution. Accordingly, these dispersions are very useful.
  • Dispersion treatment was conducted as in Example 1 except that the high-molecular dispersant-1 (170 parts) was replaced by the high-molecular dispersant-3 (41 parts) and in the dispersion of the pigment before the precipitation of the dispersant, the dispersion was performed by replacing the disperser with an ultrasonic disperser.
  • the ultrasonic dispersion treatment was conducted by stirring a mill base with a magnetic stirrer, defoaming the mill base for 15 minutes in an ultrasonic defoaming apparatus, and after a break of 1 minute, applying ultrasonic waves for 15 minutes from the ultrasonic disperser, the output of which was 1,200 Hz, while externally cooling a vessel with ice.
  • An aqueous blue pigment dispersion-2 was obtained as described above.
  • the high-molecular dispersant was used in a smaller amount relative to the pigment.
  • the dispersant was used in an amount of 20% based on the pigment.
  • the amount of the dispersant was as small as 5% based on the pigment.
  • ultrasonic dispersion treatment was also conducted likewise.
  • the aqueous pigment dispersions obtained as described above were also tested for storage stability and dried-film re-dispersibility as in Example 1. The results are shown in Table 10.
  • aqueous pigment dispersions were obtained, respectively, as in Example 1. Described specifically, the high-molecular dispersant-4 was used to obtain the aqueous yellow pigment dispersion as an aqueous yellow pigment dispersion-2; the high-molecular dispersant-9 was used to obtain the aqueous magenta pigment dispersion as an aqueous magenta pigment dispersion-3; and the high-molecular dispersant-6 was used to obtain the aqueous black pigment dispersion as an aqueous black pigment dispersion-2. Those pigment dispersions were equipped with similar storage stability and dried-film re-dispersibility as demonstrated in the above-described test.
  • Titanium oxide (“R-930”, product of Ishihara Sangyo Kaisha Ltd.) (20 parts), the high-molecular dispersant-8 (18.5 parts) and water (61.5 parts) were placed in a 250-mL plastic bottle, and were dispersed together with 1-mm zirconia beads for 4 hours by a paint conditioner.
  • the particle size of the pigment in the resulting dispersion was 236 nm, and its maximum particle size was 1.51 ⁇ m.
  • the high-molecular dispersant was caused to precipitate, and the coated titanium oxide was collected by filtration.
  • the solid content of the resulting paste was 28.7%.
  • the mill base obtained by the paint conditioner as described above was diluted with water to have a similar pigment content as the above-described aqueous white pigment dispersion. This will be called “the comparative aqueous white pigment dispersion”.
  • a commercial halogenated phthalocyanine green pigment (C.I.P.G. 36) (100 parts), monosulfonated copper phthalocyanine (5 parts), diethylene glycol (200 parts) and common salt (700 parts) were charged into a 3-L kneader.
  • the kneader was controlled to maintain its temperature at from 100° C. to 120° C.
  • the high-molecular dispersant-10 (40 parts) was added, followed by milling for 8 hours.
  • the resulting kneaded mixture (800 parts) was then charged into water (2,000 parts), and the thus-obtained mixture was stirred at high speed for 4 hours. Filtration and washing were then conducted to obtain a water-based paste of the green pigment (pigment content: 29.3%).
  • aqueous green pigment dispersion-1 To the water-based paste (100 parts), 28% aqueous ammonia (0.6 parts) and water (94.7 parts) were added, followed by dispersion in a medium-containing horizontal disperser as in Example 1.
  • the particle size of the pigment in the dispersion and the viscosity of the dispersion were 89 nm and 2.66 mPa ⁇ s, respectively, at that time.
  • the particle size of the pigment and the viscosity of the dispersion were found to be 82 nm and 2.58 mPa ⁇ s, respectively. Therefore, the dispersion was good in storage stability.
  • a re-dispersibility test of a dried film the dried film showed good re-dispersibility, and was re-dispersed well. This dispersion will be called an “aqueous green pigment dispersion-1”.
