WO2008007776A1 - Polyester dispersant, process for production of the same, and pigment composition using the same - Google Patents

Polyester dispersant, process for production of the same, and pigment composition using the same Download PDF

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Publication number
WO2008007776A1
WO2008007776A1 PCT/JP2007/063997 JP2007063997W WO2008007776A1 WO 2008007776 A1 WO2008007776 A1 WO 2008007776A1 JP 2007063997 W JP2007063997 W JP 2007063997W WO 2008007776 A1 WO2008007776 A1 WO 2008007776A1
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WIPO (PCT)
Prior art keywords
group
acid anhydride
compound
dispersant
polyester
Prior art date
Application number
PCT/JP2007/063997
Other languages
French (fr)
Japanese (ja)
Inventor
Tsutomu Hiroshima
Atsushi Nakazato
Joji Mikami
Original Assignee
Toyo Ink Manufacturing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Ink Manufacturing Co., Ltd. filed Critical Toyo Ink Manufacturing Co., Ltd.
Priority to KR1020097002686A priority Critical patent/KR101354265B1/en
Priority to CN2007800267222A priority patent/CN101490128B/en
Priority to JP2008524858A priority patent/JP4396777B2/en
Publication of WO2008007776A1 publication Critical patent/WO2008007776A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • 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
    • C08F8/14—Esterification
    • 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
    • C09K23/34—Higher-molecular-weight carboxylic acid esters
    • C09K23/36—Esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
    • C09B67/0035—Mixtures of phthalocyanines
    • 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
    • C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
    • 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
    • C09B67/0069—Non aqueous dispersions of pigments containing only a solvent and a dispersing agent
    • 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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D17/002—Pigment pastes, e.g. for mixing in paints in organic 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
    • C09D7/45—Anti-settling agents
    • 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

Definitions

  • the present invention relates to a polyester dispersant, and more specifically, it is possible to produce a dispersion excellent in non-aggregability, fluidity, and storage stability, which is suitable for fields such as paints and colored resin compositions.
  • the present invention relates to a polyester dispersant, a production method thereof, and a pigment composition using the same.
  • a dispersant is used to maintain a good dispersion state.
  • the dispersant combines the structure of the part that adsorbs to the pigment and the part that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance between these two functional parts.
  • Various dispersants are used according to the surface condition of the pigment to be dispersed.
  • an acidic dispersant is used for a pigment having a surface that is biased toward basicity. In this case, the acidic functional group becomes the adsorption site of the pigment.
  • Dispersants having a carboxylic acid as an acidic functional group are described in, for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and the like.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 61-61623
  • Patent Document 2 JP-A-1-141968
  • Patent Document 3 JP-A-2-219866
  • Patent Document 4 Japanese Patent Laid-Open No. 11-349842
  • An object of the present invention is to provide a dispersant for obtaining a pigment dispersion which is excellent in dispersibility, fluidity and storage stability at a low use amount. Furthermore, the present invention is suitable for offset inks, gravure inks, color filter resist inks and ink jet inks, paints, colored resin compositions, etc., and has dispersibility and stability excellent in non-aggregation and fluidity. It is an object of the present invention to provide a polyester dispersant.
  • the present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule.
  • the present invention relates to a polyester dispersant produced by reaction of
  • the present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule.
  • It also relates to a polyester dispersant produced by reacting.
  • the present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule,
  • a hydroxyl group in the vinyl polymer (a) having two hydroxyl groups is a hydroxyl group in the vinyl polymer (a) having two hydroxyl groups
  • the present invention relates to a polyester dispersant produced by reaction of
  • the present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, A hydroxyl group in the vinyl polymer (a) having two hydroxyl groups, and a hydroxyl group in the polyol compound (c) other than the vinyl polymer (a);
  • the present invention relates to a polyester dispersant produced by reaction of
  • the present invention is produced by reacting a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in a tetracarboxylic acid anhydride (b).
  • the present invention relates to a polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of the compound (a2).
  • the present invention relates to a compound (al) having two hydroxyl groups and one thiol group in the molecule, and a hydroxyl group and tetracarboxylic acid anhydride in the polyol compound (c ') having no thiol group.
  • the present invention relates to a polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a3) produced by reacting with an acid anhydride group in (b).
  • the present invention relates to a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group in a tetracarboxylic acid anhydride (b), and a tricarboxylic acid anhydride (
  • the present invention relates to a polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a4) produced by reacting with an acid anhydride group in d).
  • the present invention relates to a compound (al) having two hydroxyl groups and one thiol group in the molecule, and a hydroxyl group and tetracarboxylic acid anhydride in the polyol compound (c ') having no thiol group.
  • the compound (a5) produced by reacting the acid anhydride group in (b) with the acid anhydride group in tricarboxylic anhydride (d) the ethylenically unsaturated monomer is radicalized.
  • the present invention relates to a polyester dispersant produced by polymerization.
  • the weight average molecular weight is 2000 to 35000, and the acid value power is 5 to 200.
  • a tetracarboxylic acid anhydride (b) Is represented by the following general formula (1) or general formula (2):
  • the weight average molecular weight of the bulle polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer is 1,000 to 10,000.
  • the glass transition temperature force of the bulle polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer is ⁇ 50 to 70 ° C.
  • the ethylenically unsaturated monomer force benzyl (meth) acrylate is contained in an amount of 20% to 70% by weight based on the whole monomer.
  • an ethylenically unsaturated monomer force includes a monomer represented by the following general formula (3).
  • the present invention relates to a pigment composition containing the above polyester dispersant and a pigment.
  • the present invention relates to a basic derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an attaridone derivative having a basic group, and a triazine derivative having a basic group.
  • the present invention relates to the above pigment composition containing at least one kind.
  • the present invention relates to a pigment dispersion obtained by dispersing the pigment composition in a varnish.
  • the present invention is directed to radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, so that Step A1 for producing a vinyl polymer (a) having a hydroxyl group,
  • the present invention is directed to radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, so that Step A2 for producing a vinyl polymer (a) having a hydroxyl group,
  • the present invention is directed to radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, so that Step A3 for producing a vinyl polymer (a) having a hydroxyl group,
  • the present invention is directed to radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, so that Step A4 for producing a vinyl polymer (a) having a hydroxyl group,
  • a step B4 of reacting the vinyl polymer (a), a tetracarboxylic acid anhydride (b), a polyol compound (c) other than the vinyl polymer (a), and a tricarboxylic acid anhydride (d), and a polyester comprising:
  • the present invention relates to a method for producing a dispersant.
  • the present invention provides a compound by reacting a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in a tetracarboxylic acid anhydride (b). Step B5 for producing (a2),
  • the present invention relates to a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule and a hydroxyl group in a polyol compound (c ') having no thiol group.
  • the present invention relates to a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group and a tricarboxylic acid anhydride in tetracarboxylic acid anhydride (b). (B) reacting with an acid anhydride group in step B7 to produce compound (a4);
  • the present invention has a hydroxyl group in the compound (al) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group and a thiol group in the tetracarboxylic acid anhydride (b).
  • the tetracarboxylic acid anhydride (b) is represented by the following general formula (1) or general formula (2):
  • the ethylenically unsaturated monomer contains benzyl (meth) acrylate in an amount of 20% to 70% by weight of the total monomer.
  • the ethylenically unsaturated monomer includes a monomer represented by the following general formula (3):
  • R represents a linear or branched alkyl group having 1 to 4 carbon atoms.
  • polyester dispersant of the present invention it is possible to provide a pigment composition having strong dispersibility, fluidity, and storage stability that has not been obtained conventionally. Furthermore, it is suitable for offset ink, gravure ink, resist ink and ink jet ink for color filters, paints, colored resin compositions, etc., has excellent dispersibility and stability with excellent non-aggregability and fluidity, and high storage stability. And a pigment dispersion having high stability with time.
  • a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a solvent as a dispersion medium, and the performance of the dispersant is determined by the balance of these two parts.
  • both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important.
  • the tetracarboxylic acid anhydride (b) used in the present invention can react with a hydroxyl group to form an ester bond and leave a pendant carboxyl group on the resulting polyester main chain. Polio-Ruich compound with two hydroxyl groups in one end region (one end region)
  • reaction process formulas of tetracarboxylic anhydride and polyol compound are shown in the following reaction process formulas (4) and (6).
  • n is the number of repeating units.
  • the product of this reaction process will have 2 or 3 carboxyl groups in the X part of the structural formula.
  • the plurality of carboxyl groups are effective as pigment adsorption sites.
  • polyester dispersant of the present invention it is bonded to the core portion X.
  • carboxyl group out of the scope of the present invention
  • the terminal region of A is, for example, a linear or branched trivalent aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms) (for vinyl polymer portion B). And will be described later).
  • the two hydroxyl groups contained in this one terminal region may be bonded to the same carbon atom or may be bonded to different carbon atoms.
  • a preferable form of the core part X is a reaction residue after reacting with a tetracarboxylic acid anhydride polyolide compound represented by the following general formula (1) or general formula (2).
  • polyester dispersant of the present invention by reacting a vinyl polymer (a) having two hydroxyl groups in one terminal region with a tetracarboxylic acid anhydride (b), the above reaction process formula (4) A plurality of carboxyl group moieties bonded to the core part in the product function as a pigment adsorbing part, and a vinyl polymer part B functions as a solvent affinity part.
  • the compound (al) having two hydroxyl groups and one thiol group is reacted with the tetracarboxylic acid anhydride (b) to contain the vinyl polymer portion B.
  • the compounds (a2) to (a5) are first produced, followed by radical polymerization using the remaining thiol groups of the compounds (a2) to (a5) as chain transfer agents, so that By introducing B, it is possible to obtain a resin having a similar structure.
  • a plurality of carboxyl group moieties bonded to the core portion X in the product are formed in the first steps B5 to B8 to form a pigment adsorbing portion, and then the butyl introduced in the subsequent steps A5 to A8.
  • the polymer part B can function as a solvent affinity part.
  • Step B5 and Step A5 when reacting a compound having two hydroxyl groups and one thiol group (al) with tetracarboxylic anhydride (b) and then introducing an ethylenically unsaturated monomer]:
  • Step B6 and Step A6 [compound having two hydroxyl groups and one thiol group (al), tetracarboxylic anhydride (b) and no thiol group! /, Polyol compound (c,), Subsequently, when ethylenically unsaturated monomer is introduced]:
  • Step B7 and Step A7 [compounds having two hydroxyl groups and one thiol group (al), tetracarboxylic anhydride (b) and tricarboxylic anhydride (d) are reacted, followed by ethylenically unsaturated monoester When introducing a polymer]:
  • Step B8 and Step A8 Compound having two hydroxyl groups and one thiol group (al), tetracarboxylic acid anhydride (b), polyol compound (c ') and tricarboxylic acid anhydride (without thiol group) Reaction with d) followed by introduction of ethylenically unsaturated monomer]: Reaction process formula (10)
  • a plurality of pendant carboxyl groups can be formed to function as a pigment adsorbing portion, and further, radical polymerization can be performed as a chain transfer agent using the remaining thiol groups. It is possible to make the combined part function as a solvent affinity part.
  • the “bule polymer portion formed by radical polymerization of an ethylenically unsaturated monomer” is derived from a tetracarboxylic acid anhydride (b) or a tricarboxylic acid anhydride (d).
  • a plurality of vinyl polymer parts B are usually contained in one molecule constituting the polyester dispersant of the present invention.
  • This part is the affinity part for the solvent that is the dispersion medium.
  • the weight average molecular weight of the vinyl polymer part is less than 1000, the effect of steric repulsion by the solvent affinity part is reduced, and it becomes difficult to prevent the aggregation of the pigment, and the dispersion stability may be insufficient.
  • it exceeds 10000 the absolute amount of the solvent compatible portion increases, and the dispersibility effect itself may decrease. In addition, the viscosity of the dispersion may increase.
  • the vinyl polymer (a) can be easily adjusted in molecular weight to the above range, and has good affinity for the solvent.
  • the glass transition temperature of the bull polymer portion B formed by radical polymerization of an ethylenically unsaturated monomer is preferably 50 to 70 ° C in view of higher dispersibility of the pigment. 50 ⁇ 40 ° C is more preferred.
  • Tg glass transition temperature
  • a skeleton derived from a compound having two hydroxyl groups and one thiol group in the molecule is also present in the vinyl polymer (a), but is excluded from the following calculation for calculating the glass transition temperature.
  • Tg is the glass transition temperature of the entire Bule polymer part B
  • W1 to Wn are the weight fractions of the monomers used
  • Tgl to Tgn are the glass weights of each homopolymer.
  • the Tg of the main homopolymer used for calculation is shown below.
  • Methyl metatalylate 105 ° C (378K)
  • the glass of the buule polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer synthesized using 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate.
  • the transition temperature is 36.1 ° C.
  • a vinyl polymer having two hydroxyl groups in one terminal region is obtained by laminating an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule of the present invention.
  • the following method can also be used.
  • the method power S for radical polymerization of ethylenically unsaturated monomers in the presence of a compound having two hydroxyl groups and one thiol group is most preferable.
  • a vinyl polymer (a) having two hydroxyl groups at one end region is obtained by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. Can be obtained at
  • Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1 mercapto 1,1 methanediol, 1 mercapto 1,1 ethanediol, 3 mercapto 1,2-propanediol (thiol).
  • a compound having two hydroxyl groups and one thiol group in the molecule can be obtained by mixing and heating.
  • the compound having two hydroxyl groups and one thiol group is based on 100 parts by weight of ethylenically unsaturated monomer. It is preferable to perform bulk polymerization or solution polymerization using 1 to 30 parts by weight, more preferably 3 to 12 parts by weight, still more preferably 4 to 12 parts by weight, and particularly preferably 5 to 9 parts by weight.
  • the reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C.
  • a polymerization initiator in the polymerization, 0.005 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer.
  • a polymerization initiator azo compounds and organic peroxides can be used.
  • azo compounds examples include 2,2'-azobisisobutyryl-tolyl, 2,2, -azobis (2-methylbutybutoxy-tolyl), 1,1, -azobis (cyclohexane 1-carbo-tolyl) ), 2, 2, -azobis (2,4 dimethylvale-tolyl), 2, 2, monoazobis (2,4 dimethyl-4-methoxyvaleronitryl), dimethyl 2,2'-azobis (2 methylpropio) Nate), 4, 4, azobis (4 cyanoberic acid), 2, 2, azobis (2-hydroxymethylpropio-tolyl), 2, 2, azobis [2- (2-imidazoline-2-yl) Propane] and the like.
  • organic peroxides examples include benzoyl peroxide, t-butyl perbenzoate, tamen hydroperoxide, diisopropyl peroxydicarbonate, di-propinoliver oxydicarbonate, di (2-ethoxyethyl) per Examples include oxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropio-peroxide, dicetylba 1-year-old oxide. These polymerization initiators can be used alone or in combination of two or more.
  • a polymerization solvent ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, etc. are used. It is not limited. These polymerization solvents may be used as a mixture of two or more.
  • Examples of the ethylenically unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( (Meth) Atalylate, Isobutyl (Meth) Atalylate, t-Butyl (Meth) Atalylate, 2—Ethylhexyl (Meth) Atalylate, Cyclohexyl (Meth) Atalylate, Stearyl (Meth) Atalylate, Lauryl ( (Meth) Atarylate, Tetrahydrofurfuryl (Meth) Atarylate, Isobol (Meth) Atarylate, Phenol (Meth) Atarylate, Benzyl (Meth) Atrelyle , Oxetane (meth) acrylate, etc., methoxypolypropylene glycol (meth) acryl
  • Examples of monomers that can be used in combination with the above acrylic monomers include styrenes such as styrene and a-methylstyrene, vinyl ethers such as ethyl vinyl ether, n -propyl vinyl ether, isopropyl vinyl ether, n -butyl vinyl ether, and isobutyl vinyl ether. And fatty acid burs such as vinyl acetate and vinyl propionate.
  • a carboxyl group-containing ethylenically unsaturated monomer may be used in combination.
  • the carboxyl group-containing ethylenically unsaturated monomer one or more kinds can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.
  • benzyl (meth) acrylate is used in an amount of 20 to 70% by weight based on the whole monomer. It is preferably 30 to 60% by weight. If it is less than 20% by weight, the solvent affinity becomes low, and sufficient steric repulsion effect cannot be obtained, and the pigment dispersibility may decrease. If it exceeds 70% by weight, the benzyl part and the pigment interact with each other. As a result, the pigment dispersibility may decrease.
  • a monomer represented by the following general formula (3) is preferably 20 to 70% by weight, more preferably 20 to 100% by weight, based on the whole monomer.
  • the solvent affinity is improved and the pigment dispersibility is improved.
  • R represents a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the polyester dispersant of the present invention comprises a hydroxyl group of a vinyl polymer (a) having two hydroxyl groups in one end region obtained in steps A1 to A4, and an acid anhydride group of a tetracarboxylic acid anhydride (b). It is obtained by reacting (Steps Bl to B4).
  • the tetracarboxylic acid anhydride (b) used in the present invention includes 1, 2, 3, 4 butanetetracarboxylic acid anhydride, 1, 2, 3, 4 cyclobutanetetracarboxylic acid anhydride, 1, 3 Dimethyl 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentane tetracarboxylic anhydride, 2,3,5 tricarboxycyclopentylacetic anhydride, 3,5,6 tricarboxy Norbornane-2-acetic anhydride, 2, 3, 4, 5-tetrahydrofuran tetracarboxylic anhydride, 5- (2,5 dioxotetrahydrofural) -3-methyl-3-cyclohexene 1,2-dicarboxylic anhydride , Bicyclo [2, 2, 2] -Otato 7-en 2, 2, 5, 5, 6-tetracarboxylic anhydride and other aliphatic tetracarbox
  • the tetracarboxylic acid anhydride used in the present invention is not limited to the compound exemplified above, and any structure having two forceful rubonic acid anhydride groups can be used! Powerful! These can be used alone or in combination.
  • what is preferably used in the present invention is an aromatic tetracarboxylic acid anhydride from the viewpoint of reducing the viscosity of the pigment dispersion, more preferably a tetracarboxylic acid anhydride having two or more aromatic rings. is there.
  • a compound having one carboxylic anhydride group in the molecule or a compound having three or more can be used in combination.
  • tricarboxylic acid anhydrides include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.
  • Examples of the aliphatic tricarboxylic acid anhydride include, for example, 3 carboxymethyldaltaric acid anhydrous, 1, 2, 4 butanetricarboxylic acid 1, 2 anhydride, cis propene-1, 2, 3 tricarboxylic acid 1 , 2 anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride and the like.
  • aromatic tricarboxylic acid for example, benzenetricarboxylic acid anhydride (1, 2, 3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1, 2, 4 benzenetricarboxylic acid anhydride], etc.), Naphthalene tricarboxylic acid anhydride (1, 2, 4 naphthalene tricarboxylic acid anhydride, 1, 4, 5 naphthalene tricarboxylic acid anhydride, 2, 3, 6 naphthalene tricarboxylic acid anhydride, 1, 2, 8 naphthalene tricarboxylic acid anhydride 3, 4, 4 'monobenzophenone tricarboxylic acid anhydride, 3, 4, 4, biphenyl ether tricarboxylic acid anhydride, 3, 4, 4, biphenyl tricarboxylic acid anhydride, 2, 3 1, 2, -biphenyl tricarboxylic acid anhydride, 3, 4, 4, 4, 4, 4, 4, 4, 4,
  • a polyol compound (c) other than the vinyl polymer (a) in an arbitrary ratio in the step B2 and the step B4.
  • a polyol compound (c) other than the vinyl polymer (a) it becomes easy to adjust the density of the carboxylic acid group and the proportion of the solvent-soluble portion.
  • polyol compound (c) other than the vinyl polymer (a) used in the present invention, a known one can be used. For example, it has 2 to 4 hydroxyl groups in one molecule. Polio-Iloui compound can be used. Among them, there are those belonging to the following groups (1) to (7) if only typical ones are illustrated.
  • Polyester polyols obtained by co-condensation of one or more of the above-mentioned various polyhydric alcohols with polyvalent carboxylic acids which are polyvalent carboxylic acids such as succinic acid, adipic acid, sebacin Acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1, 2, 5 monohexanetricarboxylic acid, 1,4-cyclohexanehical
  • boric acid 1, 2, 4 benzene tricarboxylic acid, 1, 2, 5 benzene tricarboxylic acid, 1, 2, 4 cyclohexatricarboxylic acid or 2, 5, 7 naphthalene tricarboxylic acid Resulting polyols;
  • polyester polyols obtained by polycondensation reaction of the various polyhydric alcohols, polycarboxylic acids and various latatones;
  • examples thereof include silicon resin.
  • the polyol compound (c) other than the vinyl polymer (a) optionally added as shown in (1) to (7) may be used alone or in combination of two or more.
  • the weight average molecular weight is 40 to: LOOOO force S, preferably 100 to 2000, and more preferably 100 to 1000.
  • the catalyst used for the production of the polyester dispersant of the present invention a known catalyst can be used.
  • the catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] — 7-undecene, 1,5-diazabicyclo [4.3.0] 1-5-nonene, and the like.
  • the polyester dispersant of the present invention can be produced using only the raw materials listed above, but it is preferable to use a solvent that avoids problems such as high viscosity and non-uniform reaction. preferable.
  • a solvent that avoids problems such as high viscosity and non-uniform reaction.
  • known solvents can be used. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butylacetate, toluene, xylene, and acetonitrile.
  • the solvent used for the reaction can be removed by distillation or other operation after the completion of the reaction, or used as part of the product.
  • the polyester dispersant of the present invention comprises a vinyl polymer (a) having two hydroxyl groups in one terminal region, a tetracarboxylic acid anhydride (b), and an optional addition "other than the vinyl polymer (a). It is obtained by reacting the polyol compound (c) ”.
  • the remaining acid anhydride group may be hydrolyzed with a necessary amount of water and used. If it is less than 0.3, the acid anhydride residue as the pigment adsorbing portion may be decreased, and the acid value of the resin may be decreased. On the other hand, if it exceeds 1.2, acid anhydride groups remain in the polyester, which may cause problems in storage stability of the resin. In addition, the amount of water necessary to hydrolyze the remaining acid anhydride groups may increase, resulting in poor solvent solubility.
  • the polyester dispersant of the present invention is a polyol polymer other than (a), a vinyl polymer (a) having two hydroxyl groups in one terminal region, a tetracarboxylic acid anhydride (b), and an optional addition (a). It can be obtained by reacting compound (c) and tricarboxylic anhydride (d).
  • the reaction temperature is 50 ° C to 180 ° C, preferably 80 ° C to 140 ° C.
  • the reaction rate is slow.
  • the reaction temperature is 180 ° C or higher, the carboxyl group undergoes esterification reaction, which may cause a decrease in acid value or gelling. It is ideal to stop the reaction until there is no absorption of the acid anhydride by infrared absorption. After confirming that 95% or more of the acid anhydride is half-esterified by acid value measurement Stop the reaction.
  • the weight average molecular weight of the obtained polyester dispersant is preferably 2000 to 35000, more preferably ⁇ or 4000 to 25000, more preferably ⁇ or 6000 to 20000, particularly preferably ⁇ ⁇ is between 7000 and 15000. If the weight average molecular weight is less than 2000, the stability of the pigment composition may decrease. Thickening may occur.
  • the acid value of the obtained polyester dispersant is preferably 5 to 200. More preferably, it is 10-150, More preferably, it is 15-: LOO, Especially preferably, it is 20-80. When the acid value is less than 5, the pigment adsorbing ability may be lowered and the pigment dispersibility may be problematic. When the acid value exceeds 200, the interaction between the rosils may be increased and the viscosity of the pigment dispersion composition may be increased. .
  • a compound (al) having two hydroxyl groups and one thiol group in the molecule a tetracarboxylic acid anhydride (b), a polyol compound (c ′) having no thiol group, and Steps B5 to B8 for producing compound (a2) by reacting with tricarboxylic acid anhydride (d), and thiol group of compound (a2) remaining in the presence of compound (a2)!
  • a dispersant having the same structure can be obtained by the steps A5 to A8 in which radical polymerization is performed as a chain transfer agent.
  • a compound having two hydroxyl groups and one thiol group in the molecule (al), a tetracarboxylic acid anhydride (b), and optionally a polyurich compound (c ') having no thiol group
  • Steps B5 to B8 in which compounds (a2) to (a5) are produced by further reacting with a tricarboxylic acid anhydride (d) in some cases will be described.
  • These compounds (a2) to (a5) are compounds other than the compound (al) having two hydroxyl groups and one thiol group in the molecule (al), tetracarboxylic acid anhydride (b), and optionally added (a).
  • the polyol compound (c) and the optionally added tricarboxylic acid anhydride (d) can be obtained in the same manner as in Steps A1 to A4. It has an acid anhydride group in tetracarboxylic acid anhydride (b) and triforce rubonic acid anhydride (d), a compound having two hydroxyl groups and one thiol group in the molecule (al), and a thiol group.
  • LOO parts by weight of an ethylenically unsaturated monomer is used. It is preferable to perform bulk polymerization or solution polymerization. More preferably, it is 8-25 weight part, More preferably, it is 10-20 weight part.
  • the reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C.
  • the ethylenically unsaturated monomer having a hydroxyl group used in the above production method may be any monomer having a hydroxyl group and having an ethylenically unsaturated double bond.
  • (meth) acrylate monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (Or 3 or 4) -hydroxybutyl (meth) acrylate and hydroxyalkyl (meth) acrylate, such as cyclohexane dimethanol mono (meth) acrylate, or
  • (meth) acrylamide monomers having a hydroxyl group such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) ) N- (hydroxyalkyl) (meth) acrylamide such as
  • the ethylenically unsaturated monomer obtained can also be used as the ethylenically unsaturated monomer (h) having a hydroxyl group in the production method used in the present invention.
  • the alkylene oxide to be added ethylene oxide, propylene oxide, 1, 2 1, 4 2, 3-— or 1,3-butylene oxide and a combination system of two or more of these are used.
  • the bond type may be random and either Z or block.
  • the added ratataton include ⁇ -noratolatataton, ⁇ -force prolatatatone, ⁇ -one-proteatone substituted with an alkyl group having 16 carbon atoms, and a combination of two or more of these.
  • An alkylene oxide and a rataton may be added.
  • pigments that can be dispersed with the dispersant of the present invention include various pigments used in inks and the like.
  • Such pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone pigments, anthracirimide pigments.
  • titanium dioxide, iron oxide, metal oxides such as antimony pentoxide, zinc oxide, silica, cadmium sulfate, calcium carbonate, barium carbonate, barium sulfate, clay, talc, chrome, Inorganic pigments such as carbon black can also be used. Carbon black Any carbon black such as neutral, acidic, and basic can be used.
  • the pigment composition of the present invention is not limited to the above-described pigment, and for example, solid fine particles containing metal fine particles such as gold, silver, copper, platinum, iron, cobalt, nickel, and Z or alloys thereof can be used. .
  • the pigment composition using the dispersant of the present invention further has a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an attaridone derivative having a basic group, and a basic group.
  • Group power of triazine derivatives It is preferable to include at least one basic derivative selected.
  • the pigment derivative is a product obtained by introducing a specific substituent into the organic pigment residue described in the color index.
  • a pigment derivative having a basic group is used.
  • the basic derivative that can be used in the pigment composition of the present invention has a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an attaridone derivative having a basic group, and a basic group. It is selected from the group of triazine derivatives.
  • the basic group of the basic derivative that can be used in the pigment composition of the present invention is a group force having a basic force represented by the following general formulas (6), (7), (8), and (9). At least one group selected.
  • x and xx 2 are SO CO—, CH NHCOCH-CH one or direct bond
  • n an integer of 1 to 10.
  • R 2 each independently represents an optionally substituted alkyl group, alkenyl group, phenyl group, or a heterocyclic ring formed by combining R 1 and R 2 .
  • the heterocycle may contain further nitrogen, oxygen or sulfur atoms.
  • the alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.
  • R 3 represents an alkyl group, a alkenyl group or a phenyl group which may be substituted.
  • Alkyl and alkenyl groups preferably have 1 to 10 carbon atoms! /.
  • R 4 , R 5 , R 6 , and R 7 each independently represents a hydrogen atom, an alkyl group, a alkenyl group, or a fuller group that may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.
  • Y represents NR 8 —Z—NR 9 or a direct bond.
  • R 8 and R 9 each independently represents a hydrogen atom, an optionally substituted alkyl group, an alcohol group, or a phenol group.
  • the alkyl group and the alkyl group preferably have 1 to 5 carbon atoms.
  • Z represents an optionally substituted alkylene group, alkylene group, or fullerene group.
  • Alkyl and alkenyl groups preferably have 1 to 8 carbon atoms! /.
  • P represents a substituent represented by the formula (10) or a substituent represented by the formula (11).
  • Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (10) or a substituent represented by the formula (11).
  • alkyl group in I ⁇ to R 9 in the general formula a methyl group, Echiru group, propyl group, butyl group, pentyl group, etc. hexyl group to.
  • alkenyl group include a vinyl group and a probe group.
  • Examples of the alkylene group for Z in the above general formula include a methylene group, an ethylene group, a propylene group, and a butylene group.
  • Examples of the alkellene group include a vinylene group and a p-bene group.
  • Examples of the alkoxyl group for Q in the above general formula include a methoxy group, an ethoxy group, a alkoxy group, and a butoxy group.
  • Examples of the functional group which may be substituted include a halogen group, a cyano group, an alkoxyl group, an amino group, a hydroxyl group, a nitro group, and an epoxy group.
  • Examples of the amine component used to form the substituents represented by the formulas (6) to (9) include dimethylamine, jetylamine, N, N-ethylisopropylamine, N, N- Tylpropylamine, N, N-methylbutyramine, N, N-methylisobutyramine, N, N butylethylamine, N, N-tert butylethylamine, diisopropylamine, dipropylamine, N, N-sec butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N isobutyl-sec butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N—Methyloctadecylamine, didecylamine, diarylamine, N, N ethyl-1,
  • the organic dye constituting the pigment derivative having a basic group includes, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine , Flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone and other anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes , Quinophthalone dyes, selenium dyes, metal complex dyes, and the like.
  • diketopyrrolopyrrole dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine , Flavantron, anthanthrone
  • an anthraquinone derivative having a basic group and an attaridone derivative having a basic group are alkyl groups such as a methyl group and an ethyl group, an amino group, a nitro group, a hydroxyl group, or an alkoxy group such as a methoxy group and an ethoxy group.
  • substituents such as halogens, such as chlorine.
  • triazines constituting triazine derivatives having a basic group include alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, jetramino group, dibutylamino group, etc.) ), Nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group) And may be substituted with a halogen, etc.), and a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.), etc. It is 1, 3, 5 triazine which may have the following substituents.
  • the pigment derivative, anthraquinone derivative and attaridone derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the general formulas (12) to (15) into an organic dye, anthraquinone or attaridone, it reacts with the above-described substituents to obtain a substituent represented by the general formulas (6) to (9).
  • Group-forming amine components such as N, N-dimethylaminopropylamine, N-methylbiperazine, jetylamine or 4 [4 hydroxy-6- [3- (dibutylamino) propylamino]] 1, 3, 5 triazine-2 It can be obtained by reacting —ylamino] -lin or the like.
