WO2010016523A1 - 顔料分散液、ブロックポリマーおよびその製造方法 - Google Patents
顔料分散液、ブロックポリマーおよびその製造方法 Download PDFInfo
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- WO2010016523A1 WO2010016523A1 PCT/JP2009/063878 JP2009063878W WO2010016523A1 WO 2010016523 A1 WO2010016523 A1 WO 2010016523A1 JP 2009063878 W JP2009063878 W JP 2009063878W WO 2010016523 A1 WO2010016523 A1 WO 2010016523A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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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
- 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
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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
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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
- C08F8/00—Chemical modification by after-treatment
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
Definitions
- the present invention is easy to polymerize monomers, has a good polymerization yield, is inexpensive, uses materials with low environmental impact, and is obtained by a novel polymerization method that does not require special compounds.
- the structure is controlled.
- the present invention relates to a prepared block polymer, a pigment dispersion containing the block polymer as a polymer dispersant, and use thereof.
- An acrylic copolymer which is one of polymers of ethylenically unsaturated monomers (hereinafter sometimes referred to simply as “monomers”), is used in various fields such as polymer dispersants, paints, binders, and adhesives. ing. Many of these acrylic copolymers are produced by a general radical polymerization method. However, in this method, a termination reaction such as recombination of growth radicals or disproportionation occurs, so that the resulting polymer can be obtained. It was difficult to control the molecular weight distribution. Furthermore, since radicals at the end of the polymer are deactivated during the polymerization, it was not possible to obtain a block polymer even if polymerization was carried out after adding other monomers after polymerization.
- a polymer dispersant is composed of a pigment adsorbing part that adsorbs to the pigment surface and a solvent affinity part that dissolves or has affinity with the dispersion medium.
- a polymer in which these portions are arranged in a balanced manner with respect to the pigment and the liquid medium, or a block polymer or graft polymer in which each portion is strictly controlled Must be used as a polymeric dispersant.
- the block polymer with strictly controlled structure clearly distinguishes the functional part of the pigment adsorbing part and the solvent affinity part, and obtains strong bonds by multipoint adsorption to the pigment. Spreads in the solvent, and the pigment particles can be stably dispersed by the steric effect.
- the solvent-affinity part of the polymer dispersant is a low-polar alkyl (meth) acrylate polymer
- the pigment adsorbing part has a polar group such as an acid group, amino group, or amide group (meth).
- Acrylate polymers are often used.
- Non-patent Document 1 nitroxide method
- Non-patent Document 2 heavy metals such as copper, ruthenium, nickel, and iron
- ATRP method Atom transfer radical polymerization in which a halogen compound is polymerized using a ligand as a starting compound (patent document 1 and patent document 2, non-patent document 2), dithiocarboxylic acid ester, xanthate compound, etc.
- Patent Document 3 Is a reversible addition-fragmentation chain transfer (RAFT method) (Patent Document 3) or Macromolecular Design via Interchange of polymerization using an addition polymerizable monomer and a radical initiator as a starting compound Xanthate (MADIX method) (patent document 4), organic tellurium and organic Methods using heavy metals such as Smus, organic antimony, antimony halide, organic germanium, and germanium halide (Degenerative Transfer, DT method) (Patent Document 5, Non-Patent Document 3) have been developed, and extensive research and development has been conducted. Yes.
- a polymer dispersant is produced by the NMP method (Patent Document 6), and the polymer dispersant is a polymer block of an amino group-containing monomer such as N, N-dimethylaminoethyl acrylate at the pigment adsorbing portion. And a polymer block of a hydrophobic monomer such as n-butyl acrylate is used for the solvent affinity part.
- the above-mentioned living radical polymerization method has the following problems.
- a tetramethylpiperidine oxide radical is used, and in this case, a high polymerization temperature of 100 ° C. or higher is required, and in order to increase the polymerization rate, a monomer alone is used for polymerization without using a solvent.
- the polymerization conditions are severe.
- the polymerization of the methacrylate monomer generally does not proceed. However, it is possible to lower the polymerization temperature or to polymerize a methacrylate monomer. In that case, a special nitroxide compound is required.
- the ATRP method it is necessary to use heavy metal, and it is necessary to remove the heavy metal from the polymer after the polymerization and purify the polymer even if it is a trace amount.
- heavy metals that have a high environmental load are also contained in the waste water and waste solvent, and it is also necessary to remove heavy metals from them.
- the ATRP method using copper it is necessary to perform polymerization in an inert gas. If oxygen is present in the polymerization atmosphere, the monovalent copper catalyst is oxidized to divalent copper, and the catalyst is deactivated.
- the formation of the complex is inhibited if an acidic substance is present in the polymerization system.
- the acid group of the monomer must be protected and polymerized, and the protective group must be eliminated after the polymerization. It is easy to introduce the acid group into the polymer block. is not.
- Patent Document 1 and Patent Document 2 use copper, it is necessary to remove the copper after polymerization and purify the polymer. In addition, when an acid that inhibits complex formation of copper and a ligand is present, polymerization does not proceed, and thus a monomer having an acid group cannot be directly polymerized.
- the present invention provides a pigment dispersion excellent in pigment dispersion stability, and a block polymer (polymer dispersant) used in the pigment dispersion, using a polymer dispersant free from problems of odor, coloring, heavy metals and cost.
- the purpose is to provide.
- the present invention is a pigment dispersion containing at least a pigment, a liquid medium, and a polymer dispersant, wherein the polymer dispersant is AB or ABC (A, B, C are Each represents a polymer block, and the A block and the C block may be the same or different), and the A block and the C block are ethylenically unsaturated monomers having no amino group and hydroxyl group ( A polymer block comprising a monomer a), wherein the B block is converted to a polymer block (D) comprising a monomer having a glycidyl group or an isocyanate group (monomer b) via an amino compound (E-1) via a glycidyl group or an isocyanate group. ) And a hydroxyl group-containing compound (E-2). Providing a pigment dispersion characterized by.
- the block polymer represented by AD or ADC (A, C, D each represents a polymer block, and the A block and the C block may be the same or different) is an iodine. It is a block polymer obtained by a living radical polymerization method of monomer a and monomer b using a compound as a starting compound and a phosphorus compound, nitrogen compound or oxygen compound as a catalyst; the content of B block in the polymer dispersant is The number average molecular weight of the polymer dispersant is 1,000 to 30,000; and the degree of dispersion of the polymer dispersant (weight average molecular weight / number average molecular weight) is: It is preferably 1.05 to 1.7.
- the present invention is a block polymer represented by AD or ADC (A, C, D each represents a polymer block, and the A block and the C block may be the same or different).
- the A block and the C block are polymer blocks composed of an ethylenically unsaturated monomer (monomer a) having no amino group and hydroxyl group, and the D block is composed of a monomer (monomer b) having a glycidyl group or an isocyanate group.
- a block polymer characterized by being a polymer block is provided.
- either the amino compound (E-1) or the compound (E-2) having a hydroxyl group is bonded via a glycidyl group or an isocyanate group; ) Is a polyamine selected from polyethyleneimine, polyallylamine and polyvinylamine, and the block polymer is a multi-branched block polymer; the amino compound (E-1) or the compound having a hydroxyl group (E-2) is amino It may be a coloring compound having one or more groups or hydroxyl groups.