  • dispersant By changing the dispersant to the high-molecular dispersant-13 having amino groups, dispersion was conducted. Similar results were obtained. As storage stability, the dispersion had stability as high as a viscosity change of less than 5% even after stored at 70° C. for 1 week. This high stability is considered to be attributable to the exhibition of an advantageous effect by a high degree of encapsulation as a result of ion bonding between sulfonic groups of the synergist on the pigment surfaces and the amino gtoups of the high-molecular dispersant.
  • the high-molecular dispersant-15 (25.3 parts) and BDG (60.0 parts) were mixed into a clear aqueous solution.
  • a water-based paste solid content: 29.4%; 204 parts
  • microparticulated PR-122 average particle size: 106 nm
  • the resulting mixture was dispersed together with the milling medium in the horizontal disperser to prepare a mill base.
  • a 1% aqueous solution of acetic acid was added to lower the pH of the diluted mill base to 4.5.
  • the viscosity of the diluted mill base increased and the resin was caused to precipitate, whereby a resin-treated pigment was obtained.
  • the resin-treated pigment was then collected by filtration and thoroughly washed with water to obtain a pigment paste having a solid content of 26.4%.
  • Example 2 As in Example 1, the pigment paste (75 parts), BDG (5.5 parts), deionized water (20.6 parts) and sodium hydroxide (0.67 parts) were mixed, neutralized, converted into an aqueous solution, and then dispersed by the disperser. As the resulting pigment dispersion had a pigment content of 17%, water was added to the pigment dispersion to obtain a pigment dispersion having a pigment content of 14%. This pigment dispersion will be called an “aqueous red pigment dispersion-4”.
  • the pigment content was also adjusted by adding BDG in place of water.
  • the resulting dispersion was a pigment dispersion that abundantly contained BDG as an organic solvent. This pigment dispersion will be called an “aqueous red pigment dispersion-5”.
  • dispersion was conducted likewise to obtain an aqueous red pigment dispersion-6 and an aqueous red pigment dispersion-7 that abundantly contained BDG.
  • the capsulation was maintained as the B block in the high-molecular dispersant according to the present invention were insoluble. Accordingly, good storage stability was obtained, so that those pigment dispersions were good.
  • the B blocks in the high-molecular dispersant-15 were not dissolved and the pigment dispersions retained stability despite the abundant inclusion of the solvent because the B blocks were high in molecular weight and low in solvent solubility. With the high-molecular dispersant-18, however, the dispersion turned out lacking in stability.
  • the B block in the high-molecular dispersant-18 had solvent solubility due to its composition despite its high molecular weight, and moreover, was soft because of the inclusion of 2EHMA units, and therefore, decapsulation took place to result in low stability.
  • the high-molecular dispersant-19 (70.1 parts), BDG (28.8 parts) and water (513 parts) were mixed into a clear aqueous solution.
  • a powdery pigment of microparticulated PY-74 (average particle size: 97 nm; 200 parts)
  • the powdery pigment was provided with fluidity.
  • Stirring was then conducted in a dissolver.
  • the resulting mixture was dispersed together with the milling medium in the horizontal disperser to prepare a mill base.
  • water was added to dilute the mill base to a pigment content of 5%
  • a 1% aqueous solution of acetic acid was added to lower the pH of the diluted mill base to 4.5.
  • the viscosity of the diluted mill base increased and the resin was caused to precipitate, whereby a resin-treated pigment was obtained.
  • the resin-treated pigment was then collected by filtration and thoroughly washed with water to obtain a pigment paste having a solid content of 24.6%.
  • Example 2 As in Example 1, the pigment paste (200 parts), BDG (8.9 parts), deionized water (44.6 parts) and sodium hydroxide (3.0 parts) were mixed, neutralized, converted into an aqueous solution, and then dispersed by the disperser. As the resulting pigment dispersion had a pigment content of 17%, water was added to the pigment dispersion to obtain a pigment dispersion having a pigment content of 14%. This pigment dispersion will be called an “aqueous yellow pigment dispersion-3”.
  • dispersions were prepared. Those dispersions will be called “aqueous yellow pigment dispersions-4, -5 and -6, respectively.
  • the resulting kneaded mixture (800 parts) was charged into water (2,000 parts), followed by stirring at high speed for 4 hours. Filtration and washing were then conducted to obtain a water-based paste of the red pigment (pigment content: 22.4%).