  • the organic dye is a azo dye
  • the substituents represented by the general formulas (6) to (9) are introduced into the diazo component or the coupling component, and then the coupling reaction is performed. It is also possible to produce an azo pigment derivative.
  • the triazine derivative having a basic group can be synthesized by various synthetic routes.
  • an amine component starting from cyanuric chloride and forming a substituent represented by formula (6) to formula (9) on at least one chlorine of the salt cyanuric, such as N, N-dimethylaminopropylamine or It can be obtained by reacting N-methylbiperazine or the like and then reacting the remaining chlorine of the cyanuric chloride with various amines or alcohols.
  • the amount of the basic derivative is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, most preferably 100 parts by weight of the pigment. 5 to 25 parts by weight.
  • the blending amount of the polyester dispersant is preferably 1 to 200 parts by weight, more preferably 2 to 175 parts by weight, and most preferably 5 to 150 parts by weight with respect to 100 parts by weight of the pigment.
  • the pigment composition using the polyester dispersant of the present invention may be mixed with various solvents, resin, additives, etc. as necessary to obtain a horizontal sand mill, a vertical sand mill, a Yura-la type bead mill, an attritor, etc.
  • the pigment dispersion obtained by dispersing the pigment composition in the varnish can be prepared.
  • all components may be mixed to disperse the force, but initially only the pigment and the basic derivative, or the basic derivative Only with polyester dispersant or face It is also possible to disperse the material, the basic derivative, and the polyester dispersant alone, and then add another component to perform dispersion again.
  • a kneader mixer such as an adader, 3-roll mill, etc.
  • any dispersing machine or mixer such as a speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic dispersing machine can be used to produce the pigment dispersion.
  • Examples of various solvents that can be used in the pigment dispersion include organic solvents and water.
  • an active energy ray-curable liquid monomer or liquid oligomer may be used as a medium instead of a solvent.
  • Examples of the resin that can be used in the pigment dispersion of the present invention include petroleum resin, power zein, shellac, rosin-modified maleic acid resin, rosin-modified phenol resin, nitrocellulose, cellulose acetate.
  • polyester dispersant of the present invention can be used as a binder resin for a pigment dispersion.
  • the pigment dispersion of the present invention is used for non-aqueous, aqueous or solvent-free paints, gravure ink, offset ink, ink jet ink, color filter ink, digital paper ink, plastic coloring, etc. it can.
  • a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 200 parts of n-butyl methacrylate and replaced with nitrogen gas.
  • the inside of the reaction vessel was heated to 80 ° C., and 12 parts of 3-mercapto 1,2-propanediol was added to react for 12 hours. Solid content measurement confirmed that 95% had reacted.
  • 12 parts of pyromellitic anhydride, 224 parts of cyclohexanone and 1,8 diazabicyclo [5.4.0] —7 undecene 0.40 parts as catalyst were added and reacted at 120 ° C for 7 hours. I let you.
  • a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate and replaced with nitrogen gas.
  • the reaction vessel was heated to 80 ° C, and a solution of 0.1 part of 2,2'-azobisisobutyl-tolyl was added to 12-liter of 3-menorecapto 1,2 pronogen, Reacted for hours. It was confirmed that 95% had reacted by solid content measurement.
  • n-butyl methacrylate 100 parts of relate and 100 parts of benzylmetatalylate were charged and replaced with nitrogen gas.
  • the reaction vessel was heated to 80 ° C, and a solution of 0.1 part of 2,2'-azobisisobutyl-tolyl was added to 12-liter of 3-menorecapto 1,2 pronogen, Reacted for hours. It was confirmed that 95% had reacted by solid content measurement.
  • 37 parts of BPDA, 255 parts of cyclohexanone, and 1.40 diazabicyclo- [5.4.0] -7.40 parts as a catalyst were added and reacted at 120 ° C for 7 hours.
  • a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 100 parts of n-butyl methacrylate and 100 parts of n-butyl acrylate and replaced with nitrogen gas.
  • the reaction vessel was heated to 80 ° C, and a solution of 0.1 part of 2,2'-azobisisobutyl-tolyl was added to 12-liter of 3-menorecapto 1,2 pronogen, Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 4 parts of PMA, 26 parts of trimellitic anhydride, 242 parts of cyclohexanone, 1,8 diazabicyclo [5. 4. 0] — 7 undenecene as catalyst.
  • Example 29 and 30 Synthesis was carried out in the same manner as in Example 28 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
  • a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 100 parts of n-butyl methacrylate and 100 parts of n-butyl acrylate and replaced with nitrogen gas.
  • the reaction vessel was heated to 80 ° C, and a solution of 0.1 part of 2,2'-azobisisobutyl-tolyl was added to 12-liter of 3-menorecapto 1,2 pronogen, Reacted for hours. It was confirmed that 95% had reacted by solid content measurement.
  • a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 12 parts of 3-mercapto-1,2-propanediol, 19 parts of PMA, and 31 parts of cyclohexanone and replaced with nitrogen gas.
  • the reaction vessel was heated to 100 ° C and reacted for 7 hours. After measuring the acid value to confirm that 98% or more of the acid anhydride was half-esterified, the temperature in the system was cooled to 70 ° C, and 100 parts of n-butyl metatalylate and benzyl metataliate were cooled.
  • a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 12 parts of 3-mercapto-1,2-propanediol, 37 parts of PMA, 11 parts of neopentyl glycol, and 60 parts of cyclohexanone. Replaced.
  • the inside of the reaction vessel was heated to 100 ° C and reacted for 7 hours.
  • the acid value was measured to confirm that 98% or more of the acid anhydride had been half-esterified, and then the temperature inside the system was cooled to 70 ° C., and 80 parts of methyl metatalylate and 80 parts of butyl acrylate.
  • a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 12 parts of 3-mercapto-1,2-propanediol, 12 parts of PMA, 11 parts of trimellitic anhydride, and 35 parts of cyclohexanone. Replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C and reacted for 7 hours.
  • the temperature inside the system was cooled to 70 ° C., and 80 parts of methyl metatalylate and butyl acrylate 80 Part, 20 parts of hydroxyethinoremethalate, 20 parts of 2-hydroxypropenoremethalate, 200 parts of cyclohexanone solution containing 0.5 part of 2,2'-azobisisobutyric-tolyl added. And reacted for 10 hours.
  • the solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed.
  • a polyester dispersant having an acid value of 53 and a weight average molecular weight of 10,000 was obtained.
  • Example 47 In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 3-mercapto-1,2-propanediol 12 parts, PMA 15 parts, neopentyl glycol 11 parts, trimellitic anhydride 14 parts, cyclohexanone 52 parts were charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C and reacted for 7 hours. After the acid value measurement confirmed that 98% or more of the acid anhydride had been condensed, the temperature inside the system was cooled to 70 ° C., and 80 parts of methyl methacrylate and 100 parts of butinorea tallylate were added.
  • Dispersant 9 n-Butyl methacrylate 200 100 100 90 100 100 100 100 100 100 Benzyl methacrylate 100 100 100 100 100 100 100 100 100 100 100 100 Lauryl methacrylate
  • Methyl methacrylate 140 unsaturated monomer
  • Solvents Open mouth hexanone 232 232 266 220 261 356 294 462 Glass transition temperature of vinyl polymer part (t) 36 36 6 14 14 1 36 17 Acid number 42 43 77 29 73 54 49 41 w 9100 11000 8200 18500 13000 22000 15000 23000 6]
  • butyl methacrylate 90 Benzyl methacrylate 100 100 Lauryl methacrylate
  • PMA pyromellitic anhydride (manufactured by Daicel Engineering Co., Ltd.)
  • BPDA 3, 3 ', 4, 4'-biphenyltetracarboxylic acid anhydride (Mitsubishi Chemical Co., Ltd.)
  • BPAF 9, 9 Bis (3, 4-dicarboxyphenol) fluorene dianhydride (Manufactured by JFE Chemical)
  • DMBA dimethylol butanoic acid (manufactured by Perstorp)
  • a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel was 19.8 parts of silene, 2.1 parts of octanol, 1 part of prolatatone epsilon 77.9 parts of tetrabutyl titanate 0.16 parts, heated to 150-160 ° C and reacted for 5 hours under nitrogen gas atmosphere After confirming that the caro heat residue was 78% or more, it was cooled to obtain a polyester monool. 31.86 parts of the synthesized polyester monool and 0.98 parts of trimellitic anhydride were charged and reacted at 150 to 160 ° C. in a nitrogen atmosphere.
  • YED122 (trade name: alkylphenol monoglycidyl ether, epoxy equivalent 250, manufactured by Japan Epoxy Resin Co., Ltd.), 2. 55 parts when succinic acid value becomes 22.7 or less, react at the same temperature It was.
  • succinic acid value is 1.1 or less, add 1.96 parts of trimellitic anhydride and react at the same temperature.
  • YED122 5 Charge 1 part and react at the same temperature.
  • succinic acid number drops to 1.8 or less, add 3.92 parts trimellitic anhydride and react at the same temperature.
  • the temperature became 60.1 or less the mixture was cooled and 53.6 parts of xylene was added to terminate the reaction.
  • a polyester dispersant having an acid value of 58.9 and a weight average molecular weight of 11 000 was obtained.
  • the polyester dispersant prepared in Comparative Example 4 corresponds to the polyester dispersant described in Patent Document 3.
  • polyester dispersant prepared in Comparative Example 5 corresponds to the polyester dispersant described in Patent Document 4.
  • CuPc represents a copper phthalocyanine residue.
  • CuPc represents a copper phthalocyanine residue.
  • a pigment derivative (Y4) having a basic group was obtained in the same manner as in Production Example 1 using diphenyl diketopyrrolopyrrole as the dye component and N-aminopropylmorpholine as the amine component.
  • the following pigment derivatives, anthraquinone derivatives, attaridone derivatives or triazine derivatives were obtained by the same method as in Production Examples 1 to 4 of the pigment derivative (Y) having the basic group.
  • the pigment As shown in Table 7, the pigment (CI Pigment Blue 15: 3), the polyester dispersant synthesized in Examples 1 to 9, the pigment derivative (Y1) having a basic group synthesized in Production Example 1, and A pigment composition was prepared by blending cyclohexanone and dispersing 100 parts of 2 mm diameter Zirco Your beads in a paint paint conditioner for 3 hours.
  • a pigment composition was prepared in the same manner as in Examples 51 to 59 except that the carboxyl group-containing polyester synthesized in Comparative Examples 1 and 2 was used.
  • the viscosity of the obtained composition was measured with a B-type viscometer (25 ° C, rotation speed lOOrpm), and the haze was measured with a haze meter (light transmittance 20%).
  • the performance of the dispersion was evaluated based on the initial viscosity and haze (the lower the viscosity, the better the haze, the lower the haze, the better).
  • Initial viscosity and haze are measured after standing at room temperature for 1 day after dispersion. The temperature was measured after leaving at 40 ° C for one week. The results are shown in Table 7.
  • the pigment compositions of Examples 51 to 59 using the polyester dispersant of the present invention have a low initial viscosity and are almost free from an increase in viscosity over time. It shows stability. Furthermore, the haze is also low.
  • the pigment compositions of Comparative Examples 6 and 7 were found to have problems with high dispersibility in both viscosity and haze.
  • Pigment Blue 15 9 parts as pigment, 1 part of pigment derivative (Y1) with basic group, 1 part of dispersant 3 (solid), alkyd resin (Talkid 133-60 from Hitachi Chemical Co., Ltd.) 29 parts and 60 parts of cyclohexanone were charged into a mayonnaise bottle, 250 parts of 0.5 mm diameter Zircoyu beads were charged as a dispersion medium, and this dispersion was performed with a paint shaker to obtain a facial dispersion.
  • the viscosity of the obtained pigment dispersion was measured with a B-type viscometer, and the performance of the dispersion was evaluated by viscosity and TI value (viscosity at 6 rpm, viscosity at Z60 rpm).
  • the viscosity at 6 rpm was 1 lOmPa ⁇ s
  • the viscosity at 60 rpm was lOOmPa's
  • the TI value was 1.11.
  • the obtained pigment dispersion was stored in a thermostat at 50 ° C. for 1 week and accelerated with time, and the change in viscosity of the pigment dispersion before and after aging was measured.
  • the viscosity at 6 rpm was 105 mPa's and the rate of change was 5%. After the pigment dispersion was coated on glass and the solvent was removed, the weight loss% before and after heating at 200 ° C for 1 hour was 8.5%.
  • Example 60 In the same manner as in Example 60, the pigments were mixed at the blending ratios (weight ratios) shown in Tables 8 and 9, respectively. A dispersion was obtained. The evaluation was made in the same manner as in Example 60 (the lower the viscosity, the better, the closer the TI value is to 1, the better).
  • Viscosity stability is ⁇ or 10 if the rate of change in viscosity before and after storage at 50 ° C for 1 week is within ⁇ 10%.
  • the coating weight loss is 200 ° C after removing the coating film and solvent on the glass.
  • Example 60 Pigment Blue 15: 3 9 Yl 1 Dispersant 3 1 29 60
  • Example 61 Pigment Blue 15: 3 9 Yl 1 Dispersant 7 1.5 28.5 60
  • Example 62 Pigment Blue 15: 3 9 Yl 1 Dispersant 8 1 29 60
  • Example 63 Pigment Blue 15: 3 9 Yl 1 Dispersant 10 1 29 60
  • Example 64 Pigment Blue 15: 3 9 Yl 1 Dispersant 13 1 29 60
  • Example 65 Pigment Blue 15: 3 9 Yl 1 Dispersant 14 1 29 60
  • Example 66 Pigment Blue 15: 3 9 Yl 1 Dispersant 15 1 29 60
  • Example 67 Pigment Blue 15: 3 9 Yl 1 Dispersant 16 1 29 60
  • Example 68 Pigment Blue 15: 3 9 Yl 1 Dispersant 17 1 29 60
  • Example 69 Pigment Blue 15: 3 9 Yl 1 Dispersant 21 1 29 60
  • Example 70 Pigment Blue 15: 3 9 Yl 1 Dispersant 23 1 29 60
  • Example 69 Pig
  • Example 90 Pigment Red 57 1 9 Y10 1 Dispersant 23 2 28 60
  • Example 91 Pigment Red 57 1 9 Y10 1 Dispersant 24 2 28 60
  • Example 92 Pigment Red 57 1 9 Y10 1 Dispersant 25 2 28 60
  • Example 93 Pigment Red 57 1 9 Y10 1 Dispersant 26 2 28 60
  • Example 94 Pigment Red 57 1 9 Y10 1 Dispersant 27 2 28 60
  • Example 95 Pigment Red 57 1 9 Y10 1 Dispersant 28 2 28 60
  • Example 96 Pigment Red 57 1 9 Y10 1 Dispersant 29 2 28 60
  • Example 97 Pigment Red 57 1 9 Y10 1 Dispersant 30 2 28 60
  • Example 98 Pigment Red 57 1 9 Y10 1 Dispersant 31 2 28 60
  • Example 99 Pigment Green 36 8 Y2 2 Dispersant 36 2 28 60
  • Example 100 Pigment Green 36 8 Y2 2 Dispersant 37 2 28 60
  • Example 101 Pigment Green 36
  • Example 60 110 100 1.10 ⁇ ⁇ Example 61 100 100 1.00 ⁇ 0
  • Example 62 100 95 1.05 ⁇ ⁇
  • Example 63 95 90 1.06 ⁇ ⁇
  • Example 64 85 85 1.00 ⁇ 0
  • Example 65 130 125 1.04 ⁇ ⁇
  • Example 66 120 115 1.04 ⁇ ⁇
  • Example 67 180 150 1.20 ⁇ ⁇
  • Example 68 200 150 1.33 ⁇ ⁇
  • Example 69 150 130 1.15 ⁇ 0
  • Example 70 160 145 1.10 ⁇ ⁇ Example 71 200 180 1.11 ⁇ 0
  • Example 72 220 210 1.05 0 ⁇
  • Example 73 160 150 1.07 ⁇ ⁇
  • Example 74 300 260 1.15 ⁇ ⁇
  • Example 75 400 320 1.25 ⁇ ⁇
  • Example 76 350 330 1.06 0 ⁇
  • Example 77 310 300 1.03 ⁇ 0
  • Example 78 140 140 1.00 ⁇ 0
  • Example 79 160 150 1.07
  • Example 90 300 270 1.11 0 ⁇
  • Example 100 330 300 1.10 ⁇ ⁇
  • Example 101 350 340 1.03 ⁇ 0
  • Example 103 250 210 1.19 ⁇ ⁇
  • Example 117 120 100 1.20 0 ⁇
  • Example 119 300 290 1.03 ⁇ ⁇
  • Example 60 pigment dispersions were obtained according to the blending ratios (weight ratios) shown in Table 12.
  • the evaluation was made in the same manner as in Example 60 (the lower the viscosity, the better, the closer the TI value is to 1, the better).
  • ⁇ , ⁇ 1 if the rate of change in viscosity before and after storage at 50 ° C for 1 week is within ⁇ 10%
  • it was set as X.
  • the coating weight loss is 200 after removing the coating film and solvent on the glass.
  • C, ⁇ if the weight loss before and after heating for 1 hour is within 10%, and X if it exceeds 10%.
  • Table 13 The results are shown in Table 13.
  • Comparative Example 12 200 200 1. 00 ⁇ X
  • Comparative example 19 350 300 1.17 ⁇ X
  • Comparative example 20 400 330 1.21 ⁇ X
  • the pigment dispersions of Examples 60 to 119 using the polyester dispersant of the present invention have a low initial viscosity and are excellent with little increase in viscosity over time. Stability. In addition, the coating has high resistance. On the other hand, in the pigment dispersions of Comparative Examples 8 to 24, the amount of the dispersant having a high viscosity must be increased. Also, since many dispersants with low molecular weight were used, it was obvious that there was a problem with the durability of the coating film even though there was no problem with the viscosity.
  • the polyester dispersant according to the present invention can be suitably used in fields such as paints and colored resin compositions, and specifically includes offset inks, gravure inks, color filter resist inks, and the like. It can be suitably used for ink jet inks.
  • the polyester dispersant of the present invention is used, a dispersion excellent in non-aggregability, fluidity and storage stability can be produced.

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Abstract

Disclosed is a polyester dispersant which is produced by reacting a hydroxyl group in a vinyl polymer (a) having two hydroxyl groups in one terminal region thereof and optionally a hydroxyl group in a polyol compound (c) other than the vinyl polymer (a) with an acid anhydride group in an anhydrous tetracarboxylic acid (b) and optionally an acid anhydride group in an anhydrous tricarboxylic acid (d), wherein the vinyl polymer (a) is produced by the radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule. Also disclosed is a process for producing the polyester dispersant. The polyester dispersant shows excellent dispersion property, fluidability and storage stability even when used in a small amount. The polyester dispersant is suitable for an offset ink, a gravure ink, a resist ink for a color filter, an inkjet ink, a coating, a colored resin composition and the like.

Description

明 細 書  Specification
ポリエステル分散剤とその製造方法、及びそれを用いた顔料組成物 技術分野  Polyester dispersant and method for producing the same, and pigment composition using the same
[0001] 本発明は、ポリエステル分散剤に関し、更に詳しくは、塗料及び着色榭脂組成物な どの分野に適する、非集合性、流動性、保存安定性に優れた分散体を製造すること のできるポリエステル分散剤とその製造方法、及びそれを用いた顔料組成物に関す る。  [0001] The present invention relates to a polyester dispersant, and more specifically, it is possible to produce a dispersion excellent in non-aggregability, fluidity, and storage stability, which is suitable for fields such as paints and colored resin compositions. The present invention relates to a polyester dispersant, a production method thereof, and a pigment composition using the same.
背景技術  Background art
[0002] 一般に、インキ等を製造する場合、顔料を安定に高濃度で分散することが難しぐ 製造工程や製品そのものに対して種々の問題を引き起こすことが知られている。例え ば、微細な粒子からなる顔料を含む分散体は往々にして高粘度を示し、製品の分散 機からの取り出しや輸送が困難となるば力りでなぐ悪い場合は保存中にゲルィ匕を起 こし、使用困難となることさえある。更に展色物の表面に関しては光沢の低下、レベリ ング不良等の状態不良を生じる。また、異種の顔料を混合して使用する場合、凝集 による色別れや、沈降などの現象により展色物に色むらや著しい着色力の低下が現 れることがある。  [0002] Generally, when manufacturing ink or the like, it is difficult to stably disperse a pigment at a high concentration, and it is known to cause various problems with respect to the manufacturing process and the product itself. For example, dispersions containing pigments made up of fine particles often exhibit high viscosity and cause gelling during storage if the product is difficult to remove and transport from the disperser if it is difficult to remove by force. However, it can be difficult to use. In addition, on the surface of the color-exhibited object, a poor state such as a decrease in gloss and poor leveling occurs. In addition, when different types of pigments are used in combination, color unevenness due to agglomeration or sedimentation may cause uneven color and a marked reduction in coloring power.
[0003] そこで一般的には分散状態を良好に保っために分散剤が利用されている。分散剤 は顔料に吸着する部位と、分散媒である溶剤に親和性の高い部位との構造を持ち合 わせ、この 2つの機能の部位のバランスで分散剤の性能は決まる。分散剤は被分散 物である顔料の表面状態に合わせ種々のものが使用されている力 塩基性に偏った 表面を有する顔料には酸性の分散剤が使用されるのが一般的である。この場合、酸 性官能基が顔料の吸着部位となる。酸性の官能基としてカルボン酸を有する分散剤 は、例えば特許文献 1、特許文献 2、特許文献 3、特許文献 4などに記載されている。  [0003] Therefore, in general, a dispersant is used to maintain a good dispersion state. The dispersant combines the structure of the part that adsorbs to the pigment and the part that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance between these two functional parts. Various dispersants are used according to the surface condition of the pigment to be dispersed. In general, an acidic dispersant is used for a pigment having a surface that is biased toward basicity. In this case, the acidic functional group becomes the adsorption site of the pigment. Dispersants having a carboxylic acid as an acidic functional group are described in, for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and the like.
[0004] しかし、これらはある程度の分散能力は持ち合わせるが、低粘度で安定な分散体を つくるには使用量を多くする必要があった。しかし、使用量を多くすることは、インキ、 塗料等への展開を考える上で、塗膜の耐性が落ちる場合があるなど好まし 、もので はなかった。 特許文献 1：特開昭 61— 61623号公報 [0004] However, these have some dispersibility, but it was necessary to increase the amount of use in order to produce a stable dispersion with low viscosity. However, increasing the amount used was not preferable because it could reduce the resistance of the coating film when considering the development of inks and paints. Patent Document 1: Japanese Patent Application Laid-Open No. 61-61623
特許文献 2：特開平 1― 141968号公報  Patent Document 2: JP-A-1-141968
特許文献 3 :特開平 2— 219866号公報  Patent Document 3: JP-A-2-219866
特許文献 4：特開平 11― 349842号公報  Patent Document 4: Japanese Patent Laid-Open No. 11-349842
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] 本発明は、低使用量で分散性、流動性、保存安定性に優れる顔料分散体を得るた めの分散剤の提供を目的とする。更に本発明は、オフセットインキ、グラビアインキ、 カラーフィルター用レジストインキ及びインキジェットインキ、塗料、着色榭脂組成物な どに適する、非集合性、流動性に優れた分散性や安定性をもたすことのできる、ポリ エステル分散剤の提供を目的とする。 [0005] An object of the present invention is to provide a dispersant for obtaining a pigment dispersion which is excellent in dispersibility, fluidity and storage stability at a low use amount. Furthermore, the present invention is suitable for offset inks, gravure inks, color filter resist inks and ink jet inks, paints, colored resin compositions, etc., and has dispersibility and stability excellent in non-aggregation and fluidity. It is an object of the present invention to provide a polyester dispersant.
課題を解決するための手段  Means for solving the problem
[0006] 本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)の存 在下に、エチレン性不飽和単量体をラジカル重合して生成され、片末端領域に 2つ の水酸基を有するビニル重合体 (a)中の水酸基と、 [0006] The present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule. A hydroxyl group in the vinyl polymer (a) having one hydroxyl group;
テトラカルボン酸無水物 (b)中の酸無水物基と、  An acid anhydride group in tetracarboxylic acid anhydride (b);
を反応させて生成されるポリエステル分散剤に関する。  The present invention relates to a polyester dispersant produced by reaction of
[0007] また、本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) の存在下に、エチレン性不飽和単量体をラジカル重合して生成され、片末端領域に[0007] In addition, the present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule. In
2つの水酸基を有するビニル重合体 (a)中の水酸基、及び前記ビニル重合体 (a)以 外のポリオール化合物（c)中の水酸基と、 A hydroxyl group in the vinyl polymer (a) having two hydroxyl groups, and a hydroxyl group in the polyol compound (c) other than the vinyl polymer (a);
テトラカルボン酸無水物 (b)中の酸無水物基と、  An acid anhydride group in tetracarboxylic acid anhydride (b);
を反応させて生成されるポリエステル分散剤にも関する。  It also relates to a polyester dispersant produced by reacting.
[0008] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) の存在下に、エチレン性不飽和単量体をラジカル重合して生成され、片末端領域に[0008] Further, the present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule,
2つの水酸基を有するビニル重合体 (a)中の水酸基と、 A hydroxyl group in the vinyl polymer (a) having two hydroxyl groups;
テトラカルボン酸無水物（b)中の酸無水物基及びトリカルボン酸無水物（d)中の酸 無水物基と、 を反応させて生成されるポリエステル分散剤に関する。 An acid anhydride group in the tetracarboxylic acid anhydride (b) and an acid anhydride group in the tricarboxylic acid anhydride (d); The present invention relates to a polyester dispersant produced by reaction of
[0009] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) の存在下に、エチレン性不飽和単量体をラジカル重合して生成され、片末端領域に 2つの水酸基を有するビニル重合体 (a)中の水酸基、及び前記ビニル重合体 (a)以 外のポリオール化合物（c)中の水酸基と、  Furthermore, the present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, A hydroxyl group in the vinyl polymer (a) having two hydroxyl groups, and a hydroxyl group in the polyol compound (c) other than the vinyl polymer (a);
テトラカルボン酸無水物（b)の酸無水物基及びトリカルボン酸無水物（d)中の酸無 水物基と、  An acid anhydride group of tetracarboxylic acid anhydride (b) and an acid anhydride group in tricarboxylic acid anhydride (d);
を反応させて生成されるポリエステル分散剤に関する。  The present invention relates to a polyester dispersant produced by reaction of
[0010] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) 中の水酸基とテトラカルボン酸無水物 (b)中の酸無水物基とを反応させて生成される 化合物（a2)の存在下に、エチレン性不飽和単量体をラジカル重合して生成されるポ リエステル分散剤に関する。 [0010] Further, the present invention is produced by reacting a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in a tetracarboxylic acid anhydride (b). The present invention relates to a polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of the compound (a2).
[0011] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) 及びチオール基を有さな 、ポリオール化合物（c' )中の水酸基とテトラカルボン酸無 水物 (b)中の酸無水物基とを反応させて生成される化合物（a3)の存在下に、ェチレ ン性不飽和単量体をラジカル重合して生成されるポリエステル分散剤に関する。  [0011] Further, the present invention relates to a compound (al) having two hydroxyl groups and one thiol group in the molecule, and a hydroxyl group and tetracarboxylic acid anhydride in the polyol compound (c ') having no thiol group. The present invention relates to a polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a3) produced by reacting with an acid anhydride group in (b).
[0012] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) 中の水酸基とテトラカルボン酸無水物（b)中の酸無水物基及びトリカルボン酸無水物 (d)中の酸無水物基とを反応させて生成される化合物（a4)の存在下に、エチレン性 不飽和単量体をラジカル重合して生成されるポリエステル分散剤に関する。  Furthermore, the present invention relates to a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group in a tetracarboxylic acid anhydride (b), and a tricarboxylic acid anhydride ( The present invention relates to a polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a4) produced by reacting with an acid anhydride group in d).
[0013] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) 及びチオール基を有さな 、ポリオール化合物（c' )中の水酸基とテトラカルボン酸無 水物（b)中の酸無水物基及びトリカルボン酸無水物（d)中の酸無水物基とを反応さ せて生成される化合物（a5)の存在下に、エチレン性不飽和単量体をラジカル重合し て生成されるポリエステル分散剤に関する。  [0013] Furthermore, the present invention relates to a compound (al) having two hydroxyl groups and one thiol group in the molecule, and a hydroxyl group and tetracarboxylic acid anhydride in the polyol compound (c ') having no thiol group. In the presence of the compound (a5) produced by reacting the acid anhydride group in (b) with the acid anhydride group in tricarboxylic anhydride (d), the ethylenically unsaturated monomer is radicalized. The present invention relates to a polyester dispersant produced by polymerization.
[0014] 本発明によるポリエステル分散剤の好ましい態様では、重量平均分子量が 2000〜 35000であり、かつ、酸価力 5〜200である。  In a preferred embodiment of the polyester dispersant according to the present invention, the weight average molecular weight is 2000 to 35000, and the acid value power is 5 to 200.
[0015] 本発明によるポリエステル分散剤の好ま 、態様では、テトラカルボン酸無水物 (b) が、下記一般式（1)又は一般式 (2)で表される: 一般式 (1) [0015] In a preferred embodiment of the polyester dispersant according to the present invention, a tetracarboxylic acid anhydride (b) Is represented by the following general formula (1) or general formula (2):
[化 1][Chemical 1]
Figure imgf000005_0001
Figure imgf000005_0001
で表される基、又は式: Or a group represented by the formula:
Figure imgf000006_0001
Figure imgf000006_0001
で表される基である。 ]  It is group represented by these. ]
[0016] 本発明によるポリエステル分散剤の好ましい態様では、エチレン性不飽和単量体を ラジカル重合してなるビュル重合体部分の重量平均分子量が、 1000〜10000であ る。  In a preferred embodiment of the polyester dispersant according to the present invention, the weight average molecular weight of the bulle polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer is 1,000 to 10,000.
[0017] 本発明によるポリエステル分散剤の好ましい態様では、エチレン性不飽和単量体を ラジカル重合してなるビュル重合体部分のガラス転移温度力 - 50〜70°Cである。  [0017] In a preferred embodiment of the polyester dispersant according to the present invention, the glass transition temperature force of the bulle polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer is −50 to 70 ° C.
[0018] 本発明によるポリエステル分散剤の好ましい態様では、エチレン性不飽和単量体 力 ベンジル (メタ）アタリレートを単量体全体の 20重量％〜70重量％含む。  [0018] In a preferred embodiment of the polyester dispersant according to the present invention, the ethylenically unsaturated monomer force benzyl (meth) acrylate is contained in an amount of 20% to 70% by weight based on the whole monomer.
[0019] 本発明によるポリエステル分散剤の好ましい態様では、エチレン性不飽和単量体 力 下記一般式 (3)で表わされる単量体を含む。  [0019] In a preferred embodiment of the polyester dispersant according to the present invention, an ethylenically unsaturated monomer force includes a monomer represented by the following general formula (3).