- an A block is formed from an ethylenically unsaturated monomer (monomer a) having no amino group and hydroxyl group by a living radical polymerization method, and then living from a monomer (monomer b) having a glycidyl group or an isocyanate group.
- AD or ADC characterized by forming a D block by a radical polymerization method, or further forming a C block from a monomer a by a living radical polymerization method, wherein A, C, and D represent a polymer block, respectively.
- the A block and the C block may be the same or different).
- either one of the amino compound (E-1) and the compound (E-2) having a hydroxyl group can be bonded via a glycidyl group or an isocyanate group.
- the living radical polymerization method is a polymerization method using an iodine compound as a starting compound and a phosphorus compound, a nitrogen compound or an oxygen compound as a catalyst;
- the phosphorus compound is a phosphorus halide, phosphite
- the nitrogen compound is an imide, hydantoin, barbituric acid or cyanuric acid
- the oxygen compound is a phenolic compound, an iodooxyphenyl compound or a vitamin.
- the pigment dispersion of the present invention is useful as a colorant for paints, inks, coating agents, toners or stationery, for example.
- the method for obtaining a block polymer (polymer dispersing agent) in the present invention does not require the use of a heavy metal compound, does not necessarily require purification of the polymer, does not require the synthesis of a special compound, and is relatively in the market.
- the object can be easily obtained using only inexpensive materials.
- the polymerization conditions are mild and can be carried out under the same conditions as in the conventional radical polymerization method. No special equipment is required, and conventional radical polymerization equipment can be used. During polymerization, oxygen, water and light can be used. Is not so much affected.
- it is not necessary to purify the monomer and solvent to be used monomers having various functional groups can be used, and various functional groups can be introduced into the polymer. Furthermore, the polymerization rate is very high.
- the block polymer used as the polymer dispersant in the present invention is characterized in that the polymerization is started from the starting compound. After the polymer block A is polymerized with the monomer a, the monomer b is added and polymerized. An AD block polymer having a polymer block D having a glycidyl group or an isocyanate group is obtained. Further, the monomer a is polymerized to form a C block, thereby obtaining an ADC triblock polymer.
- the resulting polymer block D having a glycidyl group or an isocyanate group is reacted with a compound E having an amino group or a hydroxyl group, whereby an addition reaction easily occurs with the glycidyl group or the isocyanate group, and various functional groups.
- a block polymer having is obtained.
- block polymers having various physical properties are obtained depending on the structure of the compound E to be added, and a polymer dispersant having a structure suitable for dispersing various pigments can be obtained.
- the polymerization method used in the present invention is a novel living radical polymerization. Unlike the conventional methods, the living radical polymerization does not use a metal compound or a ligand, and also includes nitroxide, dithiocarboxylic acid ester, xanthate, etc. The special compound is not used. This is a polymerization method that can be easily carried out simply by using an initiator compound and a catalyst in combination with conventional radical polymerization.
- the polymerization method is a general reaction formula This is a reversible activity reaction of the dormant species Polymer-X (PX) to the growth radical.
- PX dormant species Polymer-X
- the polymerization mechanism may vary depending on the type of catalyst, but is thought to proceed as follows.
- P ⁇ generated from the radical initiator reacts with XA to generate catalyst A ⁇ in situ.
- A. acts as an activator of PX, and this catalytic action activates PX at a high frequency.
- a radical generated from the radical initiator draws out the active hydrogen or active halogen atom of the catalyst and becomes the catalyst radical A.
- the A ⁇ pulls out X of the starting compound to become XA, the starting compound becomes a radical, and the monomer is polymerized to the radical, and X is immediately pulled out from XA to prevent the termination reaction.
- A. withdraws X of PX by heat or the like becomes XA and a terminal radical, the monomer reacts there, and immediately gives X to the terminal radical and stabilizes.
- the polymerization proceeds and the molecular weight and structure can be controlled.
- this polymerization method as a side reaction, there are a bimolecular termination reaction and a disproportionation reaction in which radicals at the polymer terminals are coupled to each other.
- the starting compound used in the present invention will be described.
- the starting compound used by this invention it is preferable to make the iodine compound represented by following General formula 1 into a starting compound.
- the iodine atom is bonded to a secondary carbon or tertiary carbon
- X, Y and Z may be the same or different, and hydrogen, hydrocarbon group, halogen group, cyano group, alkoxycarbonyl group Represented by an allyloxycarbonyl group, an acyloxy group, an allyloxy group, an alkoxy group, an alkylcarbonyl group, and an allylcarbonyl group.
- the polymerization can be performed from the starting compound by a novel living radical polymerization using a monomer, a radical polymerization initiator and a catalyst. Start.
- the iodine atom of the general formula 1 is bonded to secondary or tertiary carbon. This is not suitable for iodine bonded to primary carbon because it is difficult to dissociate iodine in the polymerization method of the present invention. Therefore, at least two of X, Y and Z are not hydrogen atoms. Further, X, Y and Z are specifically exemplified, but not limited thereto.
- hydrocarbon group examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an arylalkyl group.
- alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-methylpropyl, t-butyl, pentyl, dodecyl; double groups such as vinyl, allyl, 2-methylvinyl, butenyl, butadienyl
- arylalkyl group such
- the halogen group includes a fluorine atom, chlorine atom, bromine atom, and iodine atom;
- the alkoxycarbonyl group or allyloxycarbonyl group includes methoxycarbonyl, ethoxycarbonyl, propylcarbonyl, cyclohexylcarbonyl, benzyloxycarbonyl.
- acyloxy group and allyloxy group include acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, naphthylcarboxyoxy, and the like; alkoxy groups include methoxy, Ethoxy, methoxyethoxy, phenoxyethoxy and the like; examples of the alkylcarbonyl group and allylcarbonyl group include methylcarbonyl, ethylcarbonyl, phenoxy Such ylcarbonyl and the like.
- this uses a radical compound capable of extracting iodine of the starting compound or iodine of the polymer terminal, and in the present invention, in particular, phosphorus, nitrogen having the property Or it is an oxygen compound.
- phosphorus compounds include phosphorus halides containing iodine atoms, phosphite compounds, phosphinate compounds, such as dichloroiodrine, dibromoiodrine, phosphorus triiodide, dimethyl phosphite.
- nitrogen compounds include imides such as succinimide, 2,2-dimethylsuccinimide, ⁇ , ⁇ -dimethyl- ⁇ -methylsuccinimide, 3-ethyl-3-methyl-2,5-pyrrolidinedione, cis-1, 2,3,6-tetrahydrophthalimide, ⁇ -methyl- ⁇ -propylsuccinimide, 5-methylhexahydroisoindole-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-bromoisoindole -1,3 Dione, N- chlorosuccinimide, N-
- hydantoins include hydantoin, 1-methylhydantoin, 5,5-dimethylhydantoin, 5-phenylhydantoin, 1,3-diaiodo-5,5-dimethylhydantoin and the like.
- barbituric acids include barbituric acid, 5-methylbarbituric acid, 5,5-diethylbarbituric acid, 5-isopropylbarbituric acid, 5,5-dibutylbarbituric acid, thiobarbituric acid, and the like.
- cyanuric acids include cyanuric acid, N-methyl cyanuric acid, triiodo cyanuric acid and the like.