  • Example 1 To the water-based paste (1,000 parts), an aqueous solution of potassium hydroxide (1.5 parts) and water (180.5 parts) was added, followed by dispersion in a medium-containing horizontal disperser as in Example 1.
  • the particle size of the pigment in the dispersion and the viscosity of the dispersion were 110 nm and 3.12 mPa ⁇ s, respectively.
  • the particle size of the pigment and the viscosity of the dispersion were found to be 120 nm and 2.98 mPa ⁇ s, respectively, after stored at 70° C. for 1 week. Therefore, the dispersion was good in storage stability. This dispersion will be called an “aqueous red pigment dispersion-8”.
  • a water-based paste having a solid content of 24.9% was similarly obtained.
  • the average particle size was 115 nm, and the viscosity was 3.75 mPa ⁇ s .
  • the thus-obtained dispersion will be called an “aqueous red pigment dispersion-9”.
  • the particle size of the pigment and the viscosity of the dispersion were found to be 117 nm and 3.66 mPa ⁇ s, respectively, after stored at 70° C. for 1 week. Therefore, the dispersion was good in storage stability.
  • a water-based paste having a solid content of 27.6% was also obtained similarly.
  • the average particle size was 114 nm, and the viscosity was 3.81 mPa ⁇ s .
  • the thus-obtained dispersion will be called an “aqueous red pigment dispersion-10”.
  • the particle size of the pigment and the viscosity of the dispersion were found to be 111 nm and 3.45 mPa ⁇ s, respectively, after stored at 70° C. for 1 week. Therefore, the dispersion was good in storage stability.
  • aqueous blue pigment dispersion-1 Using the aqueous blue pigment dispersion-1, aqueous yellow pigment dispersion-1, aqueous red pigment dispersion-1 and aqueous black pigment dispersion-1 obtained in Example 1, water-based inkjet inks were prepared in accordance with the following formula.
  • the A blocks of the high-molecular dispersants acted as binder components, thereby making it possible to obtain prints which were very high in the gloss of printed lines, were free of misalignment, and were good in scratch resistance.
  • aqueous blue pigment dispersion-2 Using the aqueous blue pigment dispersion-2, aqueous yellow pigment dispersion-2, aqueous red pigment dispersion-3 and aqueous black pigment dispersion-2 obtained in Example 2, inks of the respective colors were obtained in accordance with a similar formula and processing as in Application Example 1. Those inks were separately filled in ink cartridges, and by an inkjet printer, gradation printing was performed on plain paper (product of Fuji Xerox Co., Ltd.). After the prints were left over for one day in a room, they were measured for optical density by using “MACBETH RD-914” (manufactured by Gretag MacBeth GmbH). As scratch resistance, the printed surfaces were rubbed with a finger to confirm whether or not the colors on the printed surfaces were separated. The results of these tests are summarized in Table 14.
  • water-based stationery pigment inks were prepared in accordance with the following formula.
  • Example 3 To the aqueous white pigment dispersion (100 parts) obtained in Example 3, an aqueous styrene-acrylic resin emulsion (solid content 40%, a styrene-acrylic acid- ⁇ -methylstyrene copolymer neutralized with ammonia, acid value: 120 mgKOH/g; 50 parts) was added, followed by thorough stirring into a homogeneous mixture in a disper mixer. The mixture was adjusted to pH 8 with aqueous ammonia. A nylon film of 20 ⁇ m thickness was subjected to corona discharge treatment, and by a No. 4 bar coater, was then coated with the white printing ink obtained as described above. After drying, the coated nylon film was aged at 80° C. for 1 hour. An adhesive strength test of the printed ink layer was then conducted by using a cellophane tape. As a result, the ink layer showed good adhesiveness without separation.
  • the aqueous pigment dispersion according to the present invention has high storage stability and dispersion stability and good post-drying re-dispersibility, offers good print quality, and provides colored products or articles with high added value.

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US20130196064A1 (en) 2013-08-01
WO2010013651A1 (ja) 2010-02-04
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JP2015083688A (ja) 2015-04-30
EP2330154B1 (en) 2017-01-11
KR20130103632A (ko) 2013-09-23
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US9120948B2 (en) 2015-09-01
JP5733608B2 (ja) 2015-06-10

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