[0020] 更に本発明は、上記ポリエステル分散剤と、顔料とを含有する顔料組成物に関する  [0020] Further, the present invention relates to a pigment composition containing the above polyester dispersant and a pigment.
[0021] 更に本発明は、塩基性基を有する顔料誘導体、塩基性基を有するアントラキノン誘 導体、塩基性基を有するアタリドン誘導体、及び塩基性基を有するトリァジン誘導体 からなる群から選ばれる塩基性誘導体少なくとも一種を含有する上記顔料組成物に 関する。 Furthermore, the present invention relates to a basic derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an attaridone derivative having a basic group, and a triazine derivative having a basic group. The present invention relates to the above pigment composition containing at least one kind.
[0022] 更に本発明は、上記顔料組成物をワニスに分散させてなる顔料分散体に関する。  Furthermore, the present invention relates to a pigment dispersion obtained by dispersing the pigment composition in a varnish.
[0023] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) の存在下に、エチレン性不飽和単量体をラジカル重合して、片末端領域に 2つの水 酸基を有するビニル重合体 (a)を製造する工程 A1と、 [0023] Furthermore, the present invention is directed to radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, so that Step A1 for producing a vinyl polymer (a) having a hydroxyl group,
前記ビュル重合体 (a)とテトラカルボン酸無水物 (b)とを反応させる工程 B1と、 を含むポリエステル分散剤の製造方法に関する。 [0024] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) の存在下に、エチレン性不飽和単量体をラジカル重合して、片末端領域に 2つの水 酸基を有するビニル重合体 (a)を製造する工程 A2と、 And a step B1 of reacting the bulle polymer (a) with the tetracarboxylic acid anhydride (b). [0024] Furthermore, the present invention is directed to radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, so that Step A2 for producing a vinyl polymer (a) having a hydroxyl group,
前記ビニル重合体 (a)とテトラカルボン酸無水物 (b)と前記ビニル重合体 (a)以外の ポリオール化合物（c)とを反応させる工程 B2と、  A step B2 of reacting the vinyl polymer (a), the tetracarboxylic acid anhydride (b) and a polyol compound (c) other than the vinyl polymer (a);
を含むポリエステル分散剤の製造方法に関する。  The manufacturing method of the polyester dispersing agent containing this.
[0025] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) の存在下に、エチレン性不飽和単量体をラジカル重合して、片末端領域に 2つの水 酸基を有するビニル重合体 (a)を製造する工程 A3と、 [0025] Furthermore, the present invention is directed to radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, so that Step A3 for producing a vinyl polymer (a) having a hydroxyl group,
前記ビニル重合体 (a)とテトラカルボン酸無水物 (b)とトリカルボン酸無水物（d)とを 反応させる工程 B3と、  A step B3 of reacting the vinyl polymer (a) with a tetracarboxylic acid anhydride (b) and a tricarboxylic acid anhydride (d);
を含むポリエステル分散剤の製造方法に関する。  The manufacturing method of the polyester dispersing agent containing this.
[0026] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) の存在下に、エチレン性不飽和単量体をラジカル重合して、片末端領域に 2つの水 酸基を有するビニル重合体 (a)を製造する工程 A4と、 [0026] Furthermore, the present invention is directed to radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, so that Step A4 for producing a vinyl polymer (a) having a hydroxyl group,
前記ビニル重合体 (a)とテトラカルボン酸無水物 (b)と前記ビニル重合体 (a)以外の ポリオール化合物（c)とトリカルボン酸無水物（d)とを反応させる工程 B4と、 を含むポリエステル分散剤の製造方法に関する。  A step B4 of reacting the vinyl polymer (a), a tetracarboxylic acid anhydride (b), a polyol compound (c) other than the vinyl polymer (a), and a tricarboxylic acid anhydride (d), and a polyester comprising: The present invention relates to a method for producing a dispersant.
[0027] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) 中の水酸基とテトラカルボン酸無水物 (b)中の酸無水物基とを反応させ、化合物（a2 )を製造する工程 B5と、 [0027] Further, the present invention provides a compound by reacting a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in a tetracarboxylic acid anhydride (b). Step B5 for producing (a2),
前記化合物（a2)の存在下に、エチレン性不飽和単量体をラジカル重合させる工程 A5と、  A step A5 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a2);
を含むポリエステル分散剤の製造方法に関する。  The manufacturing method of the polyester dispersing agent containing this.
[0028] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) 中の水酸基及びチオール基を有さないポリオ一ルイ匕合物（c ' )中の水酸基とテトラ力 ルボン酸無水物 (b)中の酸無水物基とを反応させ、化合物（a3)を製造する工程 B6 と、 前記化合物（a3)の存在下に、エチレン性不飽和単量体をラジカル重合させる工程 A6と、 [0028] Further, the present invention relates to a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule and a hydroxyl group in a polyol compound (c ') having no thiol group. Step B6 for producing a compound (a3) by reacting with an acid anhydride group in tetraforce rubonic anhydride (b), A step A6 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a3);
を含むポリエステル分散剤の製造方法に関する。  The manufacturing method of the polyester dispersing agent containing this.
[0029] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) 中の水酸基と、テトラカルボン酸無水物（b)中の酸無水物基とトリカルボン酸無水物（ d)中の酸無水物基とを反応させ、化合物 (a4)を製造する工程 B7と、 [0029] Further, the present invention relates to a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group and a tricarboxylic acid anhydride in tetracarboxylic acid anhydride (b). (B) reacting with an acid anhydride group in step B7 to produce compound (a4);
前記化合物（a4)の存在下に、エチレン性不飽和単量体をラジカル重合させる工程 A7と、  A step A7 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a4);
を含むポリエステル分散剤の製造方法に関する。  The manufacturing method of the polyester dispersing agent containing this.
[0030] 更に本発明は、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al) 中の水酸基とテトラカルボン酸無水物（b)中の酸無水物基とチオール基を有さない ポリオ一ルイ匕合物（c ' )中の水酸基とトリカルボン酸無水物（d)中の酸無水物基とを 反応させ、化合物 (a5)を製造する工程 B8と、 [0030] Further, the present invention has a hydroxyl group in the compound (al) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group and a thiol group in the tetracarboxylic acid anhydride (b). A step B8 for producing a compound (a5) by reacting a hydroxyl group in a polyol-free compound (c ′) with an acid anhydride group in a tricarboxylic acid anhydride (d);
前記化合物（a5)の存在下に、エチレン性不飽和単量体をラジカル重合させる工程 A8と、  A step A8 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a5);
を含むポリエステル分散剤の製造方法に関する。  The manufacturing method of the polyester dispersing agent containing this.
[0031] 本発明方法の好ましい態様では、テトラカルボン酸無水物 (b)が、下記一般式（1) 又は一般式（2)で表される： [0031] In a preferred embodiment of the method of the present invention, the tetracarboxylic acid anhydride (b) is represented by the following general formula (1) or general formula (2):
一般式 (1)  General formula (1)
[化 5]  [Chemical 5]
Figure imgf000008_0001
Figure imgf000008_0001
[一般式（1)中、 kは 1又は 2である。 ]  [In the general formula (1), k is 1 or 2. ]
一般式 (2)  General formula (2)
[化 6] [Chemical 6]
Figure imgf000009_0001
Figure imgf000009_0001
Figure imgf000009_0002
Figure imgf000009_0002
Figure imgf000009_0003
Figure imgf000009_0003
で表される基である。 ]  It is group represented by these. ]
[0032] 本発明方法の好まし 、態様では、エチレン性不飽和単量体が、ベンジル (メタ）ァク リレートを単量体全体の 20重量％〜70重量％含む。  [0032] In a preferred embodiment of the method of the present invention, the ethylenically unsaturated monomer contains benzyl (meth) acrylate in an amount of 20% to 70% by weight of the total monomer.
[0033] 本発明方法の好ま 、態様では、エチレン性不飽和単量体が、下記一般式（3)で 表わされる単量体を含む： [0033] In a preferred embodiment of the method of the present invention, the ethylenically unsaturated monomer includes a monomer represented by the following general formula (3):
一般式 (3)
Figure imgf000010_0001
General formula (3)
Figure imgf000010_0001
[一般式 (3)中、 Rは、炭素原子数 1〜4の直鎖状若しくは分岐状のアルキル基であ る。]  [In the general formula (3), R represents a linear or branched alkyl group having 1 to 4 carbon atoms. ]
発明の効果  The invention's effect
[0034] 本発明のポリエステル分散剤を使用することにより、従来得られな力つた分散性、流 動性、保存安定性を有する顔料組成物を提供できる。更に、オフセットインキ、グラビ ァインキ、カラーフィルター用レジストインキ及びインキジェットインキ、塗料、着色榭 脂組成物などに適する、非集合性、流動性に優れた分散性や安定性をもち、高い貯 蔵安定性及び高い経時安定性を有する顔料分散体を提供できる。  [0034] By using the polyester dispersant of the present invention, it is possible to provide a pigment composition having strong dispersibility, fluidity, and storage stability that has not been obtained conventionally. Furthermore, it is suitable for offset ink, gravure ink, resist ink and ink jet ink for color filters, paints, colored resin compositions, etc., has excellent dispersibility and stability with excellent non-aggregability and fluidity, and high storage stability. And a pigment dispersion having high stability with time.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0035] 一般に、顔料分散剤は顔料に吸着する部位と、分散媒である溶剤に親和性の高い 部位との構造を持ち合わせ、この 2つの部位のバランスで分散剤の性能が決まる。つ まり、分散性を発現させるためには、分散剤の顔料に吸着する性能と分散媒である 溶剤への親和性がともに非常に重要である。  [0035] Generally, a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a solvent as a dispersion medium, and the performance of the dispersant is determined by the balance of these two parts. In other words, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important.
[0036] 本発明に使用するテトラカルボン酸無水物 (b)は、水酸基と反応してエステル結合 を形成し、かつ、生成するポリエステル主鎖上にペンダントカルボキシル基を残すこと 力 Sできる。 2つの水酸基を片末端領域 (一方の末端領域）に有するポリオ一ルイヒ合物  [0036] The tetracarboxylic acid anhydride (b) used in the present invention can react with a hydroxyl group to form an ester bond and leave a pendant carboxyl group on the resulting polyester main chain. Polio-Ruich compound with two hydroxyl groups in one end region (one end region)
[化 10] [Chemical 10]
HO— A—— OH  HO— A—— OH
I  I
B  B
(式中、 Aは末端領域であり、 Bはビニル重合体部分である）  (Where A is the terminal region and B is the vinyl polymer moiety)
のモル量「a」と、コア部分 Xを有するテトラカルボン酸無水物のモル量「b」とについ て、  And the molar amount “b” of the tetracarboxylic anhydride having the core portion X,
(i) a>b、（ii) a=b、又は（iii) aく b としたときのテトラカルボン酸無水物とポリオ ルイ匕合物との反応工程式を下記反応 工程式 (4) （6)に示す。下記反応工程式 (4) （6)にお 、て、 nは繰り返し単位数 である。下記の反応工程式 (6)において、生成物中に残っている酸無水物基を加水 分解すれば、この反応工程による生成物は、構造式中の X部分にカルボキシル基を 2個又は 3個を有しており、この複数のカルボキシル基が顔料の吸着部位として有効 である。 (i) a> b, (ii) a = b, or (iii) a The reaction process formulas of tetracarboxylic anhydride and polyol compound are shown in the following reaction process formulas (4) and (6). In the following reaction process formulas (4) and (6), n is the number of repeating units. In the following reaction process formula (6), if the acid anhydride group remaining in the product is hydrolyzed, the product of this reaction process will have 2 or 3 carboxyl groups in the X part of the structural formula. The plurality of carboxyl groups are effective as pigment adsorption sites.
[0037] 反応工程式 (4) : (i) a>b  [0037] Reaction process formula (4): (i) a> b
[化 11]  [Chemical 11]
Figure imgf000011_0001
Figure imgf000011_0001
[0038] 反応工程式（5)： (ii) a=b  [0038] Reaction process formula (5): (ii) a = b
[化 12]  [Chemical 12]
Figure imgf000011_0002
Figure imgf000011_0002
[0039] 反応工程式（6)： (iii) a<b  [0039] Reaction process formula (6): (iii) a <b
[化 13]  [Chemical 13]
Figure imgf000011_0003
Figure imgf000011_0003
[0040] しかしながら、本発明のポリエステル分散剤において、コア部分 Xに結合している カルボキシル基が 1個のみである場合 (本発明の範囲外)では、高い分散性、流動性[0040] However, in the polyester dispersant of the present invention, it is bonded to the core portion X. When there is only one carboxyl group (out of the scope of the present invention), high dispersibility and fluidity
、及び保存安定性を発現せず好ましくない。 And storage stability is not exhibited, which is not preferable.
[0041] 本発明のポリエステル分散剤において、コア部分 Xは、テトラカルボン酸無水物が 水酸基と反応した後の反応残基、 =A— Bはポリオール化合物が酸無水物基と反応 した後の反応残基である。 Aの末端領域は、例えば、炭素原子数 1〜10 (好ましくは 炭素原子数 1〜8)の直鎖状若しくは分枝状の 3価脂肪族炭化水素基である (ビニル 重合体部分 Bにつ 、ては後述する）。この片末端領域に含まれて 、る 2つの水酸基 は、同一の炭素原子に結合していても、別異の炭素原子に結合していてもよい。好ま しいコア部分 Xの形態は、下記一般式（1)又は一般式（2)で示されるテトラカルボン 酸無水物力 ポリオ一ルイ匕合物と反応した後の反応残基である。  [0041] In the polyester dispersant of the present invention, the core part X is a reaction residue after the tetracarboxylic acid anhydride has reacted with the hydroxyl group, and = AB is a reaction after the polyol compound has reacted with the acid anhydride group. Residue. The terminal region of A is, for example, a linear or branched trivalent aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms) (for vinyl polymer portion B). And will be described later). The two hydroxyl groups contained in this one terminal region may be bonded to the same carbon atom or may be bonded to different carbon atoms. A preferable form of the core part X is a reaction residue after reacting with a tetracarboxylic acid anhydride polyolide compound represented by the following general formula (1) or general formula (2).
[0042] 一般式（1)  [0042] General formula (1)
[化 14]  [Chemical 14]
Figure imgf000012_0001
Figure imgf000012_0001
[化 16] [Chemical 16]
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0002
で表される基である。 ]  It is group represented by these. ]
[0044] 本発明のポリエステル分散剤では、片末端領域に 2つの水酸基を有するビニル重 合体 (a)とテトラカルボン酸無水物 (b)とを反応させることにより、上記反応工程式 (4) における生成物中のコア部分 ェに結合する複数のカルボキシル基部分が顔料吸着 部として機能し、ビニル重合体部分 Bが溶媒親和部として機能する。  [0044] In the polyester dispersant of the present invention, by reacting a vinyl polymer (a) having two hydroxyl groups in one terminal region with a tetracarboxylic acid anhydride (b), the above reaction process formula (4) A plurality of carboxyl group moieties bonded to the core part in the product function as a pigment adsorbing part, and a vinyl polymer part B functions as a solvent affinity part.
[0045] 更に本発明のポリエステル分散剤では、 2つの水酸基と 1つのチオール基を有する 化合物（al)とテトラカルボン酸無水物 (b)とを反応させて、ビニル重合体部分 Bを含 まな 、化合物（a2)〜（a5)を最初に製造し、続、て、前記化合物（a2)〜（a5)の残 存しているチオール基を連鎖移動剤としてラジカル重合することでビュル重合体部 分 Bを導入して、同様の構造の榭脂を得ることが可能である。上記反応工程式 (4)に おける生成物中のコア部分 Xに結合する複数のカルボキシル基部分を最初の工程 B5〜B8で形成させて顔料吸着部とし、続く工程 A5〜A8で導入されるビュル重合 体部分 Bを溶媒親和部として機能させることが可能である。  [0045] Further, in the polyester dispersant of the present invention, the compound (al) having two hydroxyl groups and one thiol group is reacted with the tetracarboxylic acid anhydride (b) to contain the vinyl polymer portion B. The compounds (a2) to (a5) are first produced, followed by radical polymerization using the remaining thiol groups of the compounds (a2) to (a5) as chain transfer agents, so that By introducing B, it is possible to obtain a resin having a similar structure. In the above reaction process formula (4), a plurality of carboxyl group moieties bonded to the core portion X in the product are formed in the first steps B5 to B8 to form a pigment adsorbing portion, and then the butyl introduced in the subsequent steps A5 to A8. The polymer part B can function as a solvent affinity part.
[0046] 下記反応工程式（7)〜（ 10)に示すように、前記の最初の工程 B5〜B8では、ポリ エステル主鎖上にペンダントカルボキシル基を残すことができ、続 、て実施する工程 A5〜A8でビニル重合体部分 Bを導入することができる。なお、下記反応工程式（7) 〜（10)において、 s及び tは繰り返し単位数であり、 HO— D— OHはチオール基を 有さないポリオール化合物（c' )である。この HO— D— OHは、前記ポリオール化合 物 B—A—(OH)であることもできる。 [0046] As shown in the following reaction process formulas (7) to (10), in the first steps B5 to B8, a pendant carboxyl group can be left on the polyester main chain, and the subsequent steps are carried out. Vinyl polymer portion B can be introduced at A5 to A8. In addition, the following reaction process formula (7) In (10), s and t are the number of repeating units, and HO—D—OH is a polyol compound (c ′) having no thiol group. This HO-D-OH can also be the polyol compound B-A- (OH).
2  2
工程 B5及び工程 A5〔2つの水酸基と 1つのチオール基を有する化合物（al)とテト ラカルボン酸無水物 (b)とを反応させ、続いてエチレン性不飽和単量体を導入する 場合〕：  Step B5 and Step A5 [when reacting a compound having two hydroxyl groups and one thiol group (al) with tetracarboxylic anhydride (b) and then introducing an ethylenically unsaturated monomer]:
反応工程式 (7)  Reaction process formula (7)
[化 18] [Chemical 18]
Figure imgf000014_0001
Figure imgf000014_0001
工程 B6及び工程 A6〔2つの水酸基と 1つのチオール基を有する化合物（al)とテト ラカルボン酸無水物 (b)とチオール基を有さな!/、ポリオール化合物（c， )とを反応させ 、続いてエチレン性不飽和単量体を導入する場合〕：  Step B6 and Step A6 [compound having two hydroxyl groups and one thiol group (al), tetracarboxylic anhydride (b) and no thiol group! /, Polyol compound (c,), Subsequently, when ethylenically unsaturated monomer is introduced]:
反応工程式 (8)  Reaction process formula (8)
[化 19] [Chemical 19]
HO- HO-
Figure imgf000014_0002
工程 B7及び工程 A7〔2つの水酸基と 1つのチオール基を有する化合物（al)とテト ラカルボン酸無水物 (b)とトリカルボン酸無水物（d)とを反応させ、続、てエチレン性 不飽和単量体を導入する場合〕：
Figure imgf000014_0002
Step B7 and Step A7 [compounds having two hydroxyl groups and one thiol group (al), tetracarboxylic anhydride (b) and tricarboxylic anhydride (d) are reacted, followed by ethylenically unsaturated monoester When introducing a polymer]:
反応工程式 (9)  Reaction process formula (9)
[化 20] [Chemical 20]
Figure imgf000015_0001
Figure imgf000015_0001
工程 B8及び工程 A8〔2つの水酸基と 1つのチオール基を有する化合物（al)とテト ラカルボン酸無水物（b)とチオール基を有さな 、ポリオール化合物（c ' )とトリカルボ ン酸無水物 (d)とを反応させ、続いてエチレン性不飽和単量体を導入する場合〕： 反応工程式（10)  Step B8 and Step A8 [Compound having two hydroxyl groups and one thiol group (al), tetracarboxylic acid anhydride (b), polyol compound (c ') and tricarboxylic acid anhydride (without thiol group) Reaction with d) followed by introduction of ethylenically unsaturated monomer]: Reaction process formula (10)
[化 21]
Figure imgf000016_0001
[Chemical 21]
Figure imgf000016_0001
[0051] このように、複数のペンダントカルボキシル基を形成させ顔料吸着部として機能させ ることができ、更に残存したチオール基を用いて連鎖移動剤としてラジカル重合する 工程 A5〜A8で生成するビュル重合体部分を溶媒親和部として機能させることが可 能である。  [0051] In this way, a plurality of pendant carboxyl groups can be formed to function as a pigment adsorbing portion, and further, radical polymerization can be performed as a chain transfer agent using the remaining thiol groups. It is possible to make the combined part function as a solvent affinity part.
[0052] 本明細書にぉ 、て「エチレン性不飽和単量体をラジカル重合してなるビュル重合 体部分」とは、テトラカルボン酸無水物 (b)又はトリカルボン酸無水物（d)由来の部分 を含まない連続した部分であり、通常、本発明のポリエステル分散剤を構成する 1分 子中には、複数のビニル重合体部分 Bが含まれる。  In the present specification, the “bule polymer portion formed by radical polymerization of an ethylenically unsaturated monomer” is derived from a tetracarboxylic acid anhydride (b) or a tricarboxylic acid anhydride (d). A plurality of vinyl polymer parts B are usually contained in one molecule constituting the polyester dispersant of the present invention.
エチレン性不飽和単量体をラジカル重合してなるビニル重合体部分 Bの重量平均 分子量 ίま、 1000〜10000力 S好まし <、より好まし <ίま 2000〜8000、更に好まし <ίま 2000〜6000、特に好ましくは 3000〜5000である。この部分 Βが分散媒である溶 剤への親和性部分となる。ビニル重合体部分 Βの重量平均分子量が 1000未満では 、溶媒親和部による立体反発の効果が少なくなるとともに、顔料の凝集を防ぐことが 困難となり、分散安定性が不十分となる場合がある。また 10000を超えると、溶媒親 和部の絶対量が増えてしまい、分散性の効果自体が低下する場合がある。更に、分 散体の粘度が高くなる場合がある。ビニル重合体 (a)は、分子量を上記範囲に調整 することが容易であり、かつ、溶剤への親和性も良好である。  Weight average molecular weight of vinyl polymer part B obtained by radical polymerization of ethylenically unsaturated monomer Molecular weight ί, 1000-10000 force S preferred <, more preferred <ί or 2000-8000, more preferred <ί 2000 to 6000, particularly preferably 3000 to 5000. This part is the affinity part for the solvent that is the dispersion medium. When the weight average molecular weight of the vinyl polymer part is less than 1000, the effect of steric repulsion by the solvent affinity part is reduced, and it becomes difficult to prevent the aggregation of the pigment, and the dispersion stability may be insufficient. On the other hand, if it exceeds 10000, the absolute amount of the solvent compatible portion increases, and the dispersibility effect itself may decrease. In addition, the viscosity of the dispersion may increase. The vinyl polymer (a) can be easily adjusted in molecular weight to the above range, and has good affinity for the solvent.
[0053] エチレン性不飽和単量体をラジカル重合してなるビュル重合体部分 Bのガラス転移 温度は、顔料の分散性がより高くなるという点から、— 50〜70°Cが好ましぐ— 50〜 40°Cがより好ましい。 [0053] The glass transition temperature of the bull polymer portion B formed by radical polymerization of an ethylenically unsaturated monomer is preferably 50 to 70 ° C in view of higher dispersibility of the pigment. 50 ~ 40 ° C is more preferred.
[0054] 本明細書において、エチレン性不飽和単量体をラジカル重合してなるビニル重合 体部分 Bの Tg (ガラス転移温度）は、下記の Foxの式で算出した値を用いる。なお、 分子内に 2つの水酸基と 1つのチオール基とを有する化合物由来の骨格もビニル重 合体 (a)中に存在するが、ガラス転移温度を計算する以下の計算から除くものとする  In the present specification, the value calculated by the following Fox formula is used for Tg (glass transition temperature) of vinyl polymer portion B obtained by radical polymerization of an ethylenically unsaturated monomer. A skeleton derived from a compound having two hydroxyl groups and one thiol group in the molecule is also present in the vinyl polymer (a), but is excluded from the following calculation for calculating the glass transition temperature.
[0055] (Wl/Tgl) + (W2/Tg2) H h (Wn/Tgn) [0055] (Wl / Tgl) + (W2 / Tg2) H h (Wn / Tgn)
前記の式で、 Tgは、ビュル重合体部分 B全体のガラス転移温度であり、 W1から W nは、使用しているモノマーの重量分率を示し、 Tglから Tgnは、各ホモポリマーのガ ラス転移温度 (単位は絶対温度「K」 )を示す。  In the above formula, Tg is the glass transition temperature of the entire Bule polymer part B, W1 to Wn are the weight fractions of the monomers used, and Tgl to Tgn are the glass weights of each homopolymer. Indicates transition temperature (unit: absolute temperature “K”).
算出に使用する主なホモポリマーの Tgを下記に例示する。  The Tg of the main homopolymer used for calculation is shown below.
n—ブチルアタリレート：—45°C (228K)  n—Butyl acrylate: —45 ° C (228K)
メチルアタリレート： 8°C (281K)  Methyl acrylate: 8 ° C (281K)
n—ブチルメタタリレート： 20°C (293K)  n-Butylmetatalylate: 20 ° C (293K)
ベンジルメタタリレート： 54°C (327K)  Benzyl metatalylate: 54 ° C (327K)
ラウリルメタタリレート：一65°C (208K)  Lauryl metatalylate: 65 ° C (208K)
メチルメタタリレート： 105°C (378K)  Methyl metatalylate: 105 ° C (378K)
ヒドロキシェチルメタタリレート： 55°C (328K)  Hydroxyethyl methacrylate: 55 ° C (328K)
2—ヒドロキシプロピルメタタリレート： 26°C (299K)  2-Hydroxypropylmetatalylate: 26 ° C (299K)
アクリル酸： 105°C (378K)  Acrylic acid: 105 ° C (378K)
メタクリル酸： 130°C (403K)  Methacrylic acid: 130 ° C (403K)
スチレン： 100。C (373K)  Styrene: 100. C (373K)
[0056] 上記方法で計算を行うと、 n—ブチルメタタリレート 100部及びベンジルメタクリレー ト 100部を用いて合成したエチレン性不飽和単量体をラジカル重合してなるビュル重 合体部分のガラス転移温度は 36. 1°Cとなる。 [0056] When the calculation is performed by the above method, the glass of the buule polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer synthesized using 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate. The transition temperature is 36.1 ° C.
[0057] 片末端領域に 2つの水酸基を有するビニル重合体は、本発明の分子内に 2つの水 酸基と 1つのチオール基とを有する化合物の存在下にエチレン性不飽和単量体をラ ジカル重合する方法のほかにも以下の方法でも得ることができる。 [0058] 〔1〕片末端領域に (メタ)アクリル基を 1つ有する榭脂と、 1つのァミンと 2つの水酸基と を有する化合物とをマイケル付加させる方法 [0057] A vinyl polymer having two hydroxyl groups in one terminal region is obtained by laminating an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule of the present invention. In addition to the method of dical polymerization, the following method can also be used. [1] A method of Michael addition of a resin having one (meth) acrylic group in one end region and a compound having one amine and two hydroxyl groups
〔2〕片末端領域にカルボン酸基を 1つ有する榭脂と、 1つのエポキシ基と 1つの水酸 基とを有する化合物とをエポキシ付加させる方法  [2] Method of epoxy addition of a resin having one carboxylic acid group at one end region and a compound having one epoxy group and one hydroxyl group
〔3〕片末端領域にビニルエーテル基を 1つ有する榭脂と、 1つのカルボン酸基と 2つ の水酸基とを有する化合物とを付加させる方法  [3] Method of adding a resin having one vinyl ether group in one end region and a compound having one carboxylic acid group and two hydroxyl groups
〔4〕重合開始剤に 2つの水酸基を有する重合開始剤を用いて、ラジカル重合又は、 原子移動型ラジカル重合 (リビングラジカル重合)を行う方法  [4] A method of performing radical polymerization or atom transfer radical polymerization (living radical polymerization) using a polymerization initiator having two hydroxyl groups as a polymerization initiator
とがある。  There is.
これらの方法を用いることで片末端領域に 2つの水酸基を有する榭脂の合成が可 能であるが、多段階反応になってしまう場合が多いことや、分子量の制御が困難であ る場合が多ぐ生産性の面からも 2つの水酸基と 1つのチオール基とを有する化合物 の存在下にエチレン性不飽和単量体をラジカル重合する方法力 Sもっとも好ましい。  By using these methods, it is possible to synthesize a resin having two hydroxyl groups in one end region, but there are many cases where a multi-step reaction occurs and it is difficult to control the molecular weight. From the standpoint of productivity, the method power S for radical polymerization of ethylenically unsaturated monomers in the presence of a compound having two hydroxyl groups and one thiol group is most preferable.
[0059] まず、片末端領域に 2つの水酸基を有するビニル重合体 (a)を製造する工程 Al〜 A4について説明する。片末端領域に 2つの水酸基を有するビニル重合体 (a)は、分 子内に 2つの水酸基と 1つのチオール基とを有する化合物の存在下に、エチレン性 不飽和単量体をラジカル重合することで得ることができる。  [0059] First, steps Al to A4 for producing a vinyl polymer (a) having two hydroxyl groups in one terminal region will be described. A vinyl polymer (a) having two hydroxyl groups at one end region is obtained by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. Can be obtained at
[0060] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物としては、例えば、 1 メルカプト 1, 1 メタンジオール、 1 メルカプト 1 , 1 エタンジオール、 3 メル カプト 1, 2—プロパンジオール（チォグリセリン）、 2—メルカプト 1, 2—プロパン ジオール、 2 メルカプト 2—メチルー 1, 3 プロパンジオール、 2 メルカプト 2 ーェチルー 1, 3 プロパンジオール、 1 メルカプト 2, 2 プロパンジオール、 2 メルカプトェチルー 2—メチルー 1, 3 プロパンジオール、 2 メルカプトェチルー 2 ェチルー 1, 3 プロパンジオール、等が挙げられる。  [0060] Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1 mercapto 1,1 methanediol, 1 mercapto 1,1 ethanediol, 3 mercapto 1,2-propanediol (thiol). Glycerin), 2-mercapto 1,2-propanediol, 2 mercapto 2-methyl-1,3-propanediol, 2 mercapto-2-ethyl-1,3 propanediol, 1 mercapto 2,2-propanediol, 2 mercaptoethyl 2-methyl-1- , 3 propanediol, 2 mercaptoethyl-2-ethyl-1,3 propanediol, and the like.
[0061] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物を、目的とするビニル 重合体 (a)の分子量にあわせて、エチレン性不飽和単量体と、任意に重合開始剤と を混合して加熱することでビュル重合体 (a)を得ることができる。 2つの水酸基と 1つ のチオール基とを有する化合物は、エチレン性不飽和単量体 100重量部に対して、 1〜30重量部を用い、塊状重合又は溶液重合を行うのが好ましぐより好ましくは 3〜 12重量部、更に好ましくは 4〜12重量部、特に好ましくは 5〜9重量部である。反応 温度は 40〜150°C、好ましくは 50〜110°Cである。 [0061] According to the molecular weight of the target vinyl polymer (a), an ethylenically unsaturated monomer, and optionally a polymerization initiator, a compound having two hydroxyl groups and one thiol group in the molecule The bull polymer (a) can be obtained by mixing and heating. The compound having two hydroxyl groups and one thiol group is based on 100 parts by weight of ethylenically unsaturated monomer. It is preferable to perform bulk polymerization or solution polymerization using 1 to 30 parts by weight, more preferably 3 to 12 parts by weight, still more preferably 4 to 12 parts by weight, and particularly preferably 5 to 9 parts by weight. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C.