- oxygen-based compound examples include a phenolic compound that is a phenolic hydroxyl group having a hydroxyl group in an aromatic ring, an iodooxyphenyl compound that is an iodide of the phenolic hydroxyl group, and vitamins.
- phenols such as phenol, hydroquinone, 4-methoxyphenol, 4-tert-butylphenol, 4-tert-butyl-2-methylphenol, 2-tert-butyl-4-methylphenol, catechol, resorcin, 2,6-di-tert-butyl-4-methyl
- a monomer having a phenolic hydroxyl group such as hydroxyphenyl ethyl.
- the polymer dispersant used in the present invention is obtained by block polymerization using the monomer a and the monomer b, and AB or ABC (A, B, and C represent polymer blocks, respectively, A block and C block) May be the same or different.
- the B block is a polymer block obtained by reacting a polymer block (D) composed of a monomer b having a glycidyl group or an isocyanate group with an amino compound (E-1) in the case of a glycidyl group.
- the B block contains functional groups that are amino groups and polycyclic groups derived from the compound E (E-1 or E-2) to be reacted with each other, and these functional groups are remarkably adsorbed to the pigment.
- B block works as a pigment adsorption part.
- the A block or C block is composed of a monomer a that does not react with a glycidyl group or an isocyanate group, and this polymer block is a solvent affinity block that dissolves in a liquid medium.
- the polymer dispersant (block polymer) used in the present invention is one in which the B block is adsorbed on the pigment, the A block and the C block become solvent-soluble, and the pigment is dispersed in the liquid medium.
- various functional groups can be introduced into the B block, and the pigment can be used for various pigments.
- the polymer dispersant can be selected from functional groups on the surface.
- a polymer block D having a monomer having at least a glycidyl group or an isocyanate group as a constituent component is obtained, and a compound E that can react with the glycidyl group or the isocyanate group is added to the B block. Obtained by reaction.
- the monomer b having a glycidyl group or an isocyanate group is not particularly limited.
- Illustrative examples of the monomer having a glycidyl group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, (meth) acryloyloxyethyl glycidyl ether, (meth) Examples thereof include vinyl monomers such as (meth) acrylates such as acryloyloxyethoxyethyl glycidyl ether, glycidyl vinyl ether and allyl glycidyl ether.
- the isocyanate is protected with (meth) acryloyloxyethyl isocyanate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, and their ⁇ -caprolactone, MEK oxime, pyrazole and the like.
- examples thereof include unsaturated monomers such as monomers obtained by reacting hydroxyethyl (meth) acrylate with only one isocyanate.
- the above-mentioned monomer b may be used alone, but in addition, a monomer c that does not react with a glycidyl group or an isocyanate group may be used as a constituent component.
- the proportion of monomer c is not particularly limited, but the proportion of monomer c is preferably 50 mol% or less of the total of monomer b and monomer c.
- a monomer having a functional group that reacts with the glycidyl group is not used. Examples of functional groups that react with glycidyl groups relatively easily include carboxyl groups, amino groups, and phenolic hydroxyl groups.
- the monomer b has an isocyanate group as the monomer c
- another monomer having a functional group that reacts with the isocyanate group is not used.
- functional groups that readily react with isocyanate groups include hydroxyl groups, primary amino groups, and secondary amino groups.
- Examples of the monomer c include, for example, styrene, vinyl toluene, chloromethyl styrene, vinyl naphthalene, vinyl biphenyl, vinyl ethyl benzene, vinyl dimethyl benzene, ⁇ -methyl styrene, isoprene, butene, butadiene, -Hexene, cyclohexene, cyclodecene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, phenylmaleimide, cyclohexylmaleimide and the like.
- Examples of the aliphatic, alicyclic or aromatic alkyl monomer c include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-methyl Propane (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
- a monomer c having a hydroxyl group may be used, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 5-hydroxy-3-methylpentyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, cyclohexane Diol mono (meth) acrylate and the like can be mentioned, and these monomers c cannot be used because they react when the monomer b has an isocyanate group.
- monomer c having an acid group that is poorly reactive with the isocyanate group can be used.
- the acid groups are sulfonic acid and phosphoric acid.
- those having a sulfonic acid group include styrene sulfonic acid, dimethylpropyl sulfonic acid (meth) acrylamide, ethyl sulfonate (meth) acrylate, ethyl sulfonate ( And meth) acrylamide and vinyl sulfonic acid.
- examples of those having a phosphate group include methacryloyloxyethyl phosphate. One or more of these are used.
- the acid value of the block polymer provided by these acid groups is not particularly limited.
- a monomer having two or more addition polymerizable groups may be used for forming the B block.
- a bifunctional or higher functional monomer is used to form the B block, a bond between the two functional groups occurs, the B block is polymerized in a branched state, and a multi-branched star block polymer grafted with the A block is obtained.
- the bifunctional or higher functional monomer that can be used is not particularly limited.
- divinylbenzene (meth) acrylates at both ends of diols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and cyclohexanedimethanol; ) Acrylates; (meth) acrylates of polyhydroxyl compounds such as trimethylolpropane and pentaerythritol; those obtained by reacting a monomer having an acid group with a glycidyl group of a monomer having a glycidyl group and an acid group; a monomer having a hydroxyl group and an isocyanate And those obtained by reacting the monomer having the same.
- diols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and cyclohexanedimethanol
- Acrylates (meth) acrylates of polyhydroxyl compounds such as trimethylolpropane and pentaerythritol; those obtained by reacting
- the compound E that gives a functional group to the D block having a glycidyl group or an isocyanate group will be described.
- an amino compound (E-1) having good reactivity can be mentioned.
- the amino group reacts with the glycidyl group to open the glycidyl group to form a hydroxyl group, and when E-1 is a primary amino group, a secondary amino group, and E-1 to a secondary amino group.
- a tertiary amino group can be introduced, and in the case where E-1 is a tertiary amino group, a quaternary ammonium salt can be introduced into the D block, and the B block has a basic amino group. It becomes a block.
- the E-1 is not limited and a conventionally known amine is used.
- Illustrative examples of the primary amine include methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-octylamine, laurylamine, allylamine, ethanolamine, 3-aminopropanol, benzylamine, 1-phenylethylamine, 2-phenylethylamine, aniline, ethylenediamine, propane-1,3-diamine, 1,2-diaminopropane, 4-amino-9H-fluorene, 1-aminoanthracene, Examples include 1-aminopyrene and 1-aminoanthraquinone.
- the resulting functional group is a secondary amino group
- the group reacts with the reactive group of the D block in the other molecule
- the B block shows a crosslinked structure
- the star polymer having a higher order structure Or a multi-branched polymer.