[0062] 重合の際、エチレン性不飽和単量体 100重量部に対して、任意に 0. 001〜5重量 部の重合開始剤を使用することができる。重合開始剤としては、ァゾ系化合物及び有 機過酸ィ匕物を用いることができる。ァゾ系化合物の例としては、 2, 2'—ァゾビスイソ ブチ口-トリル、 2, 2，—ァゾビス（2—メチルブチ口-トリル）、 1, 1，—ァゾビス（シクロ へキサン 1—カルボ-トリル）、 2, 2，—ァゾビス（2, 4 ジメチルバレ口-トリル）、 2, 2 ，一ァゾビス（2, 4 ジメチル一 4—メトキシバレロ二トリル）、ジメチル 2, 2'—ァゾビス (2 メチルプロピオネート）、 4, 4，ーァゾビス（4 シァノバレリック酸）、 2, 2，ーァゾ ビス（2—ヒドロキシメチルプロピオ-トリル）、 2, 2，—ァゾビス [2— (2—イミダゾリン— 2—ィル)プロパン]等が挙げられる。有機過酸ィ匕物の例としては、過酸化ベンゾィル 、 t ブチルパーべンゾエイト、タメンヒドロパーォキシド、ジイソプロピルパーォキシジ カーボネート、ジー n プロピノレバーオキシジカーボネート、ジ（2—エトキシェチル） パーォキシジカーボネート、 t ブチルパーォキシネオデカノエート、 t ブチルパー ォキシビバレート、 (3, 5, 5—トリメチルへキサノィル）パーォキシド、ジプロピオ-ル パーォキシド、ジァセチルバ一才キシド等があげられる。これらの重合開始剤は、単 独で、もしくは 2種類以上組み合わせて用いることができる。  [0062] In the polymerization, 0.005 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, azo compounds and organic peroxides can be used. Examples of azo compounds include 2,2'-azobisisobutyryl-tolyl, 2,2, -azobis (2-methylbutybutoxy-tolyl), 1,1, -azobis (cyclohexane 1-carbo-tolyl) ), 2, 2, -azobis (2,4 dimethylvale-tolyl), 2, 2, monoazobis (2,4 dimethyl-4-methoxyvaleronitryl), dimethyl 2,2'-azobis (2 methylpropio) Nate), 4, 4, azobis (4 cyanoberic acid), 2, 2, azobis (2-hydroxymethylpropio-tolyl), 2, 2, azobis [2- (2-imidazoline-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, tamen hydroperoxide, diisopropyl peroxydicarbonate, di-propinoliver oxydicarbonate, di (2-ethoxyethyl) per Examples include oxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropio-peroxide, dicetylba 1-year-old oxide. These polymerization initiators can be used alone or in combination of two or more.
[0063] 溶液重合の場合には、重合溶媒として、酢酸ェチル、酢酸 n プチル、酢酸イソブ チル、トルエン、キシレン、アセトン、へキサン、メチルェチルケトン、シクロへキサノン 等が用いられるが特にこれらに限定されるものではない。これらの重合溶媒は、 2種 類以上混合して用いても良 、。  [0063] In the case of solution polymerization, as a polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, etc. are used. It is not limited. These polymerization solvents may be used as a mixture of two or more.
[0064] エチレン性不飽和単量体としては、例えば、メチル (メタ）アタリレート、ェチル (メタ） アタリレート、 n—プロピル (メタ）アタリレート、イソプロピル (メタ）アタリレート、 n—ブチ ル (メタ）アタリレート、イソブチル (メタ）アタリレート、 t—ブチル (メタ）アタリレート、 2— ェチルへキシル (メタ）アタリレート、シクロへキシル (メタ）アタリレート、ステアリル (メタ )アタリレート、ラウリル (メタ）アタリレート、テトラヒドロフルフリール (メタ）アタリレート、 イソボル-ル (メタ）アタリレート、フエ-ル (メタ）アタリレート、ベンジル (メタ）アタリレー ート、ォキセタン (メタ)アタリレート等、メトキシポリプロピレングリコール (メタ）アタリレー ト、エトキシポリエチレングリコール (メタ）アタリレート等のアルコキシポリアルキレング リコール (メタ）アタリレート類、（メタ）アクリルアミド、及び N, N—ジメチル (メタ）アタリ ルアミド、 N, N—ジェチル (メタ）アクリルアミド、 N—イソプロピル (メタ）アクリルアミド 、ダイアセトン (メタ）アクリルアミド、アタリロイルモルホリン等の N置換型 (メタ）アクリル アミド類、 N, N—ジメチルアミノエチル (メタ）アタリレート、 N, N—ジェチルアミノエチ ル (メタ）アタリレート等のアミノ基含有 (メタ)アタリレート類、（メタ)アクリロニトリル等の 二トリル類があげられる。 [0064] Examples of the ethylenically unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( (Meth) Atalylate, Isobutyl (Meth) Atalylate, t-Butyl (Meth) Atalylate, 2—Ethylhexyl (Meth) Atalylate, Cyclohexyl (Meth) Atalylate, Stearyl (Meth) Atalylate, Lauryl ( (Meth) Atarylate, Tetrahydrofurfuryl (Meth) Atarylate, Isobol (Meth) Atarylate, Phenol (Meth) Atarylate, Benzyl (Meth) Atrelyle , Oxetane (meth) acrylate, etc., methoxypolypropylene glycol (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate, such as ethoxy polyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-substituted (meth) acrylamides, such as N-dimethyl (meth) atrylamide, N, N-jetyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and attalyloylmorpholine, N , N-dimethylaminoethyl (meth) acrylate, N, N-jetylaminoethyl (meth) acrylate, etc. (meth) acrylate, nitriles such as (meth) acrylonitrile .
[0065] また、上記アクリル単量体と併用できる単量体として、スチレン、 aーメチルスチレン 等のスチレン類、ェチルビニルエーテル、 n—プロピルビニルエーテル、イソプロピル ビニルエーテル、 n—ブチルビニルエーテル、イソブチルビニルエーテル等のビニル エーテル類、酢酸ビニル、プロピオン酸ビニル等の脂肪酸ビュル類があげられる。 [0065] Examples of monomers that can be used in combination with the above acrylic monomers include styrenes such as styrene and a-methylstyrene, vinyl ethers such as ethyl vinyl ether, n -propyl vinyl ether, isopropyl vinyl ether, n -butyl vinyl ether, and isobutyl vinyl ether. And fatty acid burs such as vinyl acetate and vinyl propionate.
[0066] また、カルボキシル基含有エチレン性不飽和単量体を併用することもできる。カル ボキシル基含有エチレン性不飽和単量体としては、アクリル酸、メタクリル酸、ィタコン 酸、マレイン酸、フマール酸、クロトン酸などから 1種又は 2種以上を選択することがで きる。  [0066] In addition, a carboxyl group-containing ethylenically unsaturated monomer may be used in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or more kinds can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.
[0067] 本発明にお!/、ては、上記に例示したエチレン性不飽和単量体の中でも、ベンジル ( メタ)アタリレートを単量体全体に対して 20重量％〜70重量％使用するのが好ましく 、より好ましくは 30〜60重量％である。 20重量％未満では、溶媒親和性が低くなり、 十分な立体反発効果が得られず、顔料分散性が低下する場合があり、 70重量％を 超えると、ベンジル部と顔料とが相互作用してしまい、顔料分散性が低下する場合が ある。  [0067] In the present invention, among the ethylenically unsaturated monomers exemplified above, benzyl (meth) acrylate is used in an amount of 20 to 70% by weight based on the whole monomer. It is preferably 30 to 60% by weight. If it is less than 20% by weight, the solvent affinity becomes low, and sufficient steric repulsion effect cannot be obtained, and the pigment dispersibility may decrease. If it exceeds 70% by weight, the benzyl part and the pigment interact with each other. As a result, the pigment dispersibility may decrease.
[0068] 更に本発明においては、上記に例示したエチレン性不飽和単量体の中でも、下記 一般式 (3)で表わされる単量体を使用することが好ま 、。下記一般式 (3)で表され る単量体の使用量は、単量体全体に対して 20重量％〜100重量％が好ましぐ 20 〜70重量％がより好ましい。一般式 (3)で表わされる単量体を用いると、溶媒親和性 が良くなり、顔料分散性が良好になる。 [0069] 一般式（3) Furthermore, in the present invention, among the ethylenically unsaturated monomers exemplified above, it is preferable to use a monomer represented by the following general formula (3). The amount of the monomer represented by the following general formula (3) is preferably 20 to 70% by weight, more preferably 20 to 100% by weight, based on the whole monomer. When the monomer represented by the general formula (3) is used, the solvent affinity is improved and the pigment dispersibility is improved. [0069] General formula (3)
[化 22]
Figure imgf000021_0001
[Chemical 22]
Figure imgf000021_0001
[一般式 (3)中、 Rは、炭素原子数 1〜4の直鎖状若しくは分岐状のアルキル基であ る。]  [In the general formula (3), R represents a linear or branched alkyl group having 1 to 4 carbon atoms. ]
[0070] 次に、片末端領域に 2つの水酸基を有するビニル重合体 (a)とテトラカルボン酸無 水物 (b)とを反応させる工程 B1〜B4について説明する。本発明のポリエステル分散 剤は、工程 A1〜A4で得られた片末端領域に 2つの水酸基を有するビニル重合体（ a)の水酸基と、テトラカルボン酸無水物 (b)の酸無水物基とを反応させる（工程 Bl〜 B4)ことにより得られる。  [0070] Next, steps B1 to B4 in which the vinyl polymer (a) having two hydroxyl groups in one terminal region and the tetracarboxylic acid anhydride (b) are reacted will be described. The polyester dispersant of the present invention comprises a hydroxyl group of a vinyl polymer (a) having two hydroxyl groups in one end region obtained in steps A1 to A4, and an acid anhydride group of a tetracarboxylic acid anhydride (b). It is obtained by reacting (Steps Bl to B4).
[0071] 本発明で使用されるテトラカルボン酸無水物 (b)としては、 1, 2, 3, 4 ブタンテトラ カルボン酸無水物、 1, 2, 3, 4 シクロブタンテトラカルボン酸無水物、 1, 3 ジメチ ルー 1, 2, 3, 4ーシクロブタンテトラカルボン酸無水物、 1, 2, 3, 4ーシクロペンタン テトラカルボン酸無水物、 2, 3, 5 トリカルボキシシクロペンチル酢酸無水物、 3, 5 , 6 トリカルボキシノルボルナン一 2 酢酸無水物、 2, 3, 4, 5—テトラヒドロフラン テトラカルボン酸無水物、 5—（2, 5 ジォキソテトラヒドロフラル）ー3—メチルー 3— シクロへキセン一 1, 2 ジカルボン酸無水物、ビシクロ [2, 2, 2]—オタトー 7 ェン - 2, 3, 5, 6—テトラカルボン酸無水物などの脂肪族テトラカルボン酸無水物； ピロメリット酸無水物、エチレングリコールジ無水トリメリット酸エステル、プロピレングリ コールジ無水トリメリット酸エステル、ブチレングリコールジ無水トリメリット酸エステル、 3, 3' , 4, 4，一べンゾフエノンテトラカルボン酸無水物、 3, 3' , 4, 4，ービフエ-ルス ルホンテトラカルボン酸無水物、 1, 4, 5, 8 ナフタレンテトラカルボン酸無水物、 2, 3, 6, 7—ナフタレンテトラカルボン酸無水物、 3, 3' , 4, 4，ービフエ-ルエーテルテ トラカルボン酸無水物、 3, 3' , 4, 4'ージメチルジフエ-ルシランテトラカルボン酸無 水物、 3, 3' , 4, 4'ーテトラフエニルシランテトラカルボン酸無水物、 1, 2, 3, 4ーフ ランテトラカルボン酸無水物、 4, 4 '—ビス（3, 4—ジカルボキシフエノキシ）ジフエ- ルスルフイド無水物、 4, 4'—ビス（3, 4—ジカルボキシフエノキシ）ジフエ-ルスルホ ン無水物、 4, 4，—ビス（3, 4—ジカルボキシフエノキシ）ジフエ-ルプロパン無水物、 3, 3' , 4, 4，—パーフルォロイソプロピリデンジフタル酸無水物、 3, 3' , 4, 4，ービフ ェ -ルテトラカルボン酸無水物、ビス（フタル酸）フエ-ルホスフィンオキサイド無水物 、 p フエ-レン一ビス（トリフエ-ルフタル酸）無水物、 m—フエ-レン一ビス（トリフエ -ルフタル酸）無水物、ビス（トリフエ-ルフタル酸） 4, 4，ージフエ-ルエーテル無 水物、ビス（トリフエ-ルフタル酸）—4, 4，ージフエ-ルメタン無水物、 9, 9 ビス（3, 4ージカルボキシフエ-ル）フルオレン酸無水物、 9, 9 ビス [4— (3, 4—ジカルボキ シフエノキシ）フエ-ル]フルオレン酸無水物、 3, 4 ジカルボキシ 1, 2, 3, 4ーテ トラヒドロー 1 ナフタレンコハク酸無水物、 3, 4 ジカルボキシ 1, 2, 3, 4ーテトラ ヒドロ 6—メチルー 1 ナフタレンコハク酸無水物、などの芳香族テトラカルボン酸 無水物が挙げられる。 [0071] The tetracarboxylic acid anhydride (b) used in the present invention includes 1, 2, 3, 4 butanetetracarboxylic acid anhydride, 1, 2, 3, 4 cyclobutanetetracarboxylic acid anhydride, 1, 3 Dimethyl 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentane tetracarboxylic anhydride, 2,3,5 tricarboxycyclopentylacetic anhydride, 3,5,6 tricarboxy Norbornane-2-acetic anhydride, 2, 3, 4, 5-tetrahydrofuran tetracarboxylic anhydride, 5- (2,5 dioxotetrahydrofural) -3-methyl-3-cyclohexene 1,2-dicarboxylic anhydride , Bicyclo [2, 2, 2] -Otato 7-en 2, 2, 5, 5, 6-tetracarboxylic anhydride and other aliphatic tetracarboxylic anhydrides; pyromellitic anhydride, ethylene glycol dianhydride tri Mellitic acid ester, propire Glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3, 3 ', 4, 4, monobenzophenone tetracarboxylic anhydride, 3, 3', 4, 4, bibisulfurone Tetracarboxylic acid anhydride, 1, 4, 5, 8 Naphthalenetetracarboxylic acid anhydride, 2, 3, 6, 7-Naphthalenetetracarboxylic acid anhydride, 3, 3 ', 4, 4, Biphenyl ether tetracarboxylic acid Anhydride, 3, 3 ', 4, 4'-dimethyldiphenylsilane tetracarboxylic acid anhydrous, 3, 3', 4, 4'-tetraphenylsilane tetracarboxylic acid anhydride, 1, 2, 3, 4 -Furanetetracarboxylic anhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenol Rulsulfide anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfonate anhydride, 4,4, -bis (3,4-dicarboxyphenoxy) diphenylpropane anhydride 3, 3 ', 4, 4,-Perfluoroisopropylidenediphthalic anhydride, 3, 3', 4, 4, biphenyl tetracarboxylic anhydride, bis (phthalic acid) phenol Phosphine oxide anhydride, p-Phenylene monobis (triphenylphthalic acid) anhydride, m-Phenylene monobis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) 4, 4, diphenyl ether Anhydrous, bis (tri-phthalphthalic acid) —4,4, -diphenylmethane anhydride, 9,9 bis (3,4-dicarboxyphenyl) fluorenic anhydride, 9,9 bis [4— ( 3, 4-dicarboxylphenoxy) phenol] fluorenic anhydride, 3, 4 dicarboxy 1, Aromatic tetracarboxylic anhydrides such as 2, 3, 4-tetrahydro-1 naphthalene succinic anhydride, 3, 4 dicarboxy 1, 2, 3, 4-tetrahydro 6-methyl-1 naphthalene succinic anhydride It is done.
[0072] 本発明で使用されるテトラカルボン酸無水物は上記に例示したィ匕合物に限らず、力 ルボン酸無水物基を 2つ持てばどのような構造をして!/ヽても力まわな!、。これらは単 独で用いても、併用しても力まわない。更に、本発明に好ましく使用されるものは、顔 料分散体の低粘度化の観点から芳香族テトラカルボン酸無水物であり、更に好ましく は芳香族環を二つ以上有するテトラカルボン酸無水物である。また、分子中にカルボ ン酸無水物基を 1つ持つ化合物や 3つ以上持つ化合物を併用することができる。  [0072] The tetracarboxylic acid anhydride used in the present invention is not limited to the compound exemplified above, and any structure having two forceful rubonic acid anhydride groups can be used! Powerful! These can be used alone or in combination. Further, what is preferably used in the present invention is an aromatic tetracarboxylic acid anhydride from the viewpoint of reducing the viscosity of the pigment dispersion, more preferably a tetracarboxylic acid anhydride having two or more aromatic rings. is there. In addition, a compound having one carboxylic anhydride group in the molecule or a compound having three or more can be used in combination.
[0073] 分子中にカルボン酸無水物基を 1つ持つ化合物を併用するのが好ましぐ分子中 にカルボン酸無水物基を 1つ持つ化合物の中では、トリカルボン酸無水物がより好ま しい。下記の反応工程式（11)に示す生成物のコア部分 X4に結合しているカルボキ シル基が 2個となるため分散安定ィ匕が可能となる。なお、下記反応工程式（11)にお いて、 HO— Y，— OHはポリオール化合物である。 [0073] Among the compounds having one carboxylic anhydride group in the molecule, it is preferable to use a compound having one carboxylic anhydride group in the molecule, and tricarboxylic anhydride is more preferable. Since there are two carboxy groups bonded to the core part X 4 of the product shown in the following reaction process formula (11), dispersion stability can be achieved. In the following reaction process formula (11), HO—Y, —OH is a polyol compound.
[0074] 反応工程式（11)  [0074] Reaction process formula (11)
[化 23]  [Chemical 23]
HO― Υ'— OH + 2 | θ' Χ4 ] HO― Υ'— OH + 2 | θ 'Χ 4 ]
HO— C
Figure imgf000022_0001
[0075] トリカルボン酸無水物としては、まず、脂肪族トリカルボン酸無水物、又は芳香族トリ カルボン酸無水物が挙げられる。 HO— C
Figure imgf000022_0001
[0075] Examples of tricarboxylic acid anhydrides include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.
[0076] 脂肪族トリカルボン酸無水物としては、例えば、 3 カルボキシメチルダルタル酸無 水物、 1, 2, 4 ブタントリカルボン酸 1, 2 無水物、 cis プロペン—1, 2, 3 ト リカルボン酸 1, 2 無水物、 1, 3, 4ーシクロペンタントリカルボン酸無水物などが 挙げられる。 [0076] Examples of the aliphatic tricarboxylic acid anhydride include, for example, 3 carboxymethyldaltaric acid anhydrous, 1, 2, 4 butanetricarboxylic acid 1, 2 anhydride, cis propene-1, 2, 3 tricarboxylic acid 1 , 2 anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride and the like.
[0077] 芳香族トリカルボン酸としては、例えば、ベンゼントリカルボン酸無水物（1, 2, 3— ベンゼントリカルボン酸無水物、トリメリット酸無水物 [1, 2, 4 ベンゼントリカルボン 酸無水物]など）、ナフタレントリカルボン酸無水物（1, 2, 4 ナフタレントリカルボン 酸無水物、 1, 4, 5 ナフタレントリカルボン酸無水物、 2, 3, 6 ナフタレントリカル ボン酸無水物、 1, 2, 8 ナフタレントリカルボン酸無水物など）、 3, 4, 4'一べンゾフ エノントリカルボン酸無水物、 3, 4, 4，ービフエ-ルエーテルトリカルボン酸無水物、 3 , 4, 4，ービフエ-ルトリカルボン酸無水物、 2, 3, 2，ービフエ-ルトリカルボン酸無水 物、 3, 4, 4，—ビフエ-ルメタントリカルボン酸無水物、 3, 4, 4，—ビフエ-ルスルホ ントリカルボン酸無水物などが挙げられる。トリカルボン酸無水物を使用する場合、上 記のうち芳香族トリカルボン酸無水物が特に好ましい。  [0077] As the aromatic tricarboxylic acid, for example, benzenetricarboxylic acid anhydride (1, 2, 3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1, 2, 4 benzenetricarboxylic acid anhydride], etc.), Naphthalene tricarboxylic acid anhydride (1, 2, 4 naphthalene tricarboxylic acid anhydride, 1, 4, 5 naphthalene tricarboxylic acid anhydride, 2, 3, 6 naphthalene tricarboxylic acid anhydride, 1, 2, 8 naphthalene tricarboxylic acid anhydride 3, 4, 4 'monobenzophenone tricarboxylic acid anhydride, 3, 4, 4, biphenyl ether tricarboxylic acid anhydride, 3, 4, 4, biphenyl tricarboxylic acid anhydride, 2, 3 1, 2, -biphenyl tricarboxylic acid anhydride, 3, 4, 4, -biphenyl methane tricarboxylic acid anhydride, 3, 4, 4,-biphenyl sulfonic tricarboxylic acid anhydride. In the case of using a tricarboxylic acid anhydride, an aromatic tricarboxylic acid anhydride is particularly preferable among the above.
[0078] 本発明では、工程 B2及び工程 B4にお 、て、任意の割合で、前記ビニル重合体 (a )以外のポリオール化合物（c)を用いることが可能である。前記ビニル重合体 (a)以 外のポリオ一ルイ匕合物（c)を用いることで、カルボン酸基の密度や、溶剤溶解部の割 合の調整が容易になる。  In the present invention, it is possible to use a polyol compound (c) other than the vinyl polymer (a) in an arbitrary ratio in the step B2 and the step B4. By using a polyol compound (c) other than the vinyl polymer (a), it becomes easy to adjust the density of the carboxylic acid group and the proportion of the solvent-soluble portion.
[0079] 本発明に使用する「前記ビニル重合体 (a)以外のポリオール化合物（c)」としては、 公知のものを使用することができ、例えば、 1分子中に水酸基 2〜4個を有するポリオ 一ルイ匕合物を使用することができる。それらのうちでも、特に代表的なもののみを例 示するにとどめれば、次のグループ（1)〜（7)に属するものがある。  [0079] As the "polyol compound (c) other than the vinyl polymer (a)" used in the present invention, a known one can be used. For example, it has 2 to 4 hydroxyl groups in one molecule. Polio-Iloui compound can be used. Among them, there are those belonging to the following groups (1) to (7) if only typical ones are illustrated.
[0080] (1)エチレングリコール、プロピレングリコール、 1, 3 プロパンジオール、 1, 4ーブタ ンジオール、 1, 3 ブタンジオール、 1, 5 ペンタンジオール、ネオペンチルグリコ ール、 1, 6 へキサンジオール、 1, 4 ビス（ヒドロキシメチル）シクロへサン、ビスフ エノール八、水添ビスフエノール A、ヒドロキシピノくリルヒドロキシビバレート、トリメチロ ールェタン、トリメチロールプロパン、 2, 2, 4 トリメチルー 1, 3 ペンタンジオール 、グリセリンもしくは、へキサントリオールの如き多価アルコール類； [0080] (1) Ethylene glycol, propylene glycol, 1,3 propanediol, 1,4-butanediol, 1,3 butanediol, 1,5 pentanediol, neopentyl glycol, 1,6 hexanediol, 1 , 4 Bis (hydroxymethyl) cyclohexane, Bisphenol 8, Hydrogenated bisphenol A, Hydroxypinolyl hydroxybivalate, Trimethylo Polyhydric alcohols such as ruetane, trimethylolpropane, 2,2,4 trimethyl-1,3 pentanediol, glycerin or hexanetriol;
[0081] (2)ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシェチレ ンポリオキシテトラメチレングリコール、ポリオキシプロピレンポリオキシテトラメチレング リコーノレもしくは、ポリオキシエチレンポリオキシプロピレンポリオキシテトラメチレンダリ コールの如き、各種のポリエーテルグリコール類； [0081] (2) Polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol, Various polyether glycols;
[0082] (3)上記した各種の多価アルコール類と、エチレンォキシド、プロピレンォキシド、テト ラヒドロフラン、ェチルダリシジルエーテル、プロピルグリシジルエーテル、ブチルグリ シジルエーテル、フエ-ルグリシジルエーテル又はァリルグリシジルエーテルの如き 各種の（環状)エーテル結合含有ィ匕合物との開環重合によって得られる変性ポリエー テルポリオール類； [0082] (3) Various polyhydric alcohols described above and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl daricidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenol glycidyl ether or aryl glycidyl. Modified polyether polyols obtained by ring-opening polymerization with various (cyclic) ether bond-containing compounds such as ethers;
[0083] (4)上記した各種の多価アルコール類の 1種以上と、多価カルボン酸類との共縮合 によって得られるポリエステルポリオール類であって、多価カルボン酸類力 コハク酸 、アジピン酸、セバシン酸、ァゼライン酸、フタル酸、テトラヒドロフタル酸、へキサヒド ロフタル酸、マレイン酸、フマル酸、シトラコン酸、ィタコン酸、グルタコン酸、 1, 2, 5 一へキサントリカルボン酸、 1, 4ーシクロへキサンヒカルボン酸、 1, 2, 4 ベンゼント リカルボン酸、 1, 2, 5 ベンゼントリカルボン酸、 1, 2, 4 シクロへキサトリカルボン 酸又は 2, 5, 7 ナフタレントリカルボン酸などで特に代表されるものを用いて得られ るポリオール類；  [0083] (4) Polyester polyols obtained by co-condensation of one or more of the above-mentioned various polyhydric alcohols with polyvalent carboxylic acids, which are polyvalent carboxylic acids such as succinic acid, adipic acid, sebacin Acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1, 2, 5 monohexanetricarboxylic acid, 1,4-cyclohexanehical By using those specifically represented by boric acid, 1, 2, 4 benzene tricarboxylic acid, 1, 2, 5 benzene tricarboxylic acid, 1, 2, 4 cyclohexatricarboxylic acid or 2, 5, 7 naphthalene tricarboxylic acid Resulting polyols;
[0084] (5)上記した各種の多価アルコール類の 1種以上と、 ε—力プロラタトン、 δ バレロ ラタトンもしくは 3—メチルー δ—バレロラタトンの如き各種のラタトン類との重縮合反 応によって得られるラタトン系ポリエステルポリオール類、あるいは、  [0084] (5) Obtained by polycondensation reaction of one or more of the above-described various polyhydric alcohols with various ratatones such as ε-force prolatatatone, δ valero latatatone, or 3-methyl-δ-valerolatataton. Rataton-based polyester polyols, or
上記した各種の多価アルコール類と、多価カルボン酸類と、各種のラタトン類との重 縮合反応によって得られるラタトン変性ポリエステルポリオール類；  Rataton-modified polyester polyols obtained by polycondensation reaction of the various polyhydric alcohols, polycarboxylic acids and various latatones;
[0085] (6)ビスフエノール Α型エポキシ化合物、水添ビスフエノール A型エポキシ化合物、一 価及び Z又は多価アルコール類のグリシジルエーテル、あるいは、一塩基酸及び Z 又は多塩基酸類のグリシジルエステルの如き各種のエポキシ化合物を、ポリエステル ポリオールの合成時に、 1種以上併用して得られるエポキシ変性ポリエステルポリオ 一ノレ類； [0085] (6) Bisphenol Α type epoxy compound, hydrogenated bisphenol A type epoxy compound, glycidyl ether of monovalent and Z or polyhydric alcohols, or monobasic acid and glycidyl ester of Z or polybasic acids Epoxy-modified polyester polyols obtained by using one or more of these epoxy compounds together in the synthesis of polyester polyols. One nore;
[0086] (7)ポリエステルポリアミドポリオール、ポリカーボネートポリオール、ポリブタジエンポ リオール、ポリペンタジエンポリオール、ひまし油、ひまし油誘導体、水添ひまし油、 水添ひまし油誘導体、水酸基含有アクリル系共重合体、水酸基含有含フッ素化合物 又は水酸基含有シリコン榭脂などが挙げられる。  [0086] (7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound or hydroxyl group Examples thereof include silicon resin.
[0087] これら（1)〜（7)に示された任意に添加する、前記ビニル重合体 (a)以外のポリオ ール化合物（c)は、単独使用でも 2種以上の併用でもよいことは勿論である力 その 重量平均分子量としては、 40〜： LOOOO力 S好ましく、より好ましくは、 100〜2000であ り、更に好ましくは、 100〜 1000である。  [0087] The polyol compound (c) other than the vinyl polymer (a) optionally added as shown in (1) to (7) may be used alone or in combination of two or more. Needless to say, the weight average molecular weight is 40 to: LOOOO force S, preferably 100 to 2000, and more preferably 100 to 1000.
[0088] 本発明のポリエステル分散剤の製造に用いられる触媒としては、公知の触媒を使 用することができる。触媒としては 3級ァミン系化合物が好ましぐ例えばトリェチルァ ミン、トリエチレンジァミン、 N, N—ジメチルベンジルァミン、 N—メチルモルホリン、 1 , 8—ジァザビシクロ一 [5. 4. 0]— 7—ゥンデセン、 1, 5—ジァザビシクロ一 [4. 3. 0 ]一 5—ノネン等が挙げられる。  [0088] As the catalyst used for the production of the polyester dispersant of the present invention, a known catalyst can be used. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] — 7-undecene, 1,5-diazabicyclo [4.3.0] 1-5-nonene, and the like.
[0089] 本発明のポリエステル分散剤は、これまで挙げた原料のみで製造することも可能で あるが、高粘度になり反応が不均一になるなどの問題を回避すベぐ溶剤を用いるの が好ましい。使用される溶剤としては、公知のものを使用できる。例えば、アセトン、メ チルェチルケトン、メチルイソブチルケトン、シクロへキサノン、酢酸ェチル、酢酸ブチ ル、トルエン、キシレン、ァセトニトリル等が挙げられる。反応に使用した溶媒は、反応 終了後、蒸留等の操作により取り除くか、あるいはそのまま製品の一部として使用す ることちでさる。  [0089] The polyester dispersant of the present invention can be produced using only the raw materials listed above, but it is preferable to use a solvent that avoids problems such as high viscosity and non-uniform reaction. preferable. As the solvent to be used, known solvents can be used. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butylacetate, toluene, xylene, and acetonitrile. The solvent used for the reaction can be removed by distillation or other operation after the completion of the reaction, or used as part of the product.
[0090] 本発明のポリエステル分散剤は、片末端領域に 2つの水酸基を有するビニル重合 体 (a)、テトラカルボン酸無水物 (b)及び任意に添加する「前記ビニル重合体 (a)以 外のポリオール化合物（c)」を反応させることで得られる。テトラカルボン酸無水物 (b) 中の酸無水物基と、ビニル重合体 (a)及び「前記ビニル重合体 (a)以外のポリオール 化合物（c)」中の水酸基とのモル比は、 (b) / [ (a) + (c) ] =0. 3〜1. 2が好ましく、 より好ましくは (b) Z [ (a) + (c) ] = 0. 4〜： L . 1、更に好ましくは (b) / [ (a) + (c) ] = 0. 5〜1. 0、特に好ましくは(1)) 7 [ (&) + (。）] =0. 6〜0. 8の場合である。 (b) / [ ( a) + (c)]> 1で反応させる場合は、残存する酸無水物基を必要量の水で加水分解 して使用してもよい。 0. 3未満であると、顔料吸着部である酸無水物残基が少なくな る場合があり、また樹脂の酸価も低くなる場合もある。また 1. 2を超えるとポリエステル に酸無水物基が残ってしま、、榭脂の保存安定性に問題が起きてしまう場合がある。 また残存する酸無水物基を加水分解するのに必要な水の量が多くなつてしまい溶剤 溶解性が悪ィ匕する場合がある。 [0090] The polyester dispersant of the present invention comprises a vinyl polymer (a) having two hydroxyl groups in one terminal region, a tetracarboxylic acid anhydride (b), and an optional addition "other than the vinyl polymer (a). It is obtained by reacting the polyol compound (c) ”. The molar ratio of the acid anhydride group in the tetracarboxylic acid anhydride (b) to the hydroxyl group in the vinyl polymer (a) and the “polyol compound (c) other than the vinyl polymer (a)” is (b ) / [(a) + (c)] = 0.3 to 1.2, more preferably (b) Z [(a) + (c)] = 0.4 to: L.1, more preferably (B) / [(a) + (c)] = 0.5 to 1.0, particularly preferably (1)) 7 [(&) + (.)] = 0.6 to 0.8 It is. (b) / [( In the case of a) + (c)]> 1, the remaining acid anhydride group may be hydrolyzed with a necessary amount of water and used. If it is less than 0.3, the acid anhydride residue as the pigment adsorbing portion may be decreased, and the acid value of the resin may be decreased. On the other hand, if it exceeds 1.2, acid anhydride groups remain in the polyester, which may cause problems in storage stability of the resin. In addition, the amount of water necessary to hydrolyze the remaining acid anhydride groups may increase, resulting in poor solvent solubility.
[0091] 更に、本発明のポリエステル分散剤は片末端領域に 2つの水酸基を有するビニル 重合体 (a)、テトラカルボン酸無水物 (b)、任意に添加する（a)以外のポリオ一ルイ匕 合物（c)及びトリカルボン酸無水物（d)を反応させることで得られる。テトラカルボン酸 無水物 (b)及びトリカルボン酸 (d)中の酸無水物基と、ビニル重合体 (a)及び (a)以 外のポリオール化合物（c)中の水酸基とのモル比は、 [(b) + (d)]/[(a) + (c)]=0 . 3〜1. 2が好ましぐょり好ましくは[(1))+ ((1)]7[(&) + ((：)]=0.4〜1. 1、更に 好ましくは [ (b) + (d) ] Z [ (a) + (c) ] = 0. 5〜 1.0、特に好ましくは [ (b) + (d)]/[ (a) + (c)]=0.6〜0.8である。 [0091] Further, the polyester dispersant of the present invention is a polyol polymer other than (a), a vinyl polymer (a) having two hydroxyl groups in one terminal region, a tetracarboxylic acid anhydride (b), and an optional addition (a). It can be obtained by reacting compound (c) and tricarboxylic anhydride (d). The molar ratio between the acid anhydride group in tetracarboxylic acid anhydride (b) and tricarboxylic acid (d) and the hydroxyl group in the polyol compound (c) other than vinyl polymers (a) and (a) is: (b) + (d)] / [(a) + (c)] = 0.3 to 1.2 is preferred, preferably [(1)) + ((1)] 7 [(&) + ( ( :)] = 0.4 to 1.1, more preferably [(b) + (d)] Z [(a) + (c)] = 0.5 to 1.0, particularly preferably [(b) + (d)] / [(a) + (c)] = 0.6 to 0.8.
[0092] 酸無水物としてテトラカルボン酸無水物（b)とトリカルボン酸無水物（d)を併用する 際のテトラカルボン酸無水物 (b)とトリカルボン酸無水物（d)のモル比は、（b) Z[ (d) ]=0. 1〜： LOが好ましぐより好ましくは (b)Z[(d)]=0. 15〜4、特に好ましくは (b) /[(d)]=0. 3〜2である。  [0092] When the tetracarboxylic acid anhydride (b) and the tricarboxylic acid anhydride (d) are used in combination as the acid anhydride, the molar ratio of the tetracarboxylic acid anhydride (b) to the tricarboxylic acid anhydride (d) is ( b) Z [(d)] = 0.1-1: More preferably LO (b) Z [(d)] = 0.15-4, particularly preferably (b) / [(d)] = 0.3-3.
[0093] 反応温度は 50°C〜180°C、好ましくは 80°C〜140°Cの範囲で行う。反応温度が 5 0°C以下では反応速度が遅ぐ 180°C以上ではカルボキシル基がエステルイ匕反応し てしまい、酸価の減少や、ゲルィ匕を起こしてしまう場合がある。反応の停止は、赤外 吸収で酸無水物の吸収がなくなるまで反応させるのが理想である力 酸価測定にて 95%以上の酸無水物がハーフエステルイ匕していることを確認した後、反応を止めて ちょい。  [0093] The reaction temperature is 50 ° C to 180 ° C, preferably 80 ° C to 140 ° C. When the reaction temperature is 50 ° C or lower, the reaction rate is slow. When the reaction temperature is 180 ° C or higher, the carboxyl group undergoes esterification reaction, which may cause a decrease in acid value or gelling. It is ideal to stop the reaction until there is no absorption of the acid anhydride by infrared absorption. After confirming that 95% or more of the acid anhydride is half-esterified by acid value measurement Stop the reaction.
[0094] 得られたポリエステル分散剤の重量平均分子量は、好ましくは、 2000〜35000よ り好まし <ίま 4000〜25000、更【こ好まし <ίま 6000〜20000、特【こ好まし <ίま 7000 〜 15000である。重量平均分子量が 2000未満であれば顔料組成物の安定性が低 下する場合があり、 35000を超えると榭脂間の相互作用が強くなり、顔料組成物の 増粘が起きる場合がある。また、得られたポリエステル分散剤の酸価は、 5〜200が 好ましい。より好ましくは 10〜150であり、更に好ましくは、 15〜： LOOであり、特に好ま しくは、 20〜80である。酸価が 5未満では、顔料吸着能が低下し顔料分散性に問題 がでる場合があり、 200を超えると、榭脂間の相互作用が強くなり顔料分散組成物の 粘度が高くなる場合がある。 [0094] The weight average molecular weight of the obtained polyester dispersant is preferably 2000 to 35000, more preferably <ί or 4000 to 25000, more preferably <ί or 6000 to 20000, particularly preferably < ί is between 7000 and 15000. If the weight average molecular weight is less than 2000, the stability of the pigment composition may decrease. Thickening may occur. The acid value of the obtained polyester dispersant is preferably 5 to 200. More preferably, it is 10-150, More preferably, it is 15-: LOO, Especially preferably, it is 20-80. When the acid value is less than 5, the pigment adsorbing ability may be lowered and the pigment dispersibility may be problematic. When the acid value exceeds 200, the interaction between the rosils may be increased and the viscosity of the pigment dispersion composition may be increased. .
[0095] 更に本発明では、分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al )とテトラカルボン酸無水物 (b)とチオール基を有さな 、ポリオール化合物（c' )とトリ カルボン酸無水物（d)とを反応させ化合物（a2)を製造する工程 B5〜B8と、 前記化合物（a2)の存在下に、残存して!/、る化合物（a2)のチオール基を連鎖移動 剤としてラジカル重合する工程 A5〜A8により、同様の構造の分散剤を得ることがで きる。 Furthermore, in the present invention, a compound (al) having two hydroxyl groups and one thiol group in the molecule, a tetracarboxylic acid anhydride (b), a polyol compound (c ′) having no thiol group, and Steps B5 to B8 for producing compound (a2) by reacting with tricarboxylic acid anhydride (d), and thiol group of compound (a2) remaining in the presence of compound (a2)! A dispersant having the same structure can be obtained by the steps A5 to A8 in which radical polymerization is performed as a chain transfer agent.
[0096] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)とテトラカルボン 酸無水物 (b)と、場合によりチオール基を有さないポリオ一ルイヒ合物 (c')と、更に場 合によりトリカルボン酸無水物 (d)とを反応させて化合物 (a2)〜 (a5)を製造する工程 B5〜： B8について説明する。  [0096] A compound having two hydroxyl groups and one thiol group in the molecule (al), a tetracarboxylic acid anhydride (b), and optionally a polyurich compound (c ') having no thiol group Further, Steps B5 to B8 in which compounds (a2) to (a5) are produced by further reacting with a tricarboxylic acid anhydride (d) in some cases will be described.
これらの化合物（a2)〜（a5)は、分子内に 2つの水酸基と 1つのチオール基とを有 する化合物（al)、テトラカルボン酸無水物 (b)、及び任意に添加する（a)以外のポリ オール化合物（c)、及び更に、任意に添加するトリカルボン酸無水物（d)を反応させ る工程 A1〜A4と同様の方法で得ることができる。テトラカルボン酸無水物 (b)とトリ力 ルボン酸無水物（d)中の酸無水物基と、分子内に 2つの水酸基と 1つのチオール基 とを有する化合物（al)及びチオール基を有さな!/、ポリオール化合物（c' )中の水酸 基とのモル比は、 [(b) + (d)]/[(a) + (c')]=0. 3〜1. 2が好ましぐより好ましく は [(b) + (d)]Z[(a) + (c，）]=0.4〜1. 1、更に好ましくは[03) + ((1)]7[( + (c，）]=0. 5〜1.0、特に好ましくは [(b) + (d)]Z[(a) + (c')]=0.6〜0.8の場 合である。 (b)/[(a) + ( ）] >1で反応させる場合は、残存する酸無水物基を必要 量の水で加水分解して使用してもよ!、。  These compounds (a2) to (a5) are compounds other than the compound (al) having two hydroxyl groups and one thiol group in the molecule (al), tetracarboxylic acid anhydride (b), and optionally added (a). The polyol compound (c) and the optionally added tricarboxylic acid anhydride (d) can be obtained in the same manner as in Steps A1 to A4. It has an acid anhydride group in tetracarboxylic acid anhydride (b) and triforce rubonic acid anhydride (d), a compound having two hydroxyl groups and one thiol group in the molecule (al), and a thiol group. The molar ratio with the hydroxyl group in the polyol compound (c ′) is [(b) + (d)] / [(a) + (c ′)] = 0.3-3 to 1.2 More preferably, [(b) + (d)] Z [(a) + (c,)] = 0.4 to 1.1, more preferably [03) + ((1)] 7 [(+ ( c,)] = 0 to 0.5 to 1.0, particularly preferably [(b) + (d)] Z [(a) + (c ′)] = 0.6 to 0.8. a) When reacting with + ()]> 1, the remaining acid anhydride groups may be hydrolyzed with the required amount of water!
[0097] 次に、前記化合物（a2)〜（a5)の存在下に、残存して!/、る化合物（a2)〜（a5)中の チオール基を用いたエチレン性不飽和単量体をラジカル重合させる工程 A5〜A8に っ 、て説明する。片末端領域に 2つの水酸基を有するビニル重合体 (a)を製造する 工程 A1〜A4と同様の方法で得られ、残存するチオール基を連鎖移動剤として用い 、目的とする分散剤の分子量にあわせて、エチレン性不飽和単量体を任意に重合開 始剤とを混合して加熱することで分散剤が得られる。工程 B5〜B8にて使用した分子 内に 2つの水酸基と 1つのチオール基とを有する化合物（al) 1重量部に対して、ェ チレン性不飽和単量体を 3〜： LOO重量部用い、塊状重合又は溶液重合を行うのが好 ましい。より好ましくは 8〜25重量部、更に好ましくは 10〜20重量部である。反応温 度は 40〜150°C、好ましくは 50〜110°Cである。 Next, an ethylenically unsaturated monomer using a thiol group in the remaining compounds (a2) to (a5) is left in the presence of the compounds (a2) to (a5). Radical polymerization process A5-A8 I will explain. Process for producing vinyl polymer (a) having two hydroxyl groups in one end region (a) Obtained by the same method as in A1 to A4, using the remaining thiol group as a chain transfer agent, and adjusting to the molecular weight of the intended dispersant. Then, an ethylenically unsaturated monomer is optionally mixed with a polymerization initiator and heated to obtain a dispersant. For 1 part by weight of the compound (al) having two hydroxyl groups and one thiol group in the molecule used in Steps B5 to B8, 3 to: LOO parts by weight of an ethylenically unsaturated monomer is used. It is preferable to perform bulk polymerization or solution polymerization. More preferably, it is 8-25 weight part, More preferably, it is 10-20 weight part. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C.
[0098] 用いるエチレン性不飽和単量体としては、工程 B5〜B8にて酸無水物基と反応さ せているため、先に示した不飽和単量体のみならず、酸無水物基と反応性する部位 を有するものを用いることもできる。例えば、水酸基を有するエチレン性不飽和単量 体が挙げられる。 [0098] Since the ethylenically unsaturated monomer used is reacted with an acid anhydride group in steps B5 to B8, not only the unsaturated monomer shown above but also an acid anhydride group is used. Those having a reactive site can also be used. An example is an ethylenically unsaturated monomer having a hydroxyl group.
[0099] 前記の製造方法で使用される水酸基を有するエチレン性不飽和単量体としては、 水酸基を有し、エチレン性不飽和二重結合を有する単量体であればどのようなもの でも構わないが、具体的には、水酸基を有する (メタ)アタリレート系単量体、例えば、 2—ヒドロキシェチル (メタ）アタリレート、 2 (又は 3)—ヒドロキシプロピル (メタ）アタリレ ート、 2 (又は 3又は 4)ーヒドロキシブチル (メタ）アタリレート及びシクロへキサンジメタ ノールモノ（メタ）アタリレートなどのヒドロキシアルキル (メタ）アタリレート、あるいは水 酸基を有する (メタ)アクリルアミド系単量体、例えば、 N—（2—ヒドロキシェチル）（メ タ）アクリルアミド、 N— (2—ヒドロキシプロピル）（メタ）アクリルアミド、 N— (2—ヒドロキ シブチル）（メタ）アクリルアミドなどの N— (ヒドロキシアルキル）（メタ）アクリルアミド、あ るいは、水酸基を有するビュルエーテル系単量体、例えば、 2—ヒドロキシェチルビ -ルエーテル、 2—（又は 3—）ヒドロキシプロピルビュルエーテル、 2—（又は 3—又 は 4一）ヒドロキシブチルビ-ルエーテルなどのヒドロキシアルキルビュルエーテル、あ るいは水酸基を有するァリルエーテル系単量体、例えば、 2—ヒドロキシェチルァリル エーテル、 2- (又は 3—)ヒドロキシプロピルァリルエーテル、 2— (又は 3—又は 4—) ヒドロキシブチルァリルエーテルなどのヒドロキシアルキルァリルエーテルが挙げられ る。 [0100] また、上記のヒドロキシアルキル (メタ）アタリレート、 N- (ヒドロキシアルキル）（メタ） アクリルアミド、ヒドロキシアルキルビュルエーテルあるいはヒドロキシアルキルァリル エーテルにアルキレンオキサイド及び/又はラタトンを付カ卩して得られるエチレン性 不飽和単量体も、本発明で用いる製造方法において、水酸基を有するエチレン性不 飽和単量体 (h)として用いることができる。付加されるアルキレンオキサイドとしては、 エチレンオキサイド、プロピレンオキサイド、 1, 2 1, 4 2, 3—又は 1, 3—ブチ レンオキサイド及びこれらの 2種以上の併用系が用いられる。 2種以上のアルキレン オキサイドを併用するときの結合形式はランダム及び Z又はブロックのいずれでもよ い。付加されるラタトンとしては、 δ—ノ レ口ラタトン、 ε —力プロラタトン、炭素原子数 1 6のアルキル基で置換された ε一力プロラタトン及びこれらの 2種以上の併用系 が用いられる。アルキレンオキサイドとラタトンを両方とも付加したものでも構わない。 [0099] The ethylenically unsaturated monomer having a hydroxyl group used in the above production method may be any monomer having a hydroxyl group and having an ethylenically unsaturated double bond. Specifically, (meth) acrylate monomers having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (Or 3 or 4) -hydroxybutyl (meth) acrylate and hydroxyalkyl (meth) acrylate, such as cyclohexane dimethanol mono (meth) acrylate, or (meth) acrylamide monomers having a hydroxyl group, such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) ) N- (hydroxyalkyl) (meth) acrylamide such as acrylamide, or a butyl ether monomer having a hydroxyl group such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl butyl Ethers, hydroxyalkyl butyl ethers such as 2- (or 3- or 4) hydroxybutyl vinyl ethers, or aryl ether monomers having a hydroxyl group, such as 2-hydroxyethyl aryl ether, 2- Examples include (or 3-) hydroxypropyl aryl ether, and hydroxy alkyl aryl ethers such as 2- (or 3- or 4-) hydroxy butyl aryl ether. [0100] Also obtained by adding alkylene oxide and / or latathone to the above hydroxyalkyl (meth) acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl butyl ether or hydroxyalkyl butyl ether. The ethylenically unsaturated monomer obtained can also be used as the ethylenically unsaturated monomer (h) having a hydroxyl group in the production method used in the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1, 2 1, 4 2, 3-— or 1,3-butylene oxide and a combination system of two or more of these are used. When two or more alkylene oxides are used in combination, the bond type may be random and either Z or block. Examples of the added ratataton include δ-noratolatataton, ε-force prolatatatone, ε-one-proteatone substituted with an alkyl group having 16 carbon atoms, and a combination of two or more of these. An alkylene oxide and a rataton may be added.
[0101] 本発明の分散剤で分散できる顔料は、インキ等に使用される種々の顔料が挙げら れる。このような顔料としては溶性ァゾ顔料、不溶性ァゾ顔料、フタロシアニン顔料、 キナクリドン顔料、イソインドリノン顔料、イソインドリン顔料、ペリレン顔料、ペリノン顔 料、ジォキサジン顔料、アントラキノン顔料、ジアンスラキノ二ル顔料、アンスラピリミジ ン顔料、アンサンスロン顔料、インダンスロン顔料、フラノくンスロン顔料、ピランスロン 顔料、ジケトピロロピロール顔料等があり、更に具体的な例をカラーインデックスのジ エネリックネームで示すと、ビグメントブラック 7、ビグメントブルー 6, 15, 15 : 1, 15 : 3 , 15 :4, 15 : 6, 60、ビグメントグリーン 7, 36、ビグメントレッド 9, 48, 49, 52, 53, 5 7, 97, 122, 144, 146, 149, 166, 168, 177, 178, 179, 185, 206, 207, 20 9, 220, 221, 238, 242, 254, 255、ピグメントノィォレット 19, 23, 29, 30, 37, 40, 50、ビグメン卜イェロー 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 1 09, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185、ビグメントオレンジ 13, 36, 37, 38, 43, 51, 55, 59 , 61, 64, 71, 74等が挙げられる。但し、例示には限定されない。  [0101] Examples of pigments that can be dispersed with the dispersant of the present invention include various pigments used in inks and the like. Such pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone pigments, anthracirimide pigments. Pigments, Ansanthrone pigments, Indanthrone pigments, Furano-Kunthlon pigments, Pyranthrone pigments, Diketopyrrolopyrrole pigments, etc. , Pigment Blue 6, 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 5 7, 97 , 122, 144, 146, 149, 166, 168, 177, 178, 179, 185, 206, 207, 20 9, 220, 221, 238, 242, 254, 255, pigment neolet 19, 23, 29, 30, 37, 40, 50, Bigeme Nyello 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 1 09, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, pigment orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74 and the like. However, it is not limited to illustration.
[0102] また、二酸化チタン、酸化鉄、五酸ィ匕アンチモン、酸化亜鉛、シリカなどの金属酸ィ匕 物、硫ィ匕カドミウム、炭酸カルシウム、炭酸バリウム、硫酸バリウム、クレー、タルク、黄 鉛、カーボンブラックなどの無機顔料も使用することができる。カーボンブラックにつ いては中性、酸性、塩基性等のあらゆるカーボンブラックを使用することができる。本 発明の顔料組成物は、上記顔料に限らず、例えば、金、銀、銅、白金、鉄、コバルト、 ニッケル、及び Z又はこれらの合金などの金属微粒子を含む固体微粒子を使用する ことができる。 [0102] In addition, titanium dioxide, iron oxide, metal oxides such as antimony pentoxide, zinc oxide, silica, cadmium sulfate, calcium carbonate, barium carbonate, barium sulfate, clay, talc, chrome, Inorganic pigments such as carbon black can also be used. Carbon black Any carbon black such as neutral, acidic, and basic can be used. The pigment composition of the present invention is not limited to the above-described pigment, and for example, solid fine particles containing metal fine particles such as gold, silver, copper, platinum, iron, cobalt, nickel, and Z or alloys thereof can be used. .
[0103] また本発明の分散剤を用いた顔料組成物には、更に塩基性基を有する顔料誘導 体、塩基性基を有するアントラキノン誘導体、塩基性基を有するアタリドン誘導体及 び塩基性基を有するトリァジン誘導体の群力 選ばれる少なくとも一種の塩基性誘導 体を含むことが好ましい。ここで、顔料誘導体とは、前記のカラーインデックスに記載 されている有機顔料残基に、特定の置換基を導入したものであり、本発明では塩基 性基を有するものを使用する。塩基性誘導体を含むことにより、塩基性誘導体なしで は分散の難しい顔料 (特に、有機顔料の場合)も、分散性、流動性、保存安定性に優 れた顔料組成物とすることができ好ま 、。  [0103] The pigment composition using the dispersant of the present invention further has a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an attaridone derivative having a basic group, and a basic group. Group power of triazine derivatives It is preferable to include at least one basic derivative selected. Here, the pigment derivative is a product obtained by introducing a specific substituent into the organic pigment residue described in the color index. In the present invention, a pigment derivative having a basic group is used. By including a basic derivative, a pigment composition that is difficult to disperse without a basic derivative (particularly in the case of an organic pigment) can be made into a pigment composition excellent in dispersibility, fluidity, and storage stability. ,.
[0104] 本発明の顔料組成物において用いることのできる塩基性誘導体は、塩基性基を有 する顔料誘導体、塩基性基を有するアントラキノン誘導体、塩基性基を有するアタリド ン誘導体及び塩基性基を有するトリァジン誘導体の群から選ばれるものである。  [0104] The basic derivative that can be used in the pigment composition of the present invention has a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an attaridone derivative having a basic group, and a basic group. It is selected from the group of triazine derivatives.
[0105] 本発明の顔料組成物において用いることのできる塩基性誘導体の塩基性基は、下 記一般式 (6)、（7)、（8)及び（9)で示される基力 なる群力 選ばれる少なくとも 1つ の基である。  [0105] The basic group of the basic derivative that can be used in the pigment composition of the present invention is a group force having a basic force represented by the following general formulas (6), (7), (8), and (9). At least one group selected.
[0106] 一般式 (6)  [0106] General formula (6)
[化 24]  [Chemical 24]
Figure imgf000030_0001
Figure imgf000030_0001
[0107] 一般式（7)  [0107] General formula (7)
[化 25]  [Chemical 25]
R1 R 1
/  /
—— CH2N (7) —— CH 2 N (7)
R2 [0108] 一般式 (8) R 2 [0108] General formula (8)
[化 26]  [Chemical 26]
Figure imgf000031_0001
Figure imgf000031_0001
[0109] 一般式 (9)  [0109] General formula (9)
[化 27]  [Chemical 27]
Figure imgf000031_0002
Figure imgf000031_0002
[0110] 前記一般式 (6)〜 (9)にお 、て、  [0110] In the general formulas (6) to (9),
x、x x2は、 SO CO—、 CH NHCOCH - CH一又は直接結合 x and xx 2 are SO CO—, CH NHCOCH-CH one or direct bond
2  2
を表す。  Represents.
mは、 1〜10の整数を表す。  m represents an integer of 1 to 10.
R2は、それぞれ独立に、置換されていてもよい、アルキル基、ァルケ-ル基、フ ェニル基、又は R1と R2とが一体となって形成した複素環を表す。但し、前記複素環は 、さらなる窒素、酸素又は硫黄原子を含んでいてもよい。アルキル基及びアルケニル 基の炭素数は 1〜10が好ましい。 R 2 each independently represents an optionally substituted alkyl group, alkenyl group, phenyl group, or a heterocyclic ring formed by combining R 1 and R 2 . However, the heterocycle may contain further nitrogen, oxygen or sulfur atoms. The alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.
R3は、置換されていてもよい、アルキル基、ァルケ-ル基又はフエ-ル基を表す。 アルキル基及びアルケ-ル基の炭素数は 1〜 10が好まし!/、。 R 3 represents an alkyl group, a alkenyl group or a phenyl group which may be substituted. Alkyl and alkenyl groups preferably have 1 to 10 carbon atoms! /.
R4、 R5、 R6、 R7は、それぞれ独立に、水素原子、置換されていてもよい、アルキル 基、ァルケ-ル基又はフヱ-ル基を表す。アルキル基及びアルケ-ル基の炭素数は 1〜5が好ましい。 Yは、 NR8— Z— NR9 又は直接結合を表す。 R 4 , R 5 , R 6 , and R 7 each independently represents a hydrogen atom, an alkyl group, a alkenyl group, or a fuller group that may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable. Y represents NR 8 —Z—NR 9 or a direct bond.
R8、 R9は、それぞれ独立に、水素原子、置換されていてもよい、アルキル基、アル ケ-ル基又はフヱ-ル基を表す。アルキル基及びァルケ-ル基の炭素数は 1〜5が 好ましい。 R 8 and R 9 each independently represents a hydrogen atom, an optionally substituted alkyl group, an alcohol group, or a phenol group. The alkyl group and the alkyl group preferably have 1 to 5 carbon atoms.
Zは、置換されていてもよい、アルキレン基、ァルケ-レン基、又はフエ-レン基を表 す。アルキル基及びアルケ-ル基の炭素数は 1〜8が好まし!/、。  Z represents an optionally substituted alkylene group, alkylene group, or fullerene group. Alkyl and alkenyl groups preferably have 1 to 8 carbon atoms! /.
Pは、式（10)で示される置換基又は式（11)で示される置換基を表す。  P represents a substituent represented by the formula (10) or a substituent represented by the formula (11).
Qは、水酸基、アルコキシル基、式（10)で示される置換基又は式（11)で示される 置換基を表す。  Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (10) or a substituent represented by the formula (11).
[0111] 一般式（10) [0111] General formula (10)
[化 28]  [Chemical 28]
Figure imgf000032_0001
Figure imgf000032_0001
[0112] 一般式（11)  [0112] General formula (11)
[化 29]  [Chemical 29]
R4 R5 R 4 R 5
\ /  \ /
CH-CH  CH-CH
—— X— N N—— R3 (11) —— X— NN—— R 3 (11)
\ /  \ /
CH-CH  CH-CH
R' R6 R 'R 6
[0113] 上記一般式中の I^〜R9におけるアルキル基としては、メチル基、ェチル基、プロピ ル基、ブチル基、ペンチル基、へキシル基などが挙げられる。また、ァルケ-ル基とし ては、ビニル基、プロべ-ル基などが挙げられる。 [0113] The alkyl group in I ^ to R 9 in the general formula, a methyl group, Echiru group, propyl group, butyl group, pentyl group, etc. hexyl group to. Further, examples of the alkenyl group include a vinyl group and a probe group.
[0114] 上記一般式中の Zにおけるアルキレン基としては、メチレン基、エチレン基、プロピ レン基、ブチレン基などが挙げられる。また、ァルケ-レン基としては、ビニレン基、プ 口べ-レン基などが挙げられる。 [0115] 上記一般式中の Qにおけるアルコキシル基としては、メトキシ基、エトキシ基、プロボ キシ基、ブトキシ基などが挙げられる。 [0114] Examples of the alkylene group for Z in the above general formula include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the alkellene group include a vinylene group and a p-bene group. [0115] Examples of the alkoxyl group for Q in the above general formula include a methoxy group, an ethoxy group, a alkoxy group, and a butoxy group.
[0116] また、置換されてもよい官能基とは、ハロゲン基、シァノ基、アルコキシル基、ァミノ 基、水酸基、ニトロ基、エポキシ基などが挙げられる。  [0116] Examples of the functional group which may be substituted include a halogen group, a cyano group, an alkoxyl group, an amino group, a hydroxyl group, a nitro group, and an epoxy group.
[0117] 式 (6)〜式（9)で示される置換基を形成するために使用されるァミン成分としては、 例えば、ジメチルァミン、ジェチルァミン、 N, N ェチルイソプロピルァミン、 N, N— ェチルプロピルアミン、 N, N—メチルブチルァミン、 N, N—メチルイソブチルァミン、 N, N ブチルェチルァミン、 N, N— tert ブチルェチルァミン、ジイソプロピルアミ ン、ジプロピルァミン、 N, N— sec ブチルプロピルアミン、ジブチルァミン、ジ sec ーブチルァミン、ジイソブチルァミン、 N, N イソブチルー sec ブチルァミン、ジアミ ルァミン、ジイソアミルァミン、ジへキシルァミン、ジ（2—ェチルへキシル）ァミン、ジォ クチルァミン、 N, N—メチルォクタデシルァミン、ジデシルァミン、ジァリルァミン、 N, N ェチルー 1, 2—ジメチルプロピルァミン、 N, N—メチルへキシルァミン、ジォレイ ルァミン、ジステアリルァミン、 N, N ジメチルアミノメチルァミン、 N, N ジメチルァ ミノエチルァミン、 N, N ジメチルアミノアミルァミン、 N, N ジメチルアミノブチルァ ミン、 N, N ジェチルアミノエチルァミン、 N, N ジェチルァミノプロピルアミン、 N, N ジェチルァミノへキシルァミン、 N, N ジェチルアミノブチルァミン、 N, N ジ ェチルァミノペンチルァミン、 N, N ジプロピルアミノブチルァミン、 N, N—ジブチル ァミノプロピルァミン、 N, N ジブチルアミノエチルァミン、 N, N ジブチルアミノブ チルァミン、 N, N ジイソブチルァミノペンチルァミン、 N, N—メチルーラウリルアミ ノプロピルァミン、 N, N ェチルーへキシルアミノエチルァミン、 N, N ジステアリル アミノエチルァミン、 N, N ジォレイルアミノエチルァミン、 N, N ジステアリルアミノ ブチルァミン、ピぺリジン、 2 ピペコリン、 3 ピペコリン、 4 ピペコリン、 2, 4—ルぺ チジン、 2, 6—ルペチジン、 3, 5—ルペチジン、 3 ピペリジンメタノール、ピペコリン 酸、イソ-ペコチン酸、イソ-コペチン酸メチル、イソ-コペチン酸ェチル、 2—ピペリ ジンエタノール、ピロリジン、 3—ヒドロキシピロリジン、 N—アミノエチルピペリジン、 N アミノエチルー 4ーピペコリン、 N—アミノエチルモルホリン、 N ァミノプロピルピぺ リジン、 N ァミノプロピル一 2 ピペコリン、 N ァミノプロピノレー 4 ピペコリン、 N— ァミノプロピルモルホリン、 N—メチルピペラジン、 N ブチルピペラジン、 N—メチル ホモピぺラジン、 1ーシクロペンチルピペラジン、 1 アミノー 4ーメチルピペラジン、 1 ーシクロペンチルビペラジン等が挙げられる。 [0117] Examples of the amine component used to form the substituents represented by the formulas (6) to (9) include dimethylamine, jetylamine, N, N-ethylisopropylamine, N, N- Tylpropylamine, N, N-methylbutyramine, N, N-methylisobutyramine, N, N butylethylamine, N, N-tert butylethylamine, diisopropylamine, dipropylamine, N, N-sec butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N isobutyl-sec butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N—Methyloctadecylamine, didecylamine, diarylamine, N, N ethyl-1,2-dimethylpropylamine, N, N—methyl Hexylamine, dioleylamine, distearylamine, N, N dimethylaminomethylamine, N, N dimethylaminoethylamine, N, N dimethylaminoamylamine, N, N dimethylaminobutylamine, N, N jetylamino Ethylamine, N, N Jetylaminopropylamine, N, N Jetylaminohexylamine, N, N Jetylaminobutyramine, N, N Diethylaminopentylamine, N, N Dipropylaminobutyl N, N-dibutylaminopropylamine, N, N dibutylaminoethylamine, N, N dibutylaminobutylamine, N, N diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine N, N ethylhexylaminoethylamine, N, N distearyl aminoethylamine, N, N dioleylaminoe Tyramine, N, N distearylamino butyramine, piperidine, 2 pipecoline, 3 pipecoline, 4 pipecoline, 2, 4-lupetidine, 2, 6-lupetidine, 3, 5-lupetidine, 3 piperidinemethanol, pipecolic acid, Iso-pecotic acid, methyl iso-copetinate, ethyl iso-copetinate, 2-piperidine ethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N aminoethyl-4-pipecoline, N-aminoethylmorpholine, N aminopropylpipe Lysine, N-aminopropyl 1-2 pipecoline, N-aminopropynole 4 pipecoline, N— Examples include aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylbiperazine and the like.