- Secondary amines include dimethylamine, methylethylamine, diethylamine, methyl n-propylamine, di-n-propylamine, methyl n-butylamine, ethyl n-butylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di ( 2-ethylhexyl) amine, di-n-octylamine, dilaurylamine, dicyclohexylamine, diallylamine, dibenzylamine, dinaphthylmethylamine, diethanolamine, di-n-propanolamine, diisopropanolamine, diphenylamine, dinaphthylamine, pyrrole Pyrrolidine, piperazine, morpholine, indole, indoline, carbazole, 2-methylcarbazole, 3,4-benzylcarbazole, N-methylbenzylamine, N-dode
- Tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, trihexylamine, tri-n-octylamine, triallylamine, tribenzylamine, triethanolamine, triisopropanolamine, N, N -Dimethyl n-butylamine, N, N-dimethyl n-dodecylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N- Dimethyl 1,3-propanediamine, N, N-diethyl 1,3-propanediamine, N, N-dibutyl 1,3-propanediamine, 2-aminoethylpiperidine, 2-aminopropylpiperidine, 2-aminoethylmorpholine, 2-aminoprop
- amines include ammonia, imidazole, benzimidazole, pyrazole, 4-aminopyridine, 2-aminopyrimidine, 2-amino-1H-imidazole, 1H-imidazole-4-ethanamine, 2-amino-1H-benzimidazole, 3-amino-9-ethyl-9H-carbazole, 3- (aminomethyl) -9-methyl-9H-carbazole, 4- (9H-carbazol-9-yl) -4'-aminobenzophenone, 7-amino-4 -Methylcoumarin, 7-amino-3-phenylcoumarin, 4-aminobiphenyl, 8-aminoquinoline, 9-aminoacridine and the like. One or more of these are used.
- a compound (E-1) having two or more amino groups may be used.
- the B block exhibits a crosslinked structure, and can be a star polymer or a multi-branched polymer.
- the compound having two or more amino groups include low molecular weight diamines such as ethylenediamine, hexamethylenediamine, xylylenediamine, and diethylenetriamine, and triamines.
- a multi-branched block polymer can be obtained by using a polyamine which is a polymer amine having several amino groups or more. This polyamine portion is surface adsorbed to the pigment and is highly useful because it can disperse the pigment to a high degree.
- polyamine examples include polyethyleneimine, polyallylamine, and polyvinylamine.
- the degree of polymerization of the polyamine is not particularly limited, and the molecular weight is 200 to 10,000.
- Polyethyleneimine includes primary, secondary and tertiary amino groups, and when reacted with a glycidyl group, it can react with tertiary to form a quaternary salt. it can.
- a compound (E-2) having a primary amino group, a secondary amino group, or one hydroxyl group having good reactivity with the isocyanate group is reacted.
- a urethane bond is formed by the reaction of an isocyanate group and a hydroxyl group, and a urea bond is formed by a reaction with a primary or secondary amino group.
- E-2 uses a compound having one primary amino group, secondary amino group or hydroxyl group and having one or more tertiary amino groups.
- the compound having one primary amino group or secondary amino group and having one or more tertiary amino groups is as described in E-1 above, and is selected from the above. One or more are used.
- the aforementioned polyamine is used as E-1 to be reacted with an isocyanate group.
- an isocyanate group In the reaction molar ratio of the isocyanate group and amino group, by using an excess of amino group, a multi-branched block polymer having basicity in the B block can be obtained.
- the degree of polymerization of the polyamine is not limited, and the ratio between the isocyanate group and the amino group is not limited, and the amino group is used in an equimolar amount or more.
- Examples of the compound having one hydroxyl group and one or more tertiary amino groups include dimethylaminoethanol, diethylaminoethanol, dimethylaminopropanol, dimethylaminoethylmethylaminoethanol, N-methyl-3-piperidinol, N-ethyl-3-piperidinol, N-benzyl-3-piperidinol, N-benzyl-3-pyrrolidinol, N-methyl-2-piperidineethanol, 1,2,2,6,6-tetramethylpiperidinol, N -Methyl-4-piperidinol, 3-hydroxypyridine, 3-hydroxy-6-methylpyridine, 5-methyl-2-pyridineethanol and the like are not particularly limited, and one or more are used.
- a dye compound that is a polycyclic compound can be introduced to give the B block pigment adsorption performance.
- the dye compound a dye compound having a pigment-like structure or a pigment raw material skeleton and having an amino group or a hydroxyl group is used.
- conventionally known dyes are used as the dyes, and the structures of the dyes are azo, cyanine, phthalocyanine, perylene, perinone, diketopyrrolopyrrole, quinacridone, which are used for pigments and dyes.
- the dye is a fluorescein-based skeleton or a fluorescent dye, and has an amino group or a hydroxyl group in the dye skeleton.
- an amino group or a hydroxyl group may be introduced into the raw material structure for forming these dyes.
- an azo coupler Etc. These are not particularly limited, and one or more of these are used.
- a pigment raw material it may be reacted as it is with the D block and introduced into the B block as a functional group to be used as a pigment adsorbing group. It may be a functional group or a pigment containing a block polymer can be obtained by synthesizing a block polymer to which a pigment raw material is bonded as a part of the pigment raw material.
- the polymer particle of the present invention is bonded to the pigment particle surface by reacting the pigment particle having an amino group or hydroxyl group on the surface with the block polymer having the D block having the glycidyl group or isocyanate group of the present invention.
- An amino group or a hydroxyl group may be introduced on the surface of the pigment, and the active hydrogen and the glycidyl group or epoxy group of the D block polymer may be reacted and bonded.
- the monomer a constituting the A block or the C block will be described.
- the A block or the C block is one or more kinds of monomers that do not react with the glycidyl group or isocyanate group of the B block described above, and the glycidyl group. And a monomer having no isocyanate group.
- the monomer a is a monomer that does not react with the above-described glycidyl group or isocyanate group, and they are not particularly limited.
- the A block or C block is a homopolymer obtained by polymerizing one type of monomer a, a random polymer obtained by copolymerizing two or more types of monomer a, a gradient polymer having a gradient in the monomer arrangement, etc.
- the structure can be taken.
- the monomer a and the monomer c may be the same or different.
- radical initiator used in the polymerization of the present invention conventionally known ones are used, and are not particularly limited, and commonly used 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.
- AD, or AD-C block polymers can be obtained, and the block polymer AB or ABC of the present invention can be obtained by addition reaction of compound E with these block polymers.
- a polymer dispersing agent which is a polymer can be obtained.
- the polymerization used in the present invention may be bulk polymerization, but is preferably solution polymerization.
- the solid content of the polymerization liquid is not particularly limited, but is 5 to 80% by mass, preferably 10 to 60% by mass.
- a solvent that does not react with a glycidyl group or an isocyanate group is selected in each case.
- Solvents that can be used include hydrocarbon solvents such as hexane, octane, decane, isodecane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, and cumene; in the case of a glycidyl group, methanol, ethanol, propanol, isopropanol, butanol, isopropanol Alcohol solvents such as butanol, hexanol, benzyl alcohol, cyclohexanol; in the case of glycidyl group, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve
- the molecular weight of the polymer can be controlled by the amount of the starting compound.
- an arbitrary molecular weight or the magnitude of the molecular weight can be controlled.
- the polymerization method according to the present invention may involve a side reaction that is a coupling reaction between polymer radicals, and the molecular weight may be increased rather than the theoretical molecular weight. Furthermore, the polymerization may be stopped and the molecular weight may become smaller. In this invention, since it is a big point that a polymer dispersing agent is a block polymer, even if those side reactions are accompanied, there is no problem.