[0118] 塩基性基を有する顔料誘導体を構成する有機色素は、例えば、ジケトピロ口ピロ一 ル系色素、ァゾ、ジスァゾ、ポリアゾ等のァゾ系色素、フタロシアニン系色素、ジァミノ ジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、 ピラントロン、ビオラントロン等のアントラキノン系色素、キナクリドン系色素、ジォキサ ジン系色素、ペリノン系色素、ペリレン系色素、チォインジゴ系色素、イソインドリン系 色素、イソインドリノン系色素、キノフタロン系色素、スレン系色素、金属錯体系色素 等の色素である。また、塩基性基を有するアントラキノン誘導体及び塩基性基を有す るアタリドン誘導体は、メチル基、ェチル基等のアルキル基、アミノ基、ニトロ基、水酸 基又はメトキシ基、エトキシ基等のアルコキシ基又は塩素等のハロゲン等の置換基を 有していてもよい。  [0118] The organic dye constituting the pigment derivative having a basic group includes, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine , Flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone and other anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes , Quinophthalone dyes, selenium dyes, metal complex dyes, and the like. In addition, an anthraquinone derivative having a basic group and an attaridone derivative having a basic group are alkyl groups such as a methyl group and an ethyl group, an amino group, a nitro group, a hydroxyl group, or an alkoxy group such as a methoxy group and an ethoxy group. Or you may have substituents, such as halogens, such as chlorine.
[0119] また、塩基性基を有するトリァジン誘導体を構成するトリアジンは、アルキル基 (メチ ル基、ェチル基、ブチル基等）、アミノ基、アルキルアミノ基 (ジメチルァミノ基、ジェチ ルァミノ基、ジブチルァミノ基等）、ニトロ基、水酸基、アルコキシ基 (メトキシ基、ェトキ シ基、ブトキシ基等）、ハロゲン (塩素、臭素等）、フエニル基 (アルキル基、アミノ基、 アルキルアミノ基、ニトロ基、水酸基、アルコキシ基、ハロゲン等で置換されていてもよ い）、及びフエ-ルァミノ基（アルキル基、アミノ基、アルキルアミノ基、ニトロ基、水酸 基、アルコキシ基、ハロゲン等で置換されていてもよい）等の置換基を有していてもよ い 1, 3, 5 トリァジンである。  [0119] In addition, triazines constituting triazine derivatives having a basic group include alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, jetramino group, dibutylamino group, etc.) ), Nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group) And may be substituted with a halogen, etc.), and a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.), etc. It is 1, 3, 5 triazine which may have the following substituents.
[0120] 本発明の塩基性基を有する顔料誘導体、アントラキノン誘導体及びアタリドン誘導 体は、種々の合成経路で合成することができる。例えば、有機色素、アントラキノンも しくはアタリドンに一般式（ 12)〜（ 15)で示される置換基を導入した後、上記置換基 と反応して一般式 (6)〜（9)で示される置換基を形成するァミン成分、例えば、 N, N ージメチルァミノプロピルァミン、 N—メチルビペラジン、ジェチルァミン又は 4 [4 ヒドロキシ— 6— [3— (ジブチルァミノ）プロピルァミノ]— 1, 3, 5 トリアジン— 2—ィ ルァミノ]ァ-リン等を反応させることによって得られる。 一般式（12) — SO CI [0120] The pigment derivative, anthraquinone derivative and attaridone derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the general formulas (12) to (15) into an organic dye, anthraquinone or attaridone, it reacts with the above-described substituents to obtain a substituent represented by the general formulas (6) to (9). Group-forming amine components such as N, N-dimethylaminopropylamine, N-methylbiperazine, jetylamine or 4 [4 hydroxy-6- [3- (dibutylamino) propylamino]] 1, 3, 5 triazine-2 It can be obtained by reacting —ylamino] -lin or the like. Formula (12) — SO CI
2  2
一般式（13) -COC1  Formula (13) -COC1
一般式（14) -CH NHCOCH C1  Formula (14) -CH NHCOCH C1
2 2  twenty two
一般式（15) -CH C1  Formula (15) -CH C1
2  2
[0121] 一般式（12)〜（15)で示される置換基と上記アミン成分との反応の際に、一般式（ 12)〜（15)で示される置換基の一部が加水分解して、塩素原子が水酸基に置換し たものが混在していてもよい。その場合、一般式（12)又は一般式（13)で示される置 換基は、それぞれスルホン酸基又はカルボン酸基となる力 何れも遊離酸のままでも よぐまた、 1〜3価の金属又は上記のモノアミンとの塩であってもよい。  [0121] During the reaction of the substituents represented by the general formulas (12) to (15) and the amine component, some of the substituents represented by the general formulas (12) to (15) are hydrolyzed. In addition, a group in which a chlorine atom is substituted with a hydroxyl group may be present. In that case, the substituent represented by the general formula (12) or the general formula (13) may be either a free acid or a sulfonic acid group or a carboxylic acid group. Or the salt with said monoamine may be sufficient.
[0122] また、有機色素がァゾ系色素である場合は、一般式 (6)〜（9)で示される置換基を あら力じめジァゾ成分又はカップリング成分に導入し、その後カップリング反応を行う ことによってァゾ系顔料誘導体を製造することもできる。  [0122] When the organic dye is a azo dye, the substituents represented by the general formulas (6) to (9) are introduced into the diazo component or the coupling component, and then the coupling reaction is performed. It is also possible to produce an azo pigment derivative.
[0123] 前記塩基性基を有するトリァジン誘導体は、種々の合成経路で合成することができ る。例えば、塩化シァヌルを出発原料とし、塩ィ匕シァヌルの少なくとも 1つの塩素に式 (6)〜式（9)で示される置換基を形成するァミン成分、例えば、 N, N—ジメチルアミ ノプロピルアミン又は N—メチルビペラジン等を反応させ、次!、で塩化シァヌルの残り の塩素と種々のァミン又はアルコール等を反応させることによって得られる。  [0123] The triazine derivative having a basic group can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by formula (6) to formula (9) on at least one chlorine of the salt cyanuric, such as N, N-dimethylaminopropylamine or It can be obtained by reacting N-methylbiperazine or the like and then reacting the remaining chlorine of the cyanuric chloride with various amines or alcohols.
[0124] 本発明の顔料組成物にお!ヽて、塩基性誘導体の配合量は、顔料 100重量部に対 し好ましくは 1〜50重量部、更に好ましくは 3〜30重量部、最も好ましくは 5〜25重 量部である。また、ポリエステル分散剤の配合量は、顔料 100重量部に対し好ましく は 1〜200重量部、更に好ましくは 2〜175重量部、最も好ましくは 5〜 150重量部で ある。  [0124] In the pigment composition of the present invention, the amount of the basic derivative is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, most preferably 100 parts by weight of the pigment. 5 to 25 parts by weight. The blending amount of the polyester dispersant is preferably 1 to 200 parts by weight, more preferably 2 to 175 parts by weight, and most preferably 5 to 150 parts by weight with respect to 100 parts by weight of the pigment.
[0125] 本発明のポリエステル分散剤を用いた顔料組成物は、必要により各種溶剤、榭脂、 添加剤等を混合して、横型サンドミル、縦型サンドミル、ァ-ユラ一型ビーズミル、アト ライター等で分散することにより、顔料組成物をワニスに分散せしめてなる顔料分散 体を調製することができる。顔料、塩基性誘導体、ポリエステル分散剤、その他の榭 脂、添加剤は、すべての成分を混合して力も分散してもよいが、初めに顔料と塩基性 誘導体とのみ、あるいは、塩基性誘導体とポリエステル分散剤とのみ、あるいは、顔 料と塩基性誘導体とポリエステル分散剤とのみを分散し、次いで、他の成分を添加し て再度分散を行ってもよい。 [0125] The pigment composition using the polyester dispersant of the present invention may be mixed with various solvents, resin, additives, etc. as necessary to obtain a horizontal sand mill, a vertical sand mill, a Yura-la type bead mill, an attritor, etc. The pigment dispersion obtained by dispersing the pigment composition in the varnish can be prepared. For pigments, basic derivatives, polyester dispersants, other resins and additives, all components may be mixed to disperse the force, but initially only the pigment and the basic derivative, or the basic derivative Only with polyester dispersant or face It is also possible to disperse the material, the basic derivative, and the polyester dispersant alone, and then add another component to perform dispersion again.
[0126] また、横型サンドミル、縦型サンドミル、ァ-ユラ一型ビーズミル、アトライター等で分 散を行う前に、エーダー、 3本ロールミル等の練肉混合機を使用した前分散、 2本口 ールミル等による固形分散、又は顔料への塩基性誘導体、及び Z又はカルボキシル 基含有ポリエステルの処理を行ってもよい。又はィスピードミキサー、ホモミキサー、 ボールミル、ロールミル、石臼式ミル、超音波分散機等のあらゆる分散機や混合機が 顔料分散体を製造するために利用できる。前記の顔料分散体に用いることができる 各種溶剤としては、有機溶剤、水等が挙げられる。また、活性エネルギー線硬化型組 成物に用いる場合、活性エネルギー線硬化性の液状モノマーや液状オリゴマーを溶 剤代わりの媒体として用いてもよい。  [0126] In addition, before dispersion using a horizontal sand mill, vertical sand mill, air-rare type bead mill, attritor, etc., pre-dispersion using a kneader mixer such as an adader, 3-roll mill, etc. You may perform the solid dispersion | distribution by a kneading mill, etc., or the basic derivative to a pigment, and Z or a carboxyl group-containing polyester. Alternatively, any dispersing machine or mixer such as a speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic dispersing machine can be used to produce the pigment dispersion. Examples of various solvents that can be used in the pigment dispersion include organic solvents and water. In addition, when used in an active energy ray-curable composition, an active energy ray-curable liquid monomer or liquid oligomer may be used as a medium instead of a solvent.
[0127] また、本発明の顔料分散体に用いることができる榭脂の例としては、石油榭脂、力 ゼイン、セラック、ロジン変性マレイン酸榭脂、ロジン変性フエノール榭脂、ニトロセル ロース、セルロースアセテートブチレート、環化ゴム、塩化ゴム、酸化ゴム、塩酸ゴム、 フエノール榭脂、アルキド榭脂、ポリエステル榭脂、不飽和ポリエステル榭脂、ァミノ 榭脂、エポキシ榭脂、ビュル榭脂、塩化ビュル、塩ィ匕ビュル一酢酸ビュル酸性基含 有ウレタン榭脂、アクリル榭脂、メタタリル榭脂、ポリウレタン榭脂、シリコーン榭脂、フ ッ素榭脂、乾性油、合成乾性油、スチレン変性マレイン酸、ポリアミド榭脂、塩素化ポ リプロピレン、プチラール榭脂、塩ィ匕ビユリデン榭脂等が挙げられる。また、本発明の ポリエステル分散剤を顔料分散体のバインダー榭脂として使用することもできる。  [0127] Examples of the resin that can be used in the pigment dispersion of the present invention include petroleum resin, power zein, shellac, rosin-modified maleic acid resin, rosin-modified phenol resin, nitrocellulose, cellulose acetate. Butylate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, bull resin, butyl chloride, salt Bulbu monoacetate acid group containing urethane resin, acrylic resin, methallyl resin, polyurethane resin, silicone resin, fluorine resin, drying oil, synthetic drying oil, styrene-modified maleic acid, polyamide resin Examples thereof include fats, chlorinated polypropylene, petital resin, and salt vinylidene resin. Further, the polyester dispersant of the present invention can be used as a binder resin for a pigment dispersion.
[0128] 本発明の顔料分散体は、非水系、水系、又は無溶剤系の塗料、グラビアインキ、ォ フセットインキ、インキジェットインキ、カラーフィルター用インキ、デジタルペーパー用 インキ、プラスチック着色等に利用できる。  [0128] The pigment dispersion of the present invention is used for non-aqueous, aqueous or solvent-free paints, gravure ink, offset ink, ink jet ink, color filter ink, digital paper ink, plastic coloring, etc. it can.
実施例  Example
[0129] 以下、実施例によって本発明を具体的に説明するが、本発明は実施例に特に限定 されるものではない。なお、実施例中、「部」は「重量部」、「％」は「重量％」を表す。ま た、重量平均分子量は、 TSKgelカラム (東ソ一社製)を用い、 RI検出器を装備した G PC (東ソ一社製、 HLC— 8120GPC)で、展開溶媒に THFを用いたときのポリスチ レン換算分子量である。 [0129] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not particularly limited to the examples. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”. The weight average molecular weight was measured with TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) when THF was used as the developing solvent. Police The molecular weight in terms of ren.
[0130] (実施例 1)  [0130] (Example 1)
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、 n—プチルメタク リレート 200部を仕込み、窒素ガスで置換した。反応容器内を 80°Cに加熱して、 3— メルカプト 1, 2—プロパンジオール 12部を添カ卩して、 12時間反応した。固形分測 定により 95%が反応したことを確認した。次に、ピロメリット酸無水物 12部、シクロへ キサノン 224部、触媒として 1, 8 ジァザビシクロ一 [5. 4. 0]— 7 ゥンデセン 0. 4 0部を追加し、 120°Cで 7時間反応させた。酸価の測定で 98%以上の酸無水物がハ 一フェステルィ匕して ヽることを確認し反応を終了し酸価 28、重量平均分子量 5800 のポリエステル分散剤（=分散剤 1；以下同様)を得た。  A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 200 parts of n-butyl methacrylate and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 12 parts of 3-mercapto 1,2-propanediol was added to react for 12 hours. Solid content measurement confirmed that 95% had reacted. Next, 12 parts of pyromellitic anhydride, 224 parts of cyclohexanone and 1,8 diazabicyclo [5.4.0] —7 undecene 0.40 parts as catalyst were added and reacted at 120 ° C for 7 hours. I let you. When the acid value was measured, it was confirmed that 98% or more of the acid anhydride had disappeared and the reaction was terminated. The polyester dispersant having an acid value of 28 and a weight average molecular weight of 5800 (= dispersant 1; the same shall apply hereinafter) Got.
[0131] (実施例 2〜6) [0131] (Examples 2 to 6)
表 1に記載した原料と仕込み量を用いた以外は実施例 1と同様にして合成を行 、、 ポリエステル分散剤を得た。  Synthesis was carried out in the same manner as in Example 1 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0132] (実施例 7)  [0132] (Example 7)
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、 n—プチルメタク リレート 100部とベンジルメタタリレート 100部を仕込み、窒素ガスで置換した。反応 容器内を 80oCにカロ熱して、 3—メノレカプト 1, 2 プロノ ンジ才一ノレ 12咅に、 2, 2' —ァゾビスイソプチ口-トリル 0. 1部を溶解した溶液を添加して、 10時間反応した。固 形分測定により 95%が反応したことを確認した。ピロメリット酸無水物 19部、シクロへ キサノン 231部、触媒として 1, 8 ジァザビシクロ一 [5. 4. 0]— 7 ゥンデセン 0. 4 0部を追加し、 120°Cで 7時間反応させた。酸価の測定で 98%以上の酸無水物がハ 一フェステルィ匕して ヽることを確認し反応を終了し酸価 43、重量平均分子量 8500 のポリエステル分散剤を得た。 A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C, and a solution of 0.1 part of 2,2'-azobisisobutyl-tolyl was added to 12-liter of 3-menorecapto 1,2 pronogen, Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 19 parts of pyromellitic anhydride, 231 parts of cyclohexanone, and 0.48 parts of 1,8 diazabicyclo [5.4.0] —7undecene were added as a catalyst and reacted at 120 ° C for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was condensed, and the reaction was terminated to obtain a polyester dispersant having an acid value of 43 and a weight average molecular weight of 8500.
[0133] (実施例 8) [Example 8]
表 1に記載した原料と仕込み量を用いた以外は実施例 7と同様にして合成を行 、、 ポリエステル分散剤を得た。  Synthesis was carried out in the same manner as in Example 7 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0134] (実施例 9)  [Example 9]
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、 n—プチルメタク リレート 100部とベンジルメタタリレート 100部を仕込み、窒素ガスで置換した。反応 容器内を 80oCにカロ熱して、 3—メノレカプト 1, 2 プロノ ンジ才一ノレ 12咅に、 2, 2' —ァゾビスイソプチ口-トリル 0. 1部を溶解した溶液を添加して、 10時間反応した。固 形分測定により 95%が反応したことを確認した。 BPDA37部、シクロへキサノン 255 部、触媒として 1, 8 ジァザビシクロー [5. 4. 0]— 7 ゥンデセン 0. 40部を追加し 、 120°Cで 7時間反応させた。その後に、ネオペンチルダリコール 5部を追加し、酸価 の測定で 98%以上の酸無水物がハーフエステルイ匕していることを確認し反応を終了 し酸価 56、重量平均分子量 9300のポリエステル分散剤を得た。 In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, n-butyl methacrylate 100 parts of relate and 100 parts of benzylmetatalylate were charged and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C, and a solution of 0.1 part of 2,2'-azobisisobutyl-tolyl was added to 12-liter of 3-menorecapto 1,2 pronogen, Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 37 parts of BPDA, 255 parts of cyclohexanone, and 1.40 diazabicyclo- [5.4.0] -7.40 parts as a catalyst were added and reacted at 120 ° C for 7 hours. After that, 5 parts of neopentyldaricol was added, and it was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. The reaction was terminated, and the acid value was 56 and the weight average molecular weight was 9300. A polyester dispersant was obtained.
[0135] (実施例 10〜17) [0135] (Examples 10 to 17)
表 1に記載した原料と仕込み量を用いた以外は実施例 7と同様にして合成を行 、、 ポリエステル分散剤を得た。  Synthesis was carried out in the same manner as in Example 7 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0136] (実施例 18〜22)  [Examples 18-22]
表 1に記載した原料と仕込み量を用いた以外は実施例 9と同様にして合成を行 、、 ポリエステル分散剤を得た。  Synthesis was carried out in the same manner as in Example 9 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0137] (実施例 23〜27)  [0137] (Examples 23 to 27)
表 1に記載した原料と仕込み量を用いた以外は実施例 7と同様にして合成を行 、、 ポリエステル分散剤を得た。  Synthesis was carried out in the same manner as in Example 7 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0138] (実施例 28)  [Example 28]
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、 n—プチルメタク リレート 100部と n—ブチルアタリレート 100部を仕込み、窒素ガスで置換した。反応 容器内を 80oCにカロ熱して、 3—メノレカプト 1, 2 プロノ ンジ才一ノレ 12咅に、 2, 2' —ァゾビスイソプチ口-トリル 0. 1部を溶解した溶液を添加して、 10時間反応した。固 形分測定により 95%が反応したことを確認した。 PMA4部、トリメリット酸無水物 26部 、シクロへキサノン 242部、触媒として 1, 8 ジァザビシクロ一 [5. 4. 0]— 7 ゥンデ セン 0. 40部を追カ卩し、 120°Cで 7時間反応させた。酸価の測定で 98%以上の酸無 水物がハーフエステルイ匕していることを確認し反応を終了し酸価 71、重量平均分子 量 5800のポリエステル分散剤を得た。 A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 100 parts of n-butyl methacrylate and 100 parts of n-butyl acrylate and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C, and a solution of 0.1 part of 2,2'-azobisisobutyl-tolyl was added to 12-liter of 3-menorecapto 1,2 pronogen, Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 4 parts of PMA, 26 parts of trimellitic anhydride, 242 parts of cyclohexanone, 1,8 diazabicyclo [5. 4. 0] — 7 undenecene as catalyst. Reacted for hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a polyester dispersant having an acid value of 71 and a weight average molecular weight of 5800.
[0139] (実施例 29及び 30) 表 1に記載した原料と仕込み量を用いた以外は実施例 28と同様にして合成を行 ヽ 、ポリエステル分散剤を得た。 [Examples 29 and 30] Synthesis was carried out in the same manner as in Example 28 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0140] (実施例 31) [0140] (Example 31)
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、 n—プチルメタク リレート 100部と n—ブチルアタリレート 100部を仕込み、窒素ガスで置換した。反応 容器内を 80oCにカロ熱して、 3—メノレカプト 1, 2 プロノ ンジ才一ノレ 12咅に、 2, 2' —ァゾビスイソプチ口-トリル 0. 1部を溶解した溶液を添加して、 10時間反応した。固 形分測定により 95%が反応したことを確認した。 PMA12部、トリメリット酸無水物 21 部、シクロへキサノン 245部、触媒として 1, 8 ジァザビシクロ一 [5. 4. 0]— 7 ゥン デセン 0. 40部を追加し、 120°Cで 7時間反応させた。その後に、ネオペンチルダリコ ール 3部を追加し、酸価の測定で 98%以上の酸無水物がハーフエステル化して!/、る ことを確認し反応を終了し酸価 74、重量平均分子量 7500のポリエステル分散剤を 得た。 A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 100 parts of n-butyl methacrylate and 100 parts of n-butyl acrylate and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C, and a solution of 0.1 part of 2,2'-azobisisobutyl-tolyl was added to 12-liter of 3-menorecapto 1,2 pronogen, Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 12 parts of PMA, 21 parts of trimellitic anhydride, 245 parts of cyclohexanone, 1,8 diazabicyclo [5.4.0] —7. 40 parts of decenene as catalyst, add 7 parts at 120 ° C for 7 hours Reacted. After that, 3 parts of neopentyl alcohol was added, and it was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. A polyester dispersant having a molecular weight of 7500 was obtained.
[0141] (実施例 32〜34)  [0141] (Examples 32-34)
表 1に記載した原料と仕込み量を用いた以外は実施例 32と同様にして合成を行 ヽ 、ポリエステル分散剤を得た。  Synthesis was performed in the same manner as in Example 32 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0142] (実施例 35)  [0142] (Example 35)
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、 3—メルカプト— 1, 2 プロパンジオール 12部、 PMA19部、シクロへキサノン 31部を仕込み、窒素 ガスで置換した。反応容器内を 100°Cに加熱して、 7時間反応させた。酸価の測定で 98%以上の酸無水物がハーフエステルイ匕していることを確認した後、系内の温度を 70°Cに冷却し、 n—ブチルメタタリレート 100部とベンジルメタタリレート 100部を仕込 み、 2, 2，—ァゾビスイソブチ口-トリル 0. 5部を溶解したシクロへキサノン溶液 200部 を添加して、 10時間反応した。固形分測定により重合が 95%進行したことを確認し 反応を終了した。酸価 43、重量平均分子量 9000のポリエステル分散剤を得た。  A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 12 parts of 3-mercapto-1,2-propanediol, 19 parts of PMA, and 31 parts of cyclohexanone and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C and reacted for 7 hours. After measuring the acid value to confirm that 98% or more of the acid anhydride was half-esterified, the temperature in the system was cooled to 70 ° C, and 100 parts of n-butyl metatalylate and benzyl metataliate were cooled. 100 parts of the rate were charged, and 200 parts of a cyclohexanone solution in which 0.5 part of 2,2, -azobisisobutyric-tolyl was dissolved was added and reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. A polyester dispersant having an acid value of 43 and a weight average molecular weight of 9000 was obtained.
[0143] (実施例 36〜38)  [Examples 36 to 38]
表 1に記載した原料と仕込み量を用いた以外は実施例 35と同様にして合成を行 ヽ 、ポリエステル分散剤を得た。 [0144] (実施例 39) Synthesis was carried out in the same manner as in Example 35 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained. [0144] (Example 39)
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、 3—メルカプト— 1, 2—プロパンジオール 12部、 PMA37部、ネオペンチルグリコール 11部、シクロへ キサノン 60部を仕込み、窒素ガスで置換した。反応容器内を 100°Cに加熱して、 7時 間反応させた。酸価の測定で 98%以上の酸無水物がハーフエステルイ匕して 、ること を確認した後、系内の温度を 70°Cに冷却し、メチルメタタリレート 80部とブチルアタリ レート 80部、 2—ヒドロキシプロピルメタタリレート 40部を仕込み、 2, 2， 一ァゾビスイソ ブチ口-トリル 0. 5部を溶解したシクロへキサノン溶液 200部を添カ卩して、 10時間反 応した。固形分測定により重合が 95%進行したことを確認し反応を終了した。酸価 7 3、重量平均分子量 13000のポリエステル分散剤を得た。  A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 12 parts of 3-mercapto-1,2-propanediol, 37 parts of PMA, 11 parts of neopentyl glycol, and 60 parts of cyclohexanone. Replaced. The inside of the reaction vessel was heated to 100 ° C and reacted for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride had been half-esterified, and then the temperature inside the system was cooled to 70 ° C., and 80 parts of methyl metatalylate and 80 parts of butyl acrylate. Then, 40 parts of 2-hydroxypropylmetatalylate was added, and 200 parts of cyclohexanone solution in which 0.5 part of 2,2,1azobisisobutyor-tolyl was dissolved was added and reacted for 10 hours. It was confirmed that the polymerization had progressed 95% by measuring the solid content, and the reaction was completed. A polyester dispersant having an acid value of 73 and a weight average molecular weight of 13,000 was obtained.
[0145] (実施例 40〜42)  [0145] (Examples 40 to 42)
表 1に記載した原料と仕込み量を用いた以外は実施例 35と同様にして合成を行 ヽ 、ポリエステル分散剤を得た。  Synthesis was carried out in the same manner as in Example 35 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0146] (実施例 43)  [0146] (Example 43)
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、 3—メルカプト— 1, 2—プロパンジオール 12部、 PMA12部、トリメリット酸無水物 11部、シクロへキサ ノン 35部を仕込み、窒素ガスで置換した。反応容器内を 100°Cに加熱して、 7時間 反応させた。酸価の測定で 98%以上の酸無水物がハーフエステルイ匕して 、ることを 確認した後、系内の温度を 70°Cに冷却し、メチルメタタリレート 80部とブチルアタリレ ート 80部、ヒドロキシェチノレメタタリレート 20部、 2—ヒドロキシプロピノレメタタリレート 2 0部を仕込み、 2, 2'—ァゾビスイソブチ口-トリル 0. 5部を溶解したシクロへキサノン 溶液 200部を添加して、 10時間反応した。固形分測定により重合が 95%進行したこ とを確認し反応を終了した。酸価 53、重量平均分子量 10000のポリエステル分散剤 を得た。  A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 12 parts of 3-mercapto-1,2-propanediol, 12 parts of PMA, 11 parts of trimellitic anhydride, and 35 parts of cyclohexanone. Replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C and reacted for 7 hours. After the acid value was measured to confirm that 98% or more of the acid anhydride had half-esterified, the temperature inside the system was cooled to 70 ° C., and 80 parts of methyl metatalylate and butyl acrylate 80 Part, 20 parts of hydroxyethinoremethalate, 20 parts of 2-hydroxypropenoremethalate, 200 parts of cyclohexanone solution containing 0.5 part of 2,2'-azobisisobutyric-tolyl added. And reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. A polyester dispersant having an acid value of 53 and a weight average molecular weight of 10,000 was obtained.
[0147] (実施例 44〜46)  [Examples 44 to 46]
表 1に記載した原料と仕込み量を用いた以外は実施例 35と同様にして合成を行 ヽ 、ポリエステル分散剤を得た。  Synthesis was carried out in the same manner as in Example 35 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0148] (実施例 47) ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、 3—メルカプト— 1, 2—プロパンジオール 12部、 PMA15部、ネオペンチルグリコール 11部、トリメリッ ト酸無水物 14部、シクロへキサノン 52部を仕込み、窒素ガスで置換した。反応容器 内を 100°Cに加熱して、 7時間反応させた。酸価の測定で 98%以上の酸無水物がハ 一フェステルィ匕していることを確認した後、系内の温度を 70°Cに冷却し、メチルメタク リレート 80部とブチノレアタリレート 100部、 2—ヒドロキシプロピルメタタリレート 20部を 仕込み、 2, 2'—ァゾビスイソブチ口-トリル 0. 5部を溶解したシクロへキサノン溶液 2 00部を添加して、 10時間反応した。固形分測定により重合が 95%進行したことを確 認し反応を終了した。酸価 63、重量平均分子量 9000のポリエステル分散剤を得た。 [0148] (Example 47) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 3-mercapto-1,2-propanediol 12 parts, PMA 15 parts, neopentyl glycol 11 parts, trimellitic anhydride 14 parts, cyclohexanone 52 parts were charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C and reacted for 7 hours. After the acid value measurement confirmed that 98% or more of the acid anhydride had been condensed, the temperature inside the system was cooled to 70 ° C., and 80 parts of methyl methacrylate and 100 parts of butinorea tallylate were added. 20 parts of 2-hydroxypropylmetatalylate was charged, and 200 parts of cyclohexanone solution in which 0.5 part of 2,2′-azobisisobutyric-tolyl was dissolved was added and reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. A polyester dispersant having an acid value of 63 and a weight average molecular weight of 9000 was obtained.
[0149] (実施例 48〜50)  [0149] (Examples 48 to 50)
表 1に記載した原料と仕込み量を用いた以外は実施例 35と同様にして合成を行 ヽ 、ポリエステル分散剤を得た。  Synthesis was carried out in the same manner as in Example 35 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.
[0150] 実施例 1〜34で得られたポリエステル分散剤の原料及び性状を表 1〜4に、実施例 35〜50で得られたポリエステル分散剤の原料及び性状を表 5、 6に示す。  [0150] The raw materials and properties of the polyester dispersants obtained in Examples 1-34 are shown in Tables 1-4, and the raw materials and properties of the polyester dispersants obtained in Examples 35-50 are shown in Tables 5 and 6, respectively.
[0151] [表 1] [0151] [Table 1]
原 料 実施例 1 実施例 2 実施例 3 実施例 4 実施例 5 実施例 6 実施例 7 実施例 8 実施例 9 合成樹脂 分散剤 1 分散剤 2 分散剤 3 分散剤 4 分散剤 5 分散剤 6 分散剤 7 分散剤 S 分散剤 9 n—ブチルメタクリレート 200 100 100 90 100 100 100 100 100 ベンジルメタクリレ一ト 100 100 100 100 100 100 100 100 ラウリルメタクリレート Raw material Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Synthetic resin Dispersant 1 Dispersant 2 Dispersant 3 Dispersant 4 Dispersant 5 Dispersant 6 Dispersant Agent 7 Dispersant S Dispersant 9 n-Butyl methacrylate 200 100 100 90 100 100 100 100 100 Benzyl methacrylate 100 100 100 100 100 100 100 100 Lauryl methacrylate
エチレン性  Ethylenic
メチルメタクリレ一卜  List of methyl methacrylate
不飽和単量体 Unsaturated monomer
メタク 酸 10  METHACIC ACID 10
メチルァクリレート  Methyl acrylate
ブチルァクリレート  Butylacrylate
3—メルカプト 1， 2—  3—Mercapto 1, 2—
12 12 12 12 25 40 12 12 12 メルカブタン系 プロパンジオ  12 12 12 12 25 40 12 12 12 Mercabtan Propane Geo
重合開始剤 2—メルカプト 2—メチル  Polymerization initiator 2-Mercapto 2-methyl
1, 3—プロパンジオール  1, 3-propanediol
2, 2' ーァゾビス  2, 2 'azobis
重合開始剤 0.1 0.1 0.1 イソブチル二トリル  Polymerization initiator 0.1 0.1 0.1 Isobutyl nitrile
ビュル重合体（a)の Mw 4000 4000 3600 3900 2500 1900 3500 4200 4200 ビニル重合体 (a)のガラス転移温度 (V) 20 36 36 41 36 36 36 36 36  Mw of bulle polymer (a) 4000 4000 3600 3900 2500 1900 3500 4200 4200 Glass transition temperature of vinyl polymer (a) (V) 20 36 36 41 36 36 36 36 36
PMA 12 12 19 19 40 65 19 テトラカルボン酸  PMA 12 12 19 19 40 65 19 Tetracarboxylic acid
B PDA 26 37 無水物 (b)  B PDA 26 37 Anhydride (b)
B PAF  B PAF
ネオペンチルグリコール 5 ポリオール DMB A  Neopentyl glycol 5 polyol DMB A
(c) C 1015N  (c) C 1015N
C2015N  C2015N
トリカルボン酸 Tricarboxylic acid
トリメリット酸無水物  Trimellitic anhydride
無水物（d)  Anhydride (d)
溶剤 シク口へキサノン 224 224 231 231 265 305 231 238 255 触媒 DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 酸価 28 28 43 71 78 109 43 42 56 Solvent Shikuguchi Hexanone 224 224 231 231 265 305 231 238 255 Catalyst DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Acid number 28 28 43 71 78 109 43 42 56
Mw 5800 5800 8100 8300 6300 6400 8500 9000 9300 2] Mw 5800 5800 8100 8300 6300 6400 8500 9000 9300 2]
原 料 実施例 10 実施例 11 実施例 12 実施例 13 実施例 14 実施例 15 実施例 16 実施例 17 実施例 18 合成樹脂 分散剤 10 分散剤 11 分散剤 12 分散剤 13 分散剤 14 分散剤 15 分散剤 16 分散剤 17 分散剤 18 n ブチルメタクリレート 100 160 60 100 100 100 100 ベンジルメタクリレート 100 40 140 100 100 100 100 100 ラウリルメタクリレ一ト Raw materials Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 16 Example 17 Example 18 Synthetic resin Dispersant 10 Dispersant 11 Dispersant 12 Dispersant 13 Dispersant 14 Dispersant 15 Dispersant Agent 16 Dispersant 17 Dispersant 18 n Butyl methacrylate 100 160 60 100 100 100 100 Benzyl methacrylate 100 40 140 100 100 100 100 100 Lauryl methacrylate
エチレン性  Ethylenic
メチルメタクリレート  Methyl methacrylate
不飽和単量体 Unsaturated monomer
メタクリル酸  Methacrylic acid
メチルアタリレート 100 200  Methyl acrylate 100 200
ブチルァクリレート  Butylacrylate
3—メルカプト 1, 2—  3—Mercapto 1, 2—
12 12 12 12 12 12 5 60 60 メルカブタン系 プロパンジオール  12 12 12 12 12 12 5 60 60 Mercabtan propanediol
重合開始剤 2—メルカプト一 2—メチル  Polymerization initiator 2-Mercapto-2-methyl
-1, 3—プロパンジオール  -1,3-propanediol
2, 2' —ァゾビス  2, 2 '—Azobis
重合開始剤 0.1 0.1 0.1 0.1 0.1 0.1 0, 1 0.1  Polymerization initiator 0.1 0.1 0.1 0.1 0.1 0.1 0, 1 0.1
イソブチル二トリル 0.1 ビニル重合体 (a)の Mw 4200 3900 4000 3800 4100 3850 9100 1050 1100 ビュル重合体 (a)のガラス転移温度 (V) 36 26 46 29 8 36 36 36 36 Isobutyl nitrile 0.1 Mw of vinyl polymer ( a ) 4200 3900 4000 3800 4100 3850 9100 1050 1100 Glass transition temperature (V) of bur polymer ( a ) 36 26 46 29 8 36 36 36 36
PMA 19 19 19 19 24 8 97 143 テトラカルボン酸  PMA 19 19 19 19 24 8 97 143 Tetracarboxylic acid
BPDA  BPDA
無水物 (b)  Anhydride (b)
B P AF 41  B P AF 41
ネオペンチルダリコ一ル  Neopentyl Dicole
ポリオール DMB A 39 Polyol DMB A 39
(c) C 101 5N (c) C 101 5N
C 201 5N  C 201 5N
トリカルボン酸 Tricarboxylic acid
トリメリット酸無水物  Trimellitic anhydride
無水物 (d)  Anhydride (d)
溶剤 シクロへキサノン 253 231 231 231 231 236 213 357 443 触媒 DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 酸価 39 43 43 76 43 53 19 140 200 Solvent Cyclohexanone 253 231 231 231 231 236 213 357 443 Catalyst DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Acid number 39 43 43 76 43 53 19 140 200
Mw 9100 9000 9100 8800 9300 9600 20400 2200 2300 3] Mw 9100 9000 9100 8800 9300 9600 20400 2200 2300 3]
原 料 実施例 19 実施例 20 実施例 21 実施例 22 実施例 23 実施例 実施例 25 実施例 26 実施例 27 合成樹脂 分散剤 19 分散剤 20 分散剤 21 分散剤 22 分散剤 23 分散剤 24 分散剤 25 分散剤 26 分散剤 27 η—ブチルメタクリレート 100 100 100 100 100 160 60 60 ベンジルメタクリレ一ト 100 100 100 100 100 Raw materials Example 19 Example 20 Example 21 Example 22 Example 23 Example Example 25 Example 26 Example 27 Synthetic resin Dispersant 19 Dispersant 20 Dispersant 21 Dispersant 22 Dispersant 23 Dispersant 24 Dispersant 25 Dispersant 26 Dispersant 27 η-Butyl methacrylate 100 100 100 100 100 160 60 60 Benzyl methacrylate 100 100 100 100 100
ラウリルメタクリレ一ト 60 エチレン性  Lauryl methacrylate 60 Ethylene
メチルメタクリレート 140 不飽和単量体  Methyl methacrylate 140 unsaturated monomer
メタクリル酸  Methacrylic acid
メチルァクリレート 40 40 プチルァクリレー卜 140 100 Methyl acrylate 40 40
3—メルカブ卜一 1， 2— 3—Merkabu Kouichi 1, 2—
5 12 12 12 12 12 12 12 メルカブタン系 プロパンジオール  5 12 12 12 12 12 12 12 Mercabtan propanediol
重合開始剤 2—メルカプト一 2—メチル  Polymerization initiator 2-Mercapto-2-methyl
14  14
一 1, 3—プロパンジオール  1,3-Propanediol
2, 2' —ァゾビス  2, 2 '—Azobis
重合開始剤 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 イソブチル二トリル  Polymerization initiator 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Isobutyl nitrile
ビュル重合体（a)の Mw 8500 4200 3800 4200 4100 3500 3500 3500 3500 ビニル重合体 (a)のガラス転移温度 36 36 36 36 36 18 -29 -43 75 Mw of Bulle polymer (a) 8500 4200 3800 4200 4100 3500 3500 3500 3500 Glass transition temperature of vinyl polymer ( a ) 36 36 36 36 36 18 -29 -43 75
ΡΜΑ 57 39 39 29 20 19 19 19 19 テトラカルボン酸  ΡΜΑ 57 39 39 29 20 19 19 19 19 Tetracarboxylic acid
B PDA  B PDA
無水物 (b)  Anhydride (b)
BPAF  BPAF
ネオペンチルグリコール  Neopentyl glycol
ポリオール DMB A 41 15  Polyol DMB A 41 15
(c) C 1015 N 111  (c) C 1015 N 111
C 2015N 111  C 2015N 111
トリカルボン酸 Tricarboxylic acid
トリメリット酸無水物  Trimellitic anhydride
無水物 (d)  Anhydride (d)
溶剤 シク口へキサノン 303 265 251 241 220 231 231 231 231 触媒 DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 酸価 148 96 55 42 44 43 43 43 43 Solvents Open mouth hexanone 303 265 251 241 220 231 231 231 231 Catalyst DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Acid number 148 96 55 42 44 43 43 43 43
Mw 22500 3000 12000 9400 9500 8500 9200 9500 8800 表 4] Mw 22500 3000 12000 9400 9500 8500 9200 9500 8800 Table 4]
原 料 実施例 28 実施例 29 実施例 30 実施例 31 実施例 32 実施例 33 実施例 34 合成樹脂 分散剤 28 分散剤 29 分散剤 30 分散剤 31 分散剤 32 分散剤 33 分散剤 34 n—ブチルメタタリレート 100 100 100 100 100 ベンジルメタクリレート 100 100 ラウリルメタクリレート Raw material Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Synthetic resin Dispersant 28 Dispersant 29 Dispersant 30 Dispersant 31 Dispersant 32 Dispersant 33 Dispersant 34 n-Butylmeta Tallylate 100 100 100 100 100 Benzyl methacrylate 100 100 Lauryl methacrylate
エチレン性  Ethylenic
メチルメタクリレート  Methyl methacrylate
不飽和単量体 Unsaturated monomer
メタクリル酸  Methacrylic acid
メチルァクリレート  Methyl acrylate
ブチルアタリレート 100 100 100 100 100 100 100 Butyl acrylate 100 100 100 100 100 100 100
3—メルカプト一 1, 2— 3—Mercapto 1, 2—
12 12 12 12 12 12 12 メルカブタン系 プロパンジオール  12 12 12 12 12 12 12 Mercabtan propanediol
重合開始剤 2_メルカプト一 2—メチル  Polymerization initiator 2_Mercapto-1-methyl
— 1, 3—プロパンジオール  — 1, 3-Propanediol
2, 2' —ァゾビス  2, 2 '—Azobis
重合開始剤 0.1 0.1 0.1 0.1 0.1 0.1 0.1 イソブチル二トリル  Polymerization initiator 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Isobutyl nitrile
ビニル重合体（a)の Mw 3700 3700 3700 3700 3800 4200 4100 ビニル重合体 (a)のガラス転移温度 -17 -17 -17 -17 -4 -17 -4  Mw of vinyl polymer (a) 3700 3700 3700 3700 3800 4200 4100 Glass transition temperature of vinyl polymer (a) -17 -17 -17 -17 -4 -17 -4
PMA 4 17 9 12 11 テトラカルボン酸  PMA 4 17 9 12 11 Tetracarboxylic acid
B PDA  B PDA
無水物 (b)  Anhydride (b)
B PAF 39 39 ネオペンチルグリコール 3  B PAF 39 39 Neopentyl glycol 3
ポリオール DMB A 3 Polyol DMB A 3
(c) C 10 1 5N 106 (c) C 10 1 5N 106
C 20 1 5N 211 トリカルボン酸  C 20 1 5N 211 Tricarboxylic acid
トリメリット酸無水物 26 2 16 21 33 33 19 無水物 (d)  Trimellitic anhydride 26 2 16 21 33 33 19 anhydride (d)
溶剤 シクロへキサノン 242 231 238 245 357 456 245 触媒 DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 酸価 71 43 60 74 74 58 68 Solvent Cyclohexanone 242 231 238 245 357 456 245 Catalyst DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Acid number 71 43 60 74 74 58 68
Mw 5800 8400 7100 7500 9800 12000 6500 5] 原 料 実施例 35 実施例 36 実施例 37 実施例 38 実施例 39 実施例 40 実施例 41 実施伊 J42 合成榭脂 分散剤 35 分散剤 36 分散剤 37 分散剤 38 分散剤 39 分散剤 40 分散剤 41 分散剤 42 メルカブタン系 3—メルカプト一 1, 2— Mw 5800 8400 7100 7500 9800 12000 6500 5] Raw materials Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example J42 Synthetic resin Dispersant 35 Dispersant 36 Dispersant 37 Dispersant 38 Dispersant 39 Dispersant 40 Dispersant 41 Dispersant 42 Mercabtan 3—Mercapto 1, 2, —
12 12 25 8 12 12 12 12 重合開始剤 プロパンジオール  12 12 25 8 12 12 12 12 Polymerization initiator Propanediol
PMA 19 19 40 12 37 37 28 37 テトラカルボン酸  PMA 19 19 40 12 37 37 28 37 Tetracarboxylic acid
B PDA  B PDA
無水物（b)  Anhydride (b)
B P AF  B P AF
ネオペンチルダリコール 11  Neopentyl Dalicall 11
ポリオール  Polyol
C一 1 0 1 5N 106 53  C 1 1 0 1 5N 106 53
(c)  (c)
C- 20 1 5N 212 トリカルボン酸  C-20 1 5N 212 Tricarboxylic acid
トリメ リット酸無水物  Trimellitic anhydride
無水物（d)  Anhydride (d)
n—ブチルメタタリレート 100 90 90 ベンジルメタクリレート 100 100 80 80 100 ラウリルメタクリレート  n-Butylmetatalylate 100 90 90 Benzyl methacrylate 100 100 80 80 100 Lauryl methacrylate
メチルメタクリレート 80 80 80 エチレン性  Methyl methacrylate 80 80 80 Ethylene
メタクリル酸  Methacrylic acid
不飽和単量体 Unsaturated monomer
ブチルァクリレート 80 80 80 80 80 ヒドロキシェチル  Butyl acrylate 80 80 80 80 80 Hydroxyethyl
40 20 メタクリレート  40 20 Methacrylate
2—ヒドロキシプロピル  2-hydroxypropyl
10 40 40 40 10 20 メタクリレート  10 40 40 40 10 20 Methacrylate
2, 2' —ァゾビス  2, 2 '—Azobis
重合開始剤 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 イソブチル二トリル  Polymerization initiator 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Isobutyl nitrile
溶剤 シク口へキサノン 232 232 266 220 261 356 294 462 ビニル重合体部のガラス転移温度 (t) 36 36 6 14 14 1 36 17 酸価 42 43 77 29 73 54 49 41 w 9100 11000 8200 18500 13000 22000 15000 23000 6] Solvents Open mouth hexanone 232 232 266 220 261 356 294 462 Glass transition temperature of vinyl polymer part (t) 36 36 6 14 14 1 36 17 Acid number 42 43 77 29 73 54 49 41 w 9100 11000 8200 18500 13000 22000 15000 23000 6]
原 料 実施剤 43 実施剤 44 実施剤 45 実施剤 46 実施剤 47 実施剤 48 実施剤 49 実施剤 50 合成樹脂 分散剤 43 分散剤 44 分散剤 45 分散剤 46 分散剤 47 分散剤 48 分散剤 49 分散剤 50 メルカブタン系 3 メルカプト一 1, 2_ Raw materials Implementation agent 43 Implementation agent 44 Implementation agent 45 Implementation agent 46 Implementation agent 47 Implementation agent 48 Implementation agent 49 Implementation agent 50 Synthesis resin Dispersant 43 Dispersant 44 Dispersant 45 Dispersant 46 Dispersant 47 Dispersant 48 Dispersant 49 Dispersant 49 Dispersant Agent 50 Mercabtan 3 Mercapto 1, 2_
12 12 12 12 12 12 12 12 重合開始剤 プロパンジオール  12 12 12 12 12 12 12 12 Polymerization initiator Propanediol
P A 12 19 15 31 25 テトラカルボン酸  P A 12 19 15 31 25 Tetracarboxylic acid
B PDA 8 33 無水物 (b)  B PDA 8 33 Anhydride (b)
B P AF 31  B P AF 31
ネオペンチルグリコール 11 ポリオール  Neopentyl glycol 11 polyol
C- 1 0 1 5N 106  C- 1 0 1 5N 106
(c)  (c)
C- 20 1 5N 212 212 トリカルボン酸  C-20 1 5N 212 212 Tricarboxylic acid
トリメリット酸無水物 11 8 10 7 14 27 22 22 無水物（d)  Trimellitic anhydride 11 8 10 7 14 27 22 22 Anhydride (d)
n ブチルメタクリレート 90 90 ベンジルメタクリレート 100 100 ラウリルメタクリレート  n Butyl methacrylate 90 90 Benzyl methacrylate 100 100 Lauryl methacrylate
メチルメタクリレー卜 80 80 80 80 80 80 エチレン性  Methyl methacrylate 卜 80 80 80 80 80 80 Ethylene
メタクリル酸  Methacrylic acid
不飽和単量体  Unsaturated monomer
ブチルァクリレート 80 80 100 100 80 80 ヒ ドロキシェチル  Butyl acrylate 80 80 100 100 80 80
20 20  20 20
メタクリレート  Methacrylate
2—ヒドロキシプロピル  2-hydroxypropyl
20 20 10 20 20 40 10 40 メタクリレート  20 20 10 20 20 40 10 40 Methacrylate
2, 2' ーァゾビス  2, 2 'azobis
重合開始剤 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 イソブチル二トリル  Polymerization initiator 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Isobutyl nitrile
溶剤 シク口へキサノン 236 240 231 250 253 377 472 480 ビニル重合体部のガラス転移温度 C) 17 17 36 6 6 14 36 14 酸価 53 60 39 46 63 84 55 53 Solvents Open mouth hexanone 236 240 231 250 253 377 472 480 Glass transition temperature of vinyl polymer part C) 17 17 36 6 6 14 36 14 Acid number 53 60 39 46 63 84 55 53
Mw 10000 14000 8400 13000 9100 22000 32500 31000 Mw 10000 14000 8400 13000 9100 22000 32500 31000
[0157] PMA:ピロメリット酸無水物 (ダイセルィ匕学工業株式会社製） [0157] PMA: pyromellitic anhydride (manufactured by Daicel Engineering Co., Ltd.)
BPDA:3, 3', 4, 4'ービフエニルテトラカルボン酸無水物（三菱ィ匕学株式会社製） BPAF:9, 9 ビス（3, 4—ジカルボキシフエ-ル）フルオレン二酸無水物（JFEケミ カル株式会社製）  BPDA: 3, 3 ', 4, 4'-biphenyltetracarboxylic acid anhydride (Mitsubishi Chemical Co., Ltd.) BPAF: 9, 9 Bis (3, 4-dicarboxyphenol) fluorene dianhydride (Manufactured by JFE Chemical)
DMBA：ジメチロールブタン酸（パーストープ社製）  DMBA: dimethylol butanoic acid (manufactured by Perstorp)
C 1015N: 2官能ポリカーボネートポリオール、商品名クラレポリオール C 1015 N (水酸基価 112mgKOH,g、クラレ株式会社製）  C 1015N: Bifunctional polycarbonate polyol, trade name Kuraray polyol C 1015 N (Hydroxyl value 112mgKOH, g, manufactured by Kuraray Co., Ltd.)
C-2015N: 2官能ポリカーボネートポリオール、商品名クラレポリオール C -2015 N (水酸基価 56mgKOH,g、クラレ株式会社製）  C-2015N: Bifunctional polycarbonate polyol, trade name Kuraray polyol C -2015 N (Hydroxyl value 56mgKOH, g, manufactured by Kuraray Co., Ltd.)
DBU:1, 8 ジァザビシクロー [5.4.0]— 7 ゥンデセン（サンァプロ株式会社製) [0158] (比較例 1) 撹拌機、還流冷却管、ガス導入管、温度計、滴下ロートを備えた 4口フラスコに、ジ メチルテレフタレート 559部、プロピレングリコール 420部、グリセリン 21. 2部、酢酸 亜鉛 0. 2部、テトラブチルオルソチタネート 0. 025部を仕込み、窒素気流下にて撹 拌しながら 160〜220°Cでエステル交換反応を行った。理論量のメタノールの 95% ( 175g)以上が留出したらこのフラスコ内を徐々に減圧し、 1〜3トール、 240°Cで 3時 間反応を行い、末端に水酸基を有するポリエステルを得た。次にフラスコ内を窒素で 減圧解除を行い、 200°Cまで徐々に冷却した。 200°Cになったら無水コハク酸 65部 を加え 1時間反応し、酸価 40、重量平均分子量 12000のポリエステル分散剤（=比 較分散剤 1；以下同様)を得た。 DBU: 1, 8 Gazabicyclo [5.4.0] —7 Wundecene (manufactured by SanPro Corporation) [0158] (Comparative Example 1) In a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 559 parts of dimethyl terephthalate, 420 parts of propylene glycol, 21.2 parts of glycerin, 0.2 part of zinc acetate, tetrabutyl 0.025 part of orthotitanate was charged, and a transesterification reaction was performed at 160 to 220 ° C. while stirring under a nitrogen stream. When 95% (175 g) or more of the theoretical amount of methanol was distilled, the inside of the flask was gradually depressurized and reacted at 1-3 torr and 240 ° C. for 3 hours to obtain a polyester having a hydroxyl group at the terminal. Next, the flask was depressurized with nitrogen and gradually cooled to 200 ° C. When the temperature reached 200 ° C., 65 parts of succinic anhydride was added and reacted for 1 hour to obtain a polyester dispersant having an acid value of 40 and a weight average molecular weight of 12000 (= comparative dispersant 1; the same shall apply hereinafter).
[0159] (比較例 2) [0159] (Comparative Example 2)
撹拌機、還流冷却管、ガス導入管、温度計、滴下ロートを備えた 4口フラスコに、シ ク pへキサノン 75咅、 才ペンチノレグ!; =3—ノレ 17. 8咅、無水ピ Pメジッ卜酸 31. 9咅を 仕込み、 150〜160°Cに昇温し、窒素ガス雰囲気下、 5時間反応を行った。榭脂酸 価が 334以下になった時点で冷却し、 ε—力プロラタトン 249. 7部、テトラブチルチ タネート 0. 6部を加え、 150°Cで 5時間攪拌を行った。加熱残分が 76%以上になつ た時点で冷却し、シクロへキサノン 625部をカ卩え、酸価 54、重量平均分子量 12900 のポリエステル分散剤を得た。なお、本比較例 2で調製したポリエステル分散剤は、 前記特許文献 2に記載のポリエステル分散剤に相当する。  In a 4-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel An acid 31.9% was charged, the temperature was raised to 150 to 160 ° C., and the reaction was performed in a nitrogen gas atmosphere for 5 hours. When the succinic acid value became 334 or less, the mixture was cooled, 249.7 parts of ε-force prolatatone and 0.6 parts of tetrabutyl titanate were added, and the mixture was stirred at 150 ° C for 5 hours. When the heating residue reached 76% or more, the mixture was cooled to obtain 625 parts of cyclohexanone to obtain a polyester dispersant having an acid value of 54 and a weight average molecular weight of 12900. The polyester dispersant prepared in Comparative Example 2 corresponds to the polyester dispersant described in Patent Document 2.
[0160] (比較例 3) [0160] (Comparative Example 3)
撹拌機、還流冷却管、ガス導入管、温度計、滴下ロートを備えた 4口フラスコに、 1, 2, 4, 5—ベンゼンテトラカルボン酸 25. 4g、 2—ェチルへキシルアルコール 39. Og 、キシレン 50mLの混合物をカ卩え、ここにテトラブチルチタネート 0. 2gを加え窒素気 流中 160〜180°Cで 18時間加熱還流させ発生した水分はジーン 'スタークトラップで 分離した。反応終了後 150°Cにて減圧下にて、キシレンを除去した。酸価 96. OgK OH/g,淡褐色のポリエステル分散剤を得た。なお、本比較例 3で調製したポリエス テル分散剤は、前記特許文献 1に記載のポリエステル分散剤に相当する。  In a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, dropping funnel, 1, 2, 4, 5-benzenetetracarboxylic acid 25.4 g, 2-ethylhexyl alcohol 39. Og, A mixture of 50 mL of xylene was added, and 0.2 g of tetrabutyl titanate was added thereto, and heated and refluxed at 160 to 180 ° C. for 18 hours in a nitrogen gas stream. After completion of the reaction, xylene was removed under reduced pressure at 150 ° C. Acid value 96. OgK OH / g, a light brown polyester dispersant was obtained. The polyester dispersant prepared in Comparative Example 3 corresponds to the polyester dispersant described in Patent Document 1.
[0161] (比較例 4) [0161] (Comparative Example 4)
撹拌機、還流冷却管、ガス導入管、温度計、滴下ロートを備えた 4口フラスコに、キ シレン 19. 8部、ォクタノール 2. 1部、 ε一力プロラタトン 77. 9部テトラブチルチタネ ート 0. 16部を仕込み 150〜160°Cに昇温し窒素ガス雰囲気下、 5時間反応させカロ 熱残分が 78%以上になっているのを確認した後、冷却しポリエステルモノオールを 得た。合成したポリエステルモノオールを 31. 86部、無水トリメリット酸 0. 98部を仕込 み窒素雰囲気下 150〜160°Cで反応を行った。榭脂酸価が 22. 7以下になった時 点で YED122 (ジャパンエポキシレジン株式会社製、商品名アルキルフエノールモノ グリシジルエーテル、エポキシ当量 250)、 2. 55部を仕込み同じ温度で反応を行つ た。榭脂酸価が 1. 1以下になった時点で無水トリメリット酸 1. 96部を仕込み、同じ温 度で反応を行い、榭脂酸価が 38. 7以下になった時点で YED122、 5. 1部を仕込 み、同じ温度で反応を行い、榭脂酸価が 1. 8以下になった時点で無水トリメリット酸 3 . 92部を仕込み、同じ温度で反応を行い、榭脂酸価が 60. 1以下になった時点で冷 却し、キシレンを 53. 6部加え、反応を終了させた。酸価 58. 9、重量平均分子量 11 000のポリエステル分散剤を得た。なお、本比較例 4で調製したポリエステル分散剤 は、前記特許文献 3に記載のポリエステル分散剤に相当する。 A four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel was 19.8 parts of silene, 2.1 parts of octanol, 1 part of prolatatone epsilon 77.9 parts of tetrabutyl titanate 0.16 parts, heated to 150-160 ° C and reacted for 5 hours under nitrogen gas atmosphere After confirming that the caro heat residue was 78% or more, it was cooled to obtain a polyester monool. 31.86 parts of the synthesized polyester monool and 0.98 parts of trimellitic anhydride were charged and reacted at 150 to 160 ° C. in a nitrogen atmosphere. YED122 (trade name: alkylphenol monoglycidyl ether, epoxy equivalent 250, manufactured by Japan Epoxy Resin Co., Ltd.), 2. 55 parts when succinic acid value becomes 22.7 or less, react at the same temperature It was. When the succinic acid value is 1.1 or less, add 1.96 parts of trimellitic anhydride and react at the same temperature. When the succinic acid value becomes 38.7 or less, YED122, 5 Charge 1 part and react at the same temperature. When the succinic acid number drops to 1.8 or less, add 3.92 parts trimellitic anhydride and react at the same temperature. When the temperature became 60.1 or less, the mixture was cooled and 53.6 parts of xylene was added to terminate the reaction. A polyester dispersant having an acid value of 58.9 and a weight average molecular weight of 11 000 was obtained. The polyester dispersant prepared in Comparative Example 4 corresponds to the polyester dispersant described in Patent Document 3.
(比較例 5) (Comparative Example 5)
ォキシ塩化リン 26. 6部（0. 18mol)を 70部のテトラヒドロフランに溶解し、反応容 器に入れ、— 50°Cまで冷却した。プラクセル FM4 (ダイセルィ匕学工業製） 100部とト リエチルァミン 16. 7g (0. 17mol)とハイドロキノンモノメチルエーテル 0. 1部をテトラ ヒドロフラン 150部に溶解し、滴下ロートに入れた。乾燥窒素ガスを吹き込みながら、 ォキシ塩化リン溶液を攪拌し、前記プラクセル 4A溶液を滴下した。滴下中は一 45〜 — 50°Cに保ち、滴下終了後 1時 20間— 45°Cに保った。その後、 0°Cまで昇温し、水 15部とトリェチルァミン 37. 9部を 100部のテトラヒドロフランに溶解した溶液を滴下し た。滴下終了後、 15時間氷冷下攪拌し、 P— C1結合の加水分解を完了させた。そ の後析出したトリェチルアンモ -ゥムクロリドをろ別し、テトラヒドロフランを 30°C以下の 温度で減圧除去した。得られた固体を 0. 3N塩酸水溶液で洗浄した。次にトルエン で数回洗浄した後、室温にて減圧乾燥し、末端にリン酸基を有するポリエステル分散 剤が得られた。なお、本比較例 5で調製したポリエステル分散剤は、前記特許文献 4 に記載のポリエステル分散剤に相当する。 [0163] [塩基性基を有する顔料誘導体 (Y)の製造例 1] 26.6 parts (0.18 mol) of phosphorus oxychloride was dissolved in 70 parts of tetrahydrofuran, placed in a reaction vessel, and cooled to -50 ° C. 100 parts of PLACCEL FM4 (manufactured by Daicel Chemical Industries), 16.7 g (0.17 mol) of triethylamine and 0.1 part of hydroquinone monomethyl ether were dissolved in 150 parts of tetrahydrofuran and placed in a dropping funnel. While blowing dry nitrogen gas, the phosphorus oxychloride solution was stirred, and the Plaxel 4A solution was added dropwise. During dropping, the temperature was kept at 45 to 50 ° C, and kept at 45 ° C for 1-20 hours after the dropping. Thereafter, the temperature was raised to 0 ° C., and a solution of 15 parts of water and 37.9 parts of triethylamine in 100 parts of tetrahydrofuran was added dropwise. After completion of the dropwise addition, the mixture was stirred for 15 hours under ice cooling to complete hydrolysis of the P—C1 bond. Thereafter, the precipitated triethylammonium chloride was filtered off and tetrahydrofuran was removed under reduced pressure at a temperature of 30 ° C or lower. The obtained solid was washed with 0.3N hydrochloric acid aqueous solution. Next, after washing several times with toluene, it was dried under reduced pressure at room temperature to obtain a polyester dispersant having a phosphate group at the terminal. The polyester dispersant prepared in Comparative Example 5 corresponds to the polyester dispersant described in Patent Document 4. [0163] [Production Example 1 of pigment derivative (Y) having a basic group]
色素成分である銅フタロシアニン 50部をクロロスルホン化した後、ァミン成分である Ν, Ν—ジメチルァミノプロピルアミン 14部と反応させて塩基性基を有する顔料誘導 体 (Y1) 62部を得た。  Chlorosulfonated 50 parts of copper phthalocyanine as a pigment component, and then reacted with 14 parts of ァ, Ν-dimethylaminopropylamine as an amine component to obtain 62 parts of a pigment derivative (Y1) having a basic group .