- the radical initiator is used in an amount of 0.001 to 0.1 mol times, more preferably 0.002 to 0.05 mol times, still more preferably 0.005 to 0.01 mol times the number of moles of monomers. This is because polymerization does not proceed sufficiently if the amount of radical initiator is too small, and polymerization that does not participate in living radical polymerization occurs if there is too much radical initiator, and the molecular weight of the resulting block polymer is higher than the theoretical molecular weight. May be lower.
- the amount of the catalyst is less than the number of moles of the radical initiator. If the number of moles is too large, the polymerization is too controlled and the polymerization itself does not proceed. On the other hand, if the amount is too small, the polymerization cannot be controlled sufficiently, a termination reaction occurs frequently, and a polymer having a wide molecular weight distribution is formed.
- the ratio of the above blending is arbitrarily determined and is not particularly limited.
- the polymerization temperature in the present invention is not particularly limited, and is 0 ° C. to 150 ° C., more preferably 30 ° C. to 120 ° C. Adjusted by the half-life of each radical initiator.
- the polymerization time is preferably continued until the monomer runs out, but is not particularly limited. For example, 0.5 to 48 hours, practical time is preferably 1 to 24 hours, and more preferably 2 hours. ⁇ 12 hours.
- the polymerization atmosphere is not particularly limited and may be polymerized as it is, that is, oxygen may be present within the normal range in the polymerization system, and is performed in a nitrogen atmosphere to remove oxygen as necessary. May be.
- the various materials to be used may remove impurities by distillation, activated carbon or alumina, commercially available products can be used as they are.
- the polymerization may be performed under light shielding, and there is no problem even if it is performed in a transparent container such as glass.
- the molecular weight of the block polymer (polymer dispersing agent) of the present invention is 1,000 to 30 in terms of polystyrene-reduced number average molecular weight (hereinafter referred to as Mn) as measured by gel permeation chromatography (hereinafter referred to as GPC). 000, more preferably 5,000 to 20,000. Further, the molecular weight distribution (hereinafter referred to as PDI) which is the ratio of Mn to the weight average molecular weight can be set to 1.05 to 2 by the method of the present invention. The preferred range is 1.05 to 1.7.
- the AB block polymer is obtained by first polymerizing the monomer a or the monomer b by the living radical polymerization described above, and then the A block. Can be obtained by polymerizing the monomer b, and when the monomer b is polymerized first, the monomer a is polymerized to form an AD copolymer, which is then reacted with the compound E.
- the monomer a was further added to polymerize to AD, and then Compound E was added.
- the target ABC polymer can be obtained.
- the polymer blocks of A and C may be the same or different, but the A and C blocks (mass fraction of the two blocks combined); 40-99% by weight, B block; 1 to 60% by mass. Since the influence of the B block on the pigment is particularly important in the present invention, the B block is 1 to 60% by mass in the block polymer.
- the amount of the compound E to be added after the formation of the D block is preferably 1 to 120%, more preferably 25 to 100% in terms of a molar ratio with respect to the glycidyl group or the isocyanate group.
- the molar ratio is 1% or less, there are few adsorbed portions of the block polymer to the pigment, and sufficient pigment dispersibility cannot be exhibited.
- the temperature at which the compound E is reacted with the glycidyl group or isocyanate group of the D block is not particularly limited, and is 0 ° C. to 150 ° C., more preferably 20 ° C. to 120 ° C.
- the reaction time is preferably continued until the unreacted compound E disappears, but is not particularly limited.
- the practical time is 0.5 to 24 hours, preferably 1 to 24 hours. More preferably, it is 2 hours to 12 hours.
- a conventionally known catalyst may be added.
- the catalyst is not particularly limited, and examples thereof include quaternary ammonium salts such as benzyltriethylammonium chloride and benzyltriethylammonium bromide, tetraethylphosphonium bromide, dibutyltin dilaurate, tin dilaurate and diazabicyclooctane.
- quaternary ammonium salts such as benzyltriethylammonium chloride and benzyltriethylammonium bromide, tetraethylphosphonium bromide, dibutyltin dilaurate, tin dilaurate and diazabicyclooctane.
- a block polymer of AB or ABC having a B block that is pigment-adsorbing can be obtained.
- the pigment dispersion of the present invention contains the above-mentioned polymer dispersant, pigment, liquid medium, and various other additives as necessary.
- the polymer dispersant of the present invention is useful as a polymer dispersant for pigment dispersions of paints, inks, stationery, inkjet inks, color filters, etc.
- the block polymer of the present invention is a paint, ink, coating It can also be used as a binder for agents, stationery, textile printing, inkjet inks, and color filters.
- dye or a pigment as needed it can also be used for the above-mentioned use as a pigment
- the amount of the polymer dispersant (block polymer) for these uses is 1 to 200%, more preferably 5 to 100% by mass with respect to the pigment.
- the formulation and dispersion method of the pigment dispersion are conventionally known methods and are not particularly limited. Further, two or more conventionally known dispersants can be used in combination for dispersion.
- the pigment concentration of the pigment dispersion is 0.5 to 70% by mass, preferably 0.5 to 60% by mass in the dispersion, although it depends on the type of pigment.
- the pigment used in the present invention is not limited, and conventionally known pigments are used.
- the inorganic pigment include titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, silica, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead, and carbon black.
- Organic pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, Ansanthrone pigment, indanthrone pigment, flavanthrone pigment, pyranthrone pigment, diketopyrrolopyrrole pigment and the like.
- liquid medium of the pigment dispersion used in the present invention one or more of water and the above organic solvents are used.
- Illustrating the method for dispersing the pigment, the polymer dispersant of the present invention, the liquid medium, and the pigment are used, and various additives are mixed as necessary, and dispersed by a disperser.
- a pigment, a polymer dispersant, and a liquid medium are mixed, premixed if necessary, and further dispersed by a disperser to obtain a pigment dispersion.
- the disperser that can be used in the present invention is not particularly limited, and conventionally known dispersers can be used. For example, a kneader, an attritor, a ball mill, a sand mill using glass or zircon, a horizontal media disperser, a colloid mill, or the like can be used.
- various additives can be added to the pigment dispersion.
- durability improvers such as UV absorbers and antioxidants; anti-settling materials; release agents or release improvers; fragrances, antibacterial agents, antifungal agents; plasticizers, anti-drying agents, etc.
- other dispersants, dispersion aids, pigment treatment agents, dyes, and the like can be added.
- the obtained pigment dispersion may be used as it is, but it is preferable to remove the coarse particles which may be slightly present in the centrifuge, ultracentrifuge or filter in order to improve the reliability of the pigment dispersion. .
- the viscosity of the resulting pigment dispersion is arbitrary depending on the application.
- a pigment dispersion can be obtained using a polymer dispersant.
- These pigment dispersions can be used for conventionally known paints, inks, coating agents, and stationery colorants. Specifically, it can be used as a colorant for water-based paints, oil-based paints, gravure inks, water-based flexographic inks, inkjet inks, stationery inks, writing instrument inks, coating agents, color filter colors, wet toners and the like.
- the amount added cannot be generally described in terms of the pigment concentration, it can be used in accordance with each color concentration.
- the block polymer of the present invention can also be used as a binder component for paints, offset inks, gravure inks, inkjet inks, stationery colors, and textile printing.
- the method of use is the same as conventionally known and is not particularly limited.
- a strong coating film of the block polymer can be obtained by using the functional group and performing a curing reaction.
- an isocyanate crosslinking agent, a melamine-based crosslinking agent, or the like can be used as a curing agent.
- a glycidyl group or an isocyanate group is present in the block polymer, a low molecular compound or a high molecular compound capable of reacting with them can be added to make the block polymer three-dimensional and cure.
- the block polymer can be three-dimensionalized by adding and reacting with a compound capable of reacting with the compound, and performing self-condensation.
- GMA glycidyl methacrylate
- DBA di-n-butylamine
- Synthesis Example 2 Synthesis of AB Block Polymer Having Glycidyl Group Reacted with Diphenylamine
- a reaction vessel similar to Synthesis Example 1 150 parts of PGMAc, 3.0 parts of iodine, 5.9 parts of AIBN, benzyl methacrylate (hereinafter referred to as BzMA) 132.2 parts and 0.067 parts of N-iodosuccinimide (hereinafter referred to as NIS) were charged and polymerized at 80 ° C. for 3 hours while bubbling nitrogen to form an A block. Sampling and measuring the solid content, the polymerization conversion rate converted from the non-volatile content was 100%. At this time, Mn in RI was 5,400, and PDI was 1.24. Further, in the ultraviolet detector (measurement wavelength: 254 nm, hereinafter referred to as UV), there was absorption of an aromatic ring, Mn in UV was 5,300, and PDI was 1.25.
- UV ultraviolet detector
- Synthesis Example 3 Synthesis of AB Block Polymer Having Glycidyl Group Reacted with Di n-Butylamine
- a reaction vessel similar to Synthesis Example 1 250 parts of PGMAc, 6.0 parts of iodine, 10.8 parts of AIBN, n-butyl 213.3 parts of methacrylate (hereinafter referred to as BMA) and 0.134 parts of NIS were charged and polymerized at 80 ° C. for 3 hours while bubbling nitrogen to form an A block. Sampling and measuring the solid content, the polymerization conversion rate converted from the non-volatile content was 100%. At this time, Mn in RI of GPC was 4,000, and PDI was 1.26.
- Synthesis Example 6 Synthesis of AB Block Polymer Having Glycidyl Group Reacted with Polyethyleneimine
- PGM propylene glycol monomethyl ether
- V-65 manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as V-65
- BzMA 2-ethylhexyl methacrylate
- 2EHMA 2-ethylhexyl methacrylate
- Synthesis Example 7 Synthesis of AB Block Polymer Having Glycidyl Group Reacted with Polyethyleneimine
- 150 parts of PGM, 3.0 parts of iodine, 9.0 parts of V-65, 2EHMA69 4 parts, 37.1 parts of ethyl methacrylate (hereinafter referred to as EMA), 32.5 parts of MMA, 0.2 part of NIS, and 1.5 parts of dilauroyl peroxide were polymerized at 70 ° C. for 3 hours while bubbling nitrogen. A block was formed. Sampling and measuring the solid content, the polymerization conversion rate converted from the non-volatile content was 100%. At this time, Mn in RI was 6,200, and PDI was 1.24.
- MOI methacryloxyethyl isocyanate
- intermediate resin-2 1,500 parts of ion-exchanged water was added to a 3-liter beaker to a high-speed stirrer, and the resin solution obtained above was added and precipitated. When this was filtered and dried, a slightly white brown powder was obtained. This is designated as intermediate resin-2.
- a pigment-like compound having the following structure Mix 10 parts of acetic acid (2.2 parts of acetic acid and 187.8 parts of water) by diazo coupling (paraazoaniline as diazo component and acetoacetic acid paraanisidide as coupler component and reducing nitro group by conventional method) did. A slightly dull bluish yellow liquid was obtained.
- a purple dye compound N- (3-aminophenyl) -3-((9-ethyl-9H-carbazol-3-yl) diazenyl) -2-naphthamide having the following structure
- a solution of 217 parts of N-methylpyrrolidone was added to 32 parts of which was heated to 100 ° C. and reacted for 2 hours.
- 1 part of butylamine was added and the remaining isocyanate was reacted to form a B block.
- the molecular weight by GPC was 8,000, and PDI was 1.31. This is designated as BR-12.
- the molecular weight measured by a UV detector was 8,100, and the PDI was 1.32.
- the B block formation there was no UV absorption, but it was considered that absorption was generated by reacting the dye, and molecular weight measurement with a UV detector became possible.
- the above-described dye is bound to the molecular weight, it is presumed that the absorption of the column and the D block portion of the dye block are aggregated in the solvent and become smaller.
- yellow dye compound 1- (2-aminophenylthio) anthraquinone having the following structure
- a solution of 136.2 parts of N-methylpyrrolidone was added to 13.8 parts, and the mixture was heated to 100 ° C. and reacted for 2 hours.
- 1 part of butylamine was added and the remaining isocyanate was reacted to form a B block.
- the molecular weight by GPC was 13,200, and PDI was 1.41. This is designated as BR-13.
- Example 2 to 7 A pigment dispersion was obtained in the same manner as Example 1 except that BR-2 to 7 obtained in Synthesis Examples 2 to 7 were used instead of BR-1 of Example 1. These are designated as R-2 to 7.
- Example 8 to 13 Instead of PR-254 of Example 1, PR-177 which is an anthraquinone pigment was used, and BR obtained in Synthesis Examples 1, 3, 6, 8, 10, 13 instead of BR-1 of Example 1 A pigment dispersion was obtained in the same manner as in Example 1 except that 1, 3, 6, 8, 10, and 13 were used. These are designated as R-8 to 13.
- Example 14 PV-23, which is a dioxazine violet pigment, was used in place of PR-254 in Example 1, BR-12 obtained in Synthesis Example 12 was used in place of BR-1 in Example 1, and the others were A pigment dispersion was obtained in the same manner as in Example 1. This is V-1.
- Example 1 A pigment dispersion was obtained in the same manner as in Example 1 except that A-1 obtained in Comparative Synthesis Example was used in place of BR-1 in Example 1. This is designated as R-14.
- Example 2 A pigment dispersion is obtained in the same manner as in Example 1 except that A-1 obtained in Comparative Synthesis Example is used in place of BR-1 in Example 1 and PR-177 is used in place of PR-254. It was. This is designated as R-15.
- the viscosity of the pigment dispersion for color filters of the above examples and the gloss of the color development surface, and the presence or absence of aggregates were confirmed.
- the following methods were used to evaluate the viscosity and color development of the color filter color product and observe the presence of aggregates. In addition, evaluation was performed immediately after production and after storage for 1 month at room temperature.
- Viscosity The viscosity (mPa ⁇ s) of the pigment dispersion immediately after production and after storage for 1 month at 25 ° C. was measured with an E-type viscometer at room temperature (25 ° C.) and at a rotor rotation speed of 60 rpm.
- the pigment dispersion using the block polymer of the present invention as a polymer dispersant has little change in viscosity with time, good gloss, and is stable without occurrence of aggregates immediately after production and after storage for 1 month. It was found that the pigment was dispersed in.
- the block polymer of the present invention can exhibit excellent dispersibility in the preparation of a pigment dispersion.
- the block polymer can be efficiently produced by the production method of the present invention.
- a pigment dispersion having excellent physical properties can be obtained, giving excellent physical properties to various articles such as paints, inks, coating agents, etc., and high-performance articles give.
Abstract
Description
本発明で用いる重合方法は、新規なリビングラジカル重合であり、該リビングラジカル重合は従来の方法とは違い、金属化合物や配位子を使用せず、また、ニトロキサイド、ジチオカルボン酸エステルやザンテートなどの特殊な化合物も使用しない。従来のラジカル重合に、開始化合物と触媒を併用するだけで容易に行える重合方法である。
で表される反応機構で進み、ドーマント種Polymer-X(P-X)の成長ラジカルへの可逆的活性反応である。上記重合機構は、触媒の種類によって変わる可能性があるが、次のように進むと考えられる。式1では、ラジカル開始剤から発生したP・がXAと反応して、in siteで触媒A・が生成する。A・はP-Xの活性化剤として作用して、この触媒作用によってP-Xは高い頻度で活性化する。
特に、本発明では、イソシアネート基に反応させるE-1として、前記したポリアミンが使用される。そのイソシアネート基とアミノ基の反応モル比において、アミノ基を過剰に使用することで、塩基性をBブロックに持つ多分岐型ブロックポリマーとすることができる。そのポリアミンの重合度は限定されず、また、イソシアネート基とアミノ基の比率も限定されず、アミノ基は当モル以上使用される。
開始化合物1モル×モノマー分子量×モノマー対開始化合物モル比
で算出することができる。
攪拌機、逆流コンデンサー、温度計および窒素導入管を取り付けた反応容器に、プロピレングリコールモノメチルエーテルアセテート(以下PGMAc)100部、ヨウ素3.0部、2,2’-アゾビス(イソブチロニトリル)(以下AIBN)5.9部、メチルメタクリレート(以下MMA)75部およびジエチルフォスファイト(以下DEP)0.766部を仕込んで、窒素バブリングしながら80℃で2時間重合させてAブロックを作成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。また、GPCでの可視光検出機(以下RI)におけるMnは2,700であり、PDIは1.22であった。
合成例1と同様の反応容器に、PGMAc150部、ヨウ素3.0部、AIBN5.9部、ベンジルメタクリレート(以下BzMA)132.2部、N-アイオドスクシンイミド(以下NIS)0.067部を仕込んで、窒素バブリングしながら80℃で3時間重合させてAブロックを形成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。この時のRIにおけるMnは5,400であり、PDIは1.24であった。また、紫外線検出機(測定波長254nm、以下UV)では芳香環の吸収があって、UVでのMnは5,300であり、PDIは1.25であった。
合成例1と同様の反応容器に、PGMAc250部、ヨウ素6.0部、AIBN10.8部、n-ブチルメタクリレート(以下BMA)213.3部およびNIS0.134部を仕込んで、窒素バブリングしながら80℃で3時間重合させてAブロックを形成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。この時のGPCのRIにおけるMnは4,000であり、PDIは1.26であった。
合成例1と同様の反応容器に、PGMAc100部、ヨウ素3.0部、AIBN5.9部、MMA75部およびNIS0.067部を仕込んで、窒素バブリングしながら80℃で2時間重合させてAブロックを形成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。この時のGPCのRIにおけるMnは2,800であり、PDIは1.23であった。
合成例1と同様の反応容器に、PGMAc100部、ヨウ素3.0部、AIBN5.9部、MMA75部および2,6-ジ-t-ブチル-4-メチルフェノール(以下BHT)0.33部を仕込んで、窒素バブリングしながら80℃で2時間重合させてAブロックを作成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。この時のGPCのRIにおけるMnは2,800であり、PDIは1.25であった。
合成例1と同様の反応容器に、プロピレングリコールモノメチルエーテル(以下PGM)150部、ヨウ素3.0部、2,2’-アゾビス(2,4-ジメチルバレロニトリル)(和光純薬社製V-65、以下V-65)9.0部、BzMA176.2部、2-エチルヘキシルメタクリレート(以下2EHMA)59.5部、BMA28.4部、MMA50.0部、NIS0.5部、ジラウロイルパーオキサイド3.0部を仕込んで、窒素バブリングしながら70℃で3時間重合させてAブロックを形成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。この時のRIにおけるMnは12,000であり、PDIは1.30であった。また、UVでのMnは12,200であり、PDIは1.29であった。
合成例1と同様の反応容器に、PGM150部、ヨウ素3.0部、V-65を9.0部、2EHMA69.4部、エチルメタクリレート(以下EMA)37.1部、MMA32.5部、NIS0.2部、ジラウロイルパーオキサイド1.5部を仕込んで、窒素バブリングしながら70℃で3時間重合させてAブロックを形成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。この時のRIにおけるMnは6,200であり、PDIは1.24であった。
合成例1と同様の反応容器に、PGMAc150部を投入し80℃に加温した後、予め別容器に調製しておいたAIBN5.9部を溶解させたMMA75部およびGMA17.8部のモノマー溶液を反応容器中に1.5時間かけて滴下し、滴下終了後、さらに同温度で3時間重合させた。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。
合成例1と同様の反応容器に、PGMAc100部、2-アイオド-2-シアノプロパン2.2部、ジラウロイルパーオキサイド4.4部、MMA42部、BMA39.7部および4-t-ブチル-2,6-キシレノール(以下IA)0.25部を仕込んで、窒素バブリングしながら80℃で2時間重合させてAブロックを形成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。GPCのMnは4,200、PDIは1.21であった。
合成例8の4-ピリジンエタノールを2-アミノ-N-エチルカルバゾール10.3部に変えた以外は同様にして反応を行った。転化率は98%で、濃い褐色透明液体を得た。GPCにて分子量を測定したところ、Mnは4,670、PDIは1.40であり、UVではMn4,710、PDIは1.42であった。これをBR-9とする。
合成例1と同様の反応容器に、ジエチレングリコールジメチルエーテル(以下ジグライム)100部、ヨウ素1.8部、V-65を5.3部、MMA71.1部、AA12.8部およびIA0.32部を仕込んで70℃で2時間攪拌してAブロックを形成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。GPCのMnは4,970、PDIは1.51であった。
市販のピグメントイエローPY-74を100部、食塩700部およびジエチレングリコール200部を3Lのニーダーに投入して温度を100~120℃に保つように調整し、その温度で8時間磨砕した。ついで得られた混練物の800部を2,000部の水に投入し、4時間、高速攪拌し、その後ろ過、乾燥を行い、水ペースト(顔料純分32.0%)を得た。
(ジアゾ成分としてパラニトロアニリン、カップラー成分としてアセト酢酸パラアニシダイドを使用してジアゾカップルし、ニトロ基を従来の方法で還元したもの)を10部、酢酸2.2部および水187.8部を混合した。若干くすみのある青味の黄色液体となった。
合成例1と同様の反応容器に、ジグライム88部、ヨウ素0.5部、V-65を2.0部、MMA15部、エトキシジエチレングリコールメタクリレート23.7部、2EHMA19.8部、スクシンイミド0.02部を添加して、窒素バブリングしながら60℃で5時間重合させてAブロックを形成した。サンプリングし固形分を測定し、不揮発分から換算した重合転化率は100%であった。GPCのMnは7,800、PDIは1.41であった。
の32部をN-メチルピロリドン217部の溶解溶液を添加して、100℃に加温し2時間反応させた。反応後、ブチルアミン1部を添加し、残イソシアネートを反応させ、Bブロックを形成した。この時のGPCによる分子量は8,000であって、PDIは1.31であった。これをBR-12とする。
合成例の配合を次に変えて行った以外は同様にして行った。
Aブロック
MMA 15部
EMA 17.1部
BzMA 26.4部
2EHMA 29.7部
得られたAブロックのMn=11,270、PDI1.42
Bブロック
MMA 15部
MOI 7.8部
得られたブロックポリマーMn=12,600、PDI1.50
の13.8部をN-メチルピロリドン136.2部の溶解溶液を添加して、100℃に加温し2時間反応させた。反応後、ブチルアミン1部を添加し、残イソシアネートを反応させ、Bブロックを形成した。この時のGPCによる分子量は13,200であって、PDIは1.41であった。これをBR-13とする。
アクリル樹脂ワニス(メタクリル酸ベンジル/メタクリル酸/メタクリル酸2-ヒドロキシエチル=70/15/15の質量比で重合させたもの:分子量12,000、酸価100、固形分40%のPGMAc溶液)50部に、PR-254であるジケトピロロピロール顔料を15部、合成例1で得られたBR-1を5部、PGMAcを30部配合し、プレミキシングの後、横型ビーズミルで分散し、顔料分散液を得た。これをR-1とする。
実施例1のBR-1の代わりに合成例2~7で得られたBR-2~7を使用し、その他は、実施例1と同様にして顔料分散液を得た。これらをR-2~7とする。
実施例1のPR-254の代わりにアントラキノン系顔料であるPR-177を使用し、実施例1のBR-1の代わりに合成例1,3,6,8,10,13で得られたBR-1,3,6,8,10,13を使用し、その他は、実施例1と同様にして顔料分散液を得た。これらをR-8~13とする。
実施例1のPR-254の代わりにジオキサジンバイオレット顔料であるPV-23を使用し、実施例1のBR-1の代わりに合成例12で得られたBR-12を使用し、その他は、実施例1と同様にして顔料分散液を得た。これをV-1とする。
実施例1のBR-1の代わりに比較合成例で得られたA-1を使用し、その他は、実施例1と同様にして顔料分散液を得た。これをR-14とする。
実施例1のBR-1の代わりに比較合成例で得られたA-1を、PR-254の代わりにPR-177を使用し、その他は、実施例1と同様にして顔料分散液を得た。これをR-15とする。
○:良好、△:やや良好、×:不良
○:凝集物なし、△:わずかに凝集物有り、×:凝集物有り
以上の結果を表1に示す。
Claims (14)
- 少なくとも、顔料、液媒体および高分子分散剤を含有する顔料分散液であって、上記高分子分散剤が、A-BまたはA-B-C(A、B、Cはそれぞれポリマーブロックを表し、AブロックとCブロックとは同じでも異なってもよい)で表されるブロックポリマーであり、
上記AブロックおよびCブロックが、アミノ基および水酸基を有しないエチレン性不飽和モノマー(モノマーa)からなるポリマーブロックであり、
上記Bブロックが、グリシジル基またはイソシアネート基を有するモノマー(モノマーb)からなるポリマーブロック(D)に、グリシジル基またはイソシアネート基を介してアミノ化合物(E-1)および水酸基を有する化合物(E-2)のいずれか一方が結合しているポリマーブロックであることを特徴とする顔料分散液。 - A-DまたはA-D-C(A、C、Dはそれぞれポリマーブロックを表し、AブロックとCブロックは同じでも異なってもよい)で表されるブロックポリマーが、ヨウ素化合物を開始化合物とし、リン化合物、窒素化合物または酸素化合物を触媒とするモノマーaおよびモノマーbのリビングラジカル重合法によって得られたブロックポリマーである請求項1に記載の顔料分散液。
- 高分子分散剤中のBブロックの含有量が、1~60質量%である請求項1に記載の顔料分散液。
- 高分子分散剤の数平均分子量が、1,000~30,000である請求項1に記載の顔料分散液。
- 高分子分散剤の分散度(重量平均分子量/数平均分子量)が、1.05~1.7である請求項1に記載の顔料分散液。
- A-DまたはA-D-C(A、C、Dはそれぞれポリマーブロックを表し、AブロックとCブロックとは同じでも異なってもよい)で表されるブロックポリマーであり、上記AブロックおよびCブロックが、アミノ基および水酸基を有しないエチレン性不飽和モノマー(モノマーa)からなるポリマーブロックであり、上記Dブロックが、グリシジル基またはイソシアネート基を有するモノマー(モノマーb)からなるポリマーブロックであることを特徴とするブロックポリマー。
- さらにアミノ化合物(E-1)および水酸基を有する化合物(E-2)のいずれか一方が、グリシジル基またはイソシアネート基を介して結合している請求項6に記載のブロックポリマー。
- アミノ化合物(E-1)が、ポリエチレンイミン、ポリアリルアミンおよびポリビニルアミンから選ばれるポリアミンであり、ブロックポリマーが多分岐型ブロックポリマーである請求項7のブロックポリマー。
- アミノ化合物(E-1)または水酸基を有する化合物(E-2)が、アミノ基又は水酸基を1個以上有する色素化合物である請求項7に記載の色素ブロックポリマー。
- アミノ基および水酸基を有しないエチレン性不飽和モノマー(モノマーa)から、リビングラジカル重合法によりAブロックを形成し、ついでグリシジル基またはイソシアネート基を有するモノマー(モノマーb)からリビングラジカル重合法によりDブロックを形成し、またはさらにモノマーaからリビングラジカル重合法によりCブロックを形成することを特徴するA-DまたはA-D-C(A、C、Dはそれぞれポリマーブロックを表し、AブロックとCブロックとは同じでも異なってもよい)で表されるブロックポリマーの製造方法。
- さらにアミノ化合物(E-1)および水酸基を有する化合物(E-2)のいずれか一方を、グリシジル基またはイソシアネート基を介して結合させる請求項10に記載のブロックポリマーの製造方法。
- リビングラジカル重合法が、ヨウ素化合物を開始化合物とし、リン化合物、窒素化合物または酸素化合物を触媒とする重合法である請求項10に記載のブロックポリマーの製造方法。
- リン化合物が、ハロゲン化リン、フォスファイト系化合物またはフォスフィネート系化合物であり、窒素化合物が、イミド類、ヒダントイン類、バルビツル酸類またはシアヌル酸類であり、酸素化合物が、フェノール系化合物、アイオドオキシフェニル化合物またはビタミン類である請求項12に記載のブロックポリマーの製造方法。
- 請求項1に記載の顔料分散液を含有してなることを特徴とする塗料、インク、コーティング剤、トナーまたは文具。
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Also Published As
Publication number | Publication date |
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JPWO2010016523A1 (ja) | 2012-01-26 |
KR20110042103A (ko) | 2011-04-22 |
EP2311920B1 (en) | 2016-10-12 |
US20110136965A1 (en) | 2011-06-09 |
EP2311920A4 (en) | 2012-02-22 |
US8822591B2 (en) | 2014-09-02 |
KR101252371B1 (ko) | 2013-04-08 |
EP2311920A1 (en) | 2011-04-20 |
JP5223082B2 (ja) | 2013-06-26 |
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