[0164] 塩基性基を有する顔料誘導体 (Y1)  [0164] Pigment derivative having basic group (Y1)
[化 30]
Figure imgf000050_0001
[Chemical 30]
Figure imgf000050_0001
[0165] CuPcは、銅フタロシアニン残基を表す。  [0165] CuPc represents a copper phthalocyanine residue.
[0166] [塩基性基を有する顔料誘導体 (Y)の製造例 2] [0166] [Production Example 2 of pigment derivative (Y) having a basic group]
色素成分である銅フタロシアニン 50部をクロロメチルイ匕した後、ァミン成分であるジ プチルァミン 40部と反応させて塩基性基を有する顔料誘導体 (Y2) 95部を得た。  After 50 parts of copper phthalocyanine as a pigment component was chloromethylated, it was reacted with 40 parts of diptylamine as an amine component to obtain 95 parts of a pigment derivative (Y2) having a basic group.
[0167] 塩基性基を有する顔料誘導体 (Y2)  [0167] Pigment derivative having basic group (Y2)
[化 31]
Figure imgf000050_0002
[Chemical 31]
Figure imgf000050_0002
[0168] CuPcは、銅フタロシアニン残基を表す。  [0168] CuPc represents a copper phthalocyanine residue.
[0169] [塩基性基を有する顔料誘導体 (Y)の製造例 3] [0169] [Production Example 3 of pigment derivative (Y) having a basic group]
色素成分であるキナクリドン 50部をクロロアセトアミドメチルイ匕した後、ァミン成分で ある N—メチルビペラジン 40部と反応させて塩基性基を有する顔料誘導体 (Y3) 10 3部を得た。  After 50 parts of quinacridone as a pigment component was chloroacetamidomethyli, it was reacted with 40 parts of N-methylbiperazine as an amine component to obtain 103 parts of pigment derivative (Y3) having a basic group.
[0170] 塩基性基を有する顔料誘導体 (Y3)  [0170] Pigment derivative having basic group (Y3)
[化 32] CH2NHCOCH2 N N— C¾ [Chemical 32] CH 2 NHCOCH 2 NN— C¾
[0171] [塩基性基を有する顔料誘導体 (Y)の製造例 4] [0171] [Production Example 4 of pigment derivative (Y) having a basic group]
色素成分としてジフエ-ルジケトビロロピロールを、ァミン成分として N—ァミノプロピ ルモルホリンを使用し、製造例 1と同様の方法により、塩基性基を有する顔料誘導体 (Y4)を得た。  A pigment derivative (Y4) having a basic group was obtained in the same manner as in Production Example 1 using diphenyl diketopyrrolopyrrole as the dye component and N-aminopropylmorpholine as the amine component.
[0172] 塩基性基を有する顔料誘導体 (Y4)  [0172] Pigment derivative having basic group (Y4)
[化 33]  [Chemical 33]
Figure imgf000051_0001
Figure imgf000051_0001
[0173] [塩基性基を有する顔料誘導体 (Y)の製造例 5〜10]  [0173] [Production Examples 5-10 of pigment derivative (Y) having basic group]
上記塩基性基を有する顔料誘導体 (Y)の製造例 1〜4と同様の方法により、下記に 示す顔料誘導体、アントラキノン誘導体、アタリドン誘導体又はトリァジン誘導体を得 た。  The following pigment derivatives, anthraquinone derivatives, attaridone derivatives or triazine derivatives were obtained by the same method as in Production Examples 1 to 4 of the pigment derivative (Y) having the basic group.
[0174] 塩基性基を有する顔料誘導体 (Y5)  [0174] Pigment derivative having basic group (Y5)
[化 34]
Figure imgf000052_0001
[Chemical 34]
Figure imgf000052_0001
[0175] 塩基性基を有する顔料誘導体 (Y6) [化 35]
Figure imgf000052_0002
[0175] Pigment derivative having basic group (Y6)
Figure imgf000052_0002
[0176] 塩基性基を有する顔料誘導体 (Y7) [化 36]
Figure imgf000052_0003
[0176] Pigment derivative having basic group (Y7)
Figure imgf000052_0003
[0177] 塩基性基を有する顔料誘導体 (Y8) [化 37] [0177] Pigment derivative having basic group (Y8) [Chemical formula 37]
Figure imgf000052_0004
[0178] 塩基性基を有する顔料誘導体 (Y9)
Figure imgf000052_0004
[0178] Pigment derivative having basic group (Y9)
[化 38]  [Chemical 38]
Figure imgf000053_0001
Figure imgf000053_0001
[0179] 塩基性基を有する顔料誘導体 (Y10)  [0179] Pigment derivative having basic group (Y10)
[化 39]  [Chemical 39]
Figure imgf000053_0002
Figure imgf000053_0002
[0180] (実施例 51〜59) <顔料組成物の製造 >  (Examples 51 to 59) <Production of pigment composition>
表 7に示すように、顔料（C. I. Pigment Blue 15 : 3)、実施例 1〜9にて合成し たポリエステル分散剤、製造例 1で合成した塩基性基を有する顔料誘導体 (Y1)、及 びシクロへキサノンを配合し、直径 2mmのジルコユアビーズ 100部をカ卩ぇペイントコ ンデイショナ一で 3時間分散し、顔料組成物を作成した。  As shown in Table 7, the pigment (CI Pigment Blue 15: 3), the polyester dispersant synthesized in Examples 1 to 9, the pigment derivative (Y1) having a basic group synthesized in Production Example 1, and A pigment composition was prepared by blending cyclohexanone and dispersing 100 parts of 2 mm diameter Zirco Your beads in a paint paint conditioner for 3 hours.
[0181] (比較例 6及び 7) <顔料組成物の製造 >  [0181] (Comparative Examples 6 and 7) <Production of pigment composition>
比較例 1、 2にて合成したカルボキシル基含有ポリエステルを用いた以外は、実施 例 51〜59と同様に顔料組成物を作成した。  A pigment composition was prepared in the same manner as in Examples 51 to 59 except that the carboxyl group-containing polyester synthesized in Comparative Examples 1 and 2 was used.
[0182] (顔料組成物の評価）  [0182] (Evaluation of pigment composition)
本発明の顔料組成物の性能を評価するために、得られた組成物の粘度を B型粘度 計（25°C、回転速度 lOOrpm)で、ヘイズをヘイズメーター（光透過率 20%)で測定し 、初期粘度及びヘイズで分散体の性能を評価した (粘度は低いほど良好。ヘイズは 小さいほど良好)。初期粘度及びヘイズは分散後 1日室温で放置後に測定、経時粘 度は 1週間 40°Cに放置後に測定を行った。結果を表 7に示す。 In order to evaluate the performance of the pigment composition of the present invention, the viscosity of the obtained composition was measured with a B-type viscometer (25 ° C, rotation speed lOOrpm), and the haze was measured with a haze meter (light transmittance 20%). The performance of the dispersion was evaluated based on the initial viscosity and haze (the lower the viscosity, the better the haze, the lower the haze, the better). Initial viscosity and haze are measured after standing at room temperature for 1 day after dispersion. The temperature was measured after leaving at 40 ° C for one week. The results are shown in Table 7.
[0183] [表 7] [0183] [Table 7]
Figure imgf000054_0001
Figure imgf000054_0001
[0184] 以上の評価結果カゝら明らかなように、本発明のポリエステル分散剤を使用した実施 例 51〜59の顔料組成物は、低い初期粘度で、かつ経時粘度の増加がほとんどなく 良好な安定性を示している。更にヘイズも低い。これに対して、比較例 6、 7の顔料組 成物では、粘度とヘイズともに高ぐ分散性に問題があることがわ力つた。  [0184] As is apparent from the above evaluation results, the pigment compositions of Examples 51 to 59 using the polyester dispersant of the present invention have a low initial viscosity and are almost free from an increase in viscosity over time. It shows stability. Furthermore, the haze is also low. On the other hand, the pigment compositions of Comparative Examples 6 and 7 were found to have problems with high dispersibility in both viscosity and haze.
[0185] (実施例 60)  [0185] (Example 60)
顔料として Pigment Blue 15 : 3を 9部、塩基性基を有する顔料誘導体 (Y1)を 1 部、分散剤 3を 1部（固形)、アルキッド榭脂（日立化成社製けタルキッド 133— 60」） 29部、シクロへキサノン 60部を、マヨネーズ瓶に仕込み、直径 0. 5mmのジルコユア ビーズ 250部を分散メディアとして仕込み、ペイントシエイカ一にて本分散を行い、顔 料分散体を得た。  Pigment Blue 15: 9 parts as pigment, 1 part of pigment derivative (Y1) with basic group, 1 part of dispersant 3 (solid), alkyd resin (Talkid 133-60 from Hitachi Chemical Co., Ltd.) 29 parts and 60 parts of cyclohexanone were charged into a mayonnaise bottle, 250 parts of 0.5 mm diameter Zircoyu beads were charged as a dispersion medium, and this dispersion was performed with a paint shaker to obtain a facial dispersion.
[0186] 得られた顔料分散体の粘度を B型粘度計で測定し、粘度及び TI値 (6rpmでの粘 度 Z60rpmでの粘度)で分散体の性能を評価した。 6rpmでの粘度は 1 lOmPa · s、 60rpmでの粘度は lOOmPa' sで、 TI値は 1. 11であった。また、得られた顔料分散 体を 50°Cの恒温機に 1週間保存、経時促進させた後、経時前後での顔料分散体の 粘度変化について測定した。 6rpmでの粘度は 105mPa' sで変化率は 5%であつ た。顔料分散体をガラスに塗膜、溶剤除去した後に、 200°C、 1時間加熱前後の重量 損失％は 8. 5%であった。  [0186] The viscosity of the obtained pigment dispersion was measured with a B-type viscometer, and the performance of the dispersion was evaluated by viscosity and TI value (viscosity at 6 rpm, viscosity at Z60 rpm). The viscosity at 6 rpm was 1 lOmPa · s, the viscosity at 60 rpm was lOOmPa's, and the TI value was 1.11. The obtained pigment dispersion was stored in a thermostat at 50 ° C. for 1 week and accelerated with time, and the change in viscosity of the pigment dispersion before and after aging was measured. The viscosity at 6 rpm was 105 mPa's and the rate of change was 5%. After the pigment dispersion was coated on glass and the solvent was removed, the weight loss% before and after heating at 200 ° C for 1 hour was 8.5%.
[0187] (実施例 61〜119)  [0187] (Examples 61 to 119)
実施例 60と同様にして、表 8及び 9に示す配合比 (重量比）により、それぞれ顔料 分散体を得た。また、実施例 60と同様の方法で評価した (粘度は低いほど良好、 TI 値は 1に近いほど良好)。 In the same manner as in Example 60, the pigments were mixed at the blending ratios (weight ratios) shown in Tables 8 and 9, respectively. A dispersion was obtained. The evaluation was made in the same manner as in Example 60 (the lower the viscosity, the better, the closer the TI value is to 1, the better).
[0188] (顔料分散体の評価） [0188] (Evaluation of pigment dispersion)
粘度安定性は 50°C1週間保存前後の粘度の変化率が ± 10%以内なら〇、士 10 Viscosity stability is 〇 or 10 if the rate of change in viscosity before and after storage at 50 ° C for 1 week is within ± 10%.
%を超えたら Xとした。塗膜重量損失は、ガラスに塗膜、溶剤除去した後に、 200°CWhen it exceeded%, it was set as X. The coating weight loss is 200 ° C after removing the coating film and solvent on the glass.
、 1時間加熱前後の重量損失が 10%以内であれば〇、 10%を超えた場合を Xとし た。結果を表 10及び 11に示す。 When the weight loss before and after heating for 1 hour is within 10%, it was marked as ◯, and when it exceeded 10%, X was marked. The results are shown in Tables 10 and 11.
[0189] [表 8] [0189] [Table 8]
顔 料 顔料誘導体 (Y) 分散剤 アルキド樹脂 シクロへキサノンFacial pigment Pigment derivative (Y) Dispersant Alkyd resin Cyclohexanone
C. I. No. w t% 種類 wt% 種類 wt% wt% wt% 実施例 60 Pigment Blue 15:3 9 Yl 1 分散剤 3 1 29 60 実施例 61 Pigment Blue 15:3 9 Yl 1 分散剤 7 1.5 28.5 60 実施例 62 Pigment Blue 15:3 9 Yl 1 分散剤 8 1 29 60 実施例 63 Pigment Blue 15:3 9 Yl 1 分散剤 10 1 29 60 実施例 64 Pigment Blue 15:3 9 Yl 1 分散剤 13 1 29 60 実施例 65 Pigment Blue 15:3 9 Yl 1 分散剤 14 1 29 60 実施例 66 Pigment Blue 15:3 9 Yl 1 分散剤 15 1 29 60 実施例 67 Pigment Blue 15:3 9 Yl 1 分散剤 16 1 29 60 実施例 68 Pigment Blue 15:3 9 Yl 1 分散剤 17 1 29 60 実施例 69 Pigment Blue 15:3 9 Yl 1 分散剤 21 1 29 60 実施例 70 Pigment Blue 15:3 9 Yl 1 分散剤 23 1 29 60 実施例 71 Pigment Red 122 9 Y7 1 分散剤 11 2 28 60 実施例 72 Pigment Red 122 9 Y7 1 分散剤 12 2 28 60 実施例 73 Pigment Red 122 9 Y7 1 分散剤 22 2 28 60 実施例 74 Pigment Green 36 8 Y2 2 分散剤 4 2 28 60 実施例 75 Pigment Green 36 8 Y2 2 分散剤 18 2 28 60 実施例 76 Pigment Green 36 8 Y2 2 分散剤 19 2 28 60 実施例 77 Pigment Green 36 8 Y2 2 分散剤 20 2 28 60 実施例 78 Pigment Violet 23 8 Y6 2 分散剤 3 2 28 60 実施例 79 Pigment Violet 23 8 Y6 2 分散剤 5 2 28 60 実施例 80 Pigment Yellow 12 9 Y8 1 分散剤 2 2 28 60 実施例 81 Pigment Yellow 12 9 Y8 1 分散剤 6 2 28 60 実施例 82 Pigment Black 7 9 Yl 1 分散剤 1 1 29 60 実施例 83 Pigment Black 7 9 Yl 1 分散剤 8 1 29 60 実施例 84 Pigment Black 7 9 Yl 1 分散剤 9 1 29 60 実施例 85 Pigment Red 122 9 Y3 1 分散剤 7 2 28 60 実施例 86 Pigment Red 254 9 Y4 1 分散剤 14 2 28 60 実施例 87 Pigment Blue 6 8 Y5 2 分散剤 20 2 28 60 実施例 88 Pigment Violet 23 8 Y6 2 分散剤 6 2 28 60 実施例 89 Pigment Red 57:1 9 Y9 1 分散剤 21 2 28 60 9] 顔 料 顔料誘導体 (Y) 分散剤 アルキド樹脂 シクロへキサノンCI No. wt% Type wt% Type wt% wt% wt% Example 60 Pigment Blue 15: 3 9 Yl 1 Dispersant 3 1 29 60 Example 61 Pigment Blue 15: 3 9 Yl 1 Dispersant 7 1.5 28.5 60 Example 62 Pigment Blue 15: 3 9 Yl 1 Dispersant 8 1 29 60 Example 63 Pigment Blue 15: 3 9 Yl 1 Dispersant 10 1 29 60 Example 64 Pigment Blue 15: 3 9 Yl 1 Dispersant 13 1 29 60 Example 65 Pigment Blue 15: 3 9 Yl 1 Dispersant 14 1 29 60 Example 66 Pigment Blue 15: 3 9 Yl 1 Dispersant 15 1 29 60 Example 67 Pigment Blue 15: 3 9 Yl 1 Dispersant 16 1 29 60 Example 68 Pigment Blue 15: 3 9 Yl 1 Dispersant 17 1 29 60 Example 69 Pigment Blue 15: 3 9 Yl 1 Dispersant 21 1 29 60 Example 70 Pigment Blue 15: 3 9 Yl 1 Dispersant 23 1 29 60 Example 71 Pigment Red 122 9 Y7 1 Dispersant 11 2 28 60 Example 72 Pigment Red 122 9 Y7 1 Dispersant 12 2 28 60 Example 73 Pigment Red 122 9 Y7 1 Dispersant 22 2 28 60 Example 74 Pigment Green 36 8 Y2 2 Dispersant 4 2 28 60 Example 75 Pigment Green 36 8 Y2 2 Dispersant 18 2 28 60 Example 76 Pigment Gr een 36 8 Y2 2 Dispersant 19 2 28 60 Example 77 Pigment Green 36 8 Y2 2 Dispersant 20 2 28 60 Example 78 Pigment Violet 23 8 Y6 2 Dispersant 3 2 28 60 Example 79 Pigment Violet 23 8 Y6 2 Dispersant 5 2 28 60 Example 80 Pigment Yellow 12 9 Y8 1 Dispersant 2 2 28 60 Example 81 Pigment Yellow 12 9 Y8 1 Dispersant 6 2 28 60 Example 82 Pigment Black 7 9 Yl 1 Dispersant 1 1 29 60 Example 83 Pigment Black 7 9 Yl 1 Dispersant 8 1 29 60 Example 84 Pigment Black 7 9 Yl 1 Dispersant 9 1 29 60 Example 85 Pigment Red 122 9 Y3 1 Dispersant 7 2 28 60 Example 86 Pigment Red 254 9 Y4 1 Dispersant 14 2 28 60 Example 87 Pigment Blue 6 8 Y5 2 Dispersant 20 2 28 60 Example 88 Pigment Violet 23 8 Y6 2 Dispersant 6 2 28 60 Example 89 Pigment Red 57: 1 9 Y9 1 Dispersant 21 2 28 60 9] Facial pigment Pigment derivative (Y) Dispersant Alkyd resin Cyclohexanone
C. I. No. w t % 種類 w t % 種類 w t % w t % w t % 実施例 90 Pigment Red 57 1 9 Y10 1 分散剤 23 2 28 60 実施例 91 Pigment Red 57 1 9 Y10 1 分散剤 24 2 28 60 実施例 92 Pigment Red 57 1 9 Y10 1 分散剤 25 2 28 60 実施例 93 Pigment Red 57 1 9 Y10 1 分散剤 26 2 28 60 実施例 94 Pigment Red 57 1 9 Y10 1 分散剤 27 2 28 60 実施例 95 Pigment Red 57 1 9 Y10 1 分散剤 28 2 28 60 実施例 96 Pigment Red 57 1 9 Y10 1 分散剤 29 2 28 60 実施例 97 Pigment Red 57 1 9 Y10 1 分散剤 30 2 28 60 実施例 98 Pigment Red 57 1 9 Y10 1 分散剤 31 2 28 60 実施例 99 Pigment Green 36 8 Y2 2 分散剤 36 2 28 60 実施例 100 Pigment Green 36 8 Y2 2 分散剤 37 2 28 60 実施例 101 Pigment Green 36 8 Y2 2 分散剤 38 2 28 60 実施例 102 Pigment Green 36 8 Y2 2 分散剤 39 2 28 60 実施例 103 Pigment Green 36 8 Y2 2 分散剤 40 2 28 60 実施例 104 Pi ment Green 36 8 Y2 2 分散剤 41 2 28 60 実施例 105 Pigment Green 36 8 Y2 2 分散剤 42 2 28 60 実施例 106 Pigment Green 36 8 Y2 2 分散剤 43 2 28 60 実施例 107 Pigment Green 36 8 Y2 2 分散剤 44 2 28 60 実施例 108 Pigment Green 36 8 Y2 2 分散剤 45 2 28 60 実施例 109 Pigment Green 36 8 Y2 2 分散剤 46 2 28 60 実施例 110 Pi ment Green 36 8 Y2 2 分歉剤 47 2 28 60 実施例 111 Pi ment Green 36 8 Y2 2 分散剤 48 2 28 60 実施例 112 Pigment Green 36 8 Y2 2 分散剤 49 2 28 60 実施例 113 Pigment Green 36 8 Y2 2 分散剤 50 2 28 60 実施例 114 Pigment Blue 15 : 3 9 Yl 1 分散剤 30 1 29 60 実施例 115 Pigment Blue 15 : 3 9 Yl 1 分散剤 32 1 29 60 実施例 116 Pigment Blue 15: 3 9 Yl 1 分散剤 33 1 29 60 実施例 1Π Pigment Blue 15 : 3 9 Yl 1 分散剤 34 1 29 60 実施例 118 Pigment Blue 15 : 3 9 Yl 1 分散剤 35 1 29 60 実施例 119 Pigment Red 57: 1 9 Y10 1 分 »剤 35 2 28 60 10] 粘度 (mPa - s) CI No. wt% Type wt% Type wt% wt% wt% Example 90 Pigment Red 57 1 9 Y10 1 Dispersant 23 2 28 60 Example 91 Pigment Red 57 1 9 Y10 1 Dispersant 24 2 28 60 Example 92 Pigment Red 57 1 9 Y10 1 Dispersant 25 2 28 60 Example 93 Pigment Red 57 1 9 Y10 1 Dispersant 26 2 28 60 Example 94 Pigment Red 57 1 9 Y10 1 Dispersant 27 2 28 60 Example 95 Pigment Red 57 1 9 Y10 1 Dispersant 28 2 28 60 Example 96 Pigment Red 57 1 9 Y10 1 Dispersant 29 2 28 60 Example 97 Pigment Red 57 1 9 Y10 1 Dispersant 30 2 28 60 Example 98 Pigment Red 57 1 9 Y10 1 Dispersant 31 2 28 60 Example 99 Pigment Green 36 8 Y2 2 Dispersant 36 2 28 60 Example 100 Pigment Green 36 8 Y2 2 Dispersant 37 2 28 60 Example 101 Pigment Green 36 8 Y2 2 Dispersant 38 2 28 60 Example 102 Pigment Green 36 8 Y2 2 Dispersant 39 2 28 60 Example 103 Pigment Green 36 8 Y2 2 Dispersant 40 2 28 60 Example 104 Piment Green 36 8 Y2 2 Dispersant 41 2 28 60 Example 105 Pigment Green 36 8 Y2 2 Dispersant 42 2 28 60 Example 1 06 Pigment Green 36 8 Y2 2 Dispersant 43 2 28 60 Example 107 Pigment Green 36 8 Y2 2 Dispersant 44 2 28 60 Example 108 Pigment Green 36 8 Y2 2 Dispersant 45 2 28 60 Example 109 Pigment Green 36 8 Y2 2 Dispersant 46 2 28 60 Example 110 Piment Green 36 8 Y2 2 Dispersant 47 2 28 60 Example 111 Piment Green 36 8 Y2 2 Dispersant 48 2 28 60 Example 112 Pigment Green 36 8 Y2 2 Dispersant 49 2 28 60 Example 113 Pigment Green 36 8 Y2 2 Dispersant 50 2 28 60 Example 114 Pigment Blue 15: 3 9 Yl 1 Dispersant 30 1 29 60 Example 115 Pigment Blue 15: 3 9 Yl 1 Dispersion Agent 32 1 29 60 Example 116 Pigment Blue 15: 3 9 Yl 1 Dispersant 33 1 29 60 Example 1 Π Pigment Blue 15: 3 9 Yl 1 Dispersant 34 1 29 60 Example 118 Pigment Blue 15: 3 9 Yl 1 Dispersant 35 1 29 60 Example 119 Pigment Red 57: 1 9 Y10 1 min »Agent 35 2 28 60 10] Viscosity (mPa-s)
T I値 粘度安定性 塗膜重量損失 T I value Viscosity stability Paint film weight loss
6rpra 60rpra 6rpra 60rpra
実施例 60 110 100 1.10 〇 〇 実施例 61 100 100 1.00 〇 0 実施例 62 100 95 1.05 〇 〇 実施例 63 95 90 1.06 〇 〇 実施例 64 85 85 1.00 〇 0 実施例 65 130 125 1.04 〇 〇 実施例 66 120 115 1.04 〇 〇 実施例 67 180 150 1.20 〇 〇 実施例 68 200 150 1.33 〇 〇 実施例 69 150 130 1.15 〇 0 実施例 70 160 145 1.10 〇 〇 実施例 71 200 180 1.11 〇 0 実施例 72 220 210 1.05 0 〇 実施例 73 160 150 1.07 〇 〇 実施例 74 300 260 1.15 〇 〇 実施例 75 400 320 1.25 〇 〇 実施例 76 350 330 1.06 0 〇 実施例 77 310 300 1.03 〇 0 実施例 78 140 140 1.00 〇 0 実施例 79 160 150 1.07 〇 〇 実施例 80 400 320 1.25 〇 0 実施例 81 500 350 1.43 〇 0 実施例 82 80 75 1.07 〇 〇 実施例 83 50 50 1.00 〇 〇 実施例 84 65 60 1.08 〇 〇 実施例 85 200 205 0.98 〇 0 実施例 86 240 230 1.04 〇 0 実施例 87 400 380 1.05 〇 〇 実施例 88 180 160 1.13 0 〇 実施例 89 350 300 1.17 〇 0 11] 粘度 (mPa · s) Example 60 110 100 1.10 ○ ○ Example 61 100 100 1.00 ○ 0 Example 62 100 95 1.05 ○ ○ Example 63 95 90 1.06 ○ ○ Example 64 85 85 1.00 ○ 0 Example 65 130 125 1.04 ○ ○ Example 66 120 115 1.04 ○ ○ Example 67 180 150 1.20 ○ ○ Example 68 200 150 1.33 ○ ○ Example 69 150 130 1.15 ○ 0 Example 70 160 145 1.10 ○ ○ Example 71 200 180 1.11 ○ 0 Example 72 220 210 1.05 0 ○ Example 73 160 150 1.07 ○ ○ Example 74 300 260 1.15 ○ ○ Example 75 400 320 1.25 ○ ○ Example 76 350 330 1.06 0 ○ Example 77 310 300 1.03 ○ 0 Example 78 140 140 1.00 ○ 0 Example 79 160 150 1.07 ○ ○ Example 80 400 320 1.25 ○ 0 Example 81 500 350 1.43 ○ 0 Example 82 80 75 1.07 ○ ○ Example 83 50 50 1.00 ○ ○ Example 84 65 60 1.08 ○ ○ Example 85 200 205 0.98 ○ 0 Example 86 240 230 1.04 ○ 0 Example 87 400 380 1.05 ○ ○ Example 88 180 160 1.13 0 ○ Example 89 350 300 1.17 ○ 0 11] Viscosity (mPas)
T I値 粘度安定性 塗膜重量損失  T I value Viscosity stability Paint film weight loss
6rpm 60rpm  6rpm 60rpm
実施例 90 300 270 1.11 0 〇  Example 90 300 270 1.11 0 〇
実施例 91 310 300 1.03 〇 〇  Example 91 310 300 1.03 ○ ○
実施例 92 340 290 1.17 〇 〇  Example 92 340 290 1.17 ○ ○
実施例 93 390 380 1.03 〇 〇  Example 93 390 380 1.03 ○ ○
実施例 94 500 400 1.25 〇 〇  Example 94 500 400 1.25 〇 〇
実施例 95 500 450 1.11 〇 〇  Example 95 500 450 1.11 〇 〇
実施例 96 450 410 1.10 〇 〇  Example 96 450 410 1.10 〇 〇
実施例 97 330 310 1.06 〇 〇  Example 97 330 310 1.06 ○ ○
実施例 98 340 330 1.03 0 〇  Example 98 340 330 1.03 0 〇
実施例 99 370 310 1.19 〇 〇  Example 99 370 310 1.19 ○ ○
実施例 100 330 300 1.10 〇 〇  Example 100 330 300 1.10 〇 〇
実施例 101 350 340 1.03 〇 0  Example 101 350 340 1.03 〇 0
実施例 102 300 250 1.20 〇 〇  Example 102 300 250 1.20 ○ ○
実施例 103 250 210 1.19 〇 〇  Example 103 250 210 1.19 ○ ○
実施例 104 320 320 1.00 0 〇  Example 104 320 320 1.00 0 〇
実施例 105 380 350 1.09 〇 〇  Example 105 380 350 1.09 〇 〇
実施例 106 280 270 1.04 〇 〇  Example 106 280 270 1.04 ○ ○
実施例 107 280 280 1.00 〇 0  Example 107 280 280 1.00 〇 0
実施例 108 310 280 1.11 〇 〇  Example 108 310 280 1.11 〇 〇
実施例 109 280 270 1.04 0 〇  Example 109 280 270 1.04 0 〇
実施例 110 350 350 1.00 0 〇  Example 110 350 350 1.00 0 〇
実施例 111 360 320 1.13 〇 〇  Example 111 360 320 1.13 ○ ○
実施例 112 300 300 1.00 〇 〇  Example 112 300 300 1.00 〇 〇
実施例 113 280 280 1.00 〇 〇  Example 113 280 280 1.00 〇 〇
実施例 114 80 75 1.07 〇 〇  Example 114 80 75 1.07 ○ ○
実施例 115 75 75 1.00 0 0  Example 115 75 75 1.00 0 0
実施例 116 100 90 1.11 〇 〇  Example 116 100 90 1.11 〇 〇
実施例 117 120 100 1.20 0 〇  Example 117 120 100 1.20 0 〇
実施例 118 150 130 1.15 〇 〇  Example 118 150 130 1.15 〇 〇
実施例 119 300 290 1.03 〇 〇  Example 119 300 290 1.03 ○ ○
(比較例 8〜24) (Comparative Examples 8-24)
実施例 60と同様にして、表 12に示す配合比 (重量比）により、それぞれ顔料分散 体を得た。また、実施例 60と同様の方法で評価した (粘度は低いほど良好、 TI値は 1 に近いほど良好)。 50°C1週間保存前後の粘度の変化率が ±10%以内なら〇、 ±1 0%を超えたら Xとした。塗膜重量損失は、ガラスに塗膜、溶剤除去した後に、 200 。C、 1時間加熱前後の重量損失が 10%以内であれば〇、 10%を超えた場合を Xと した。結果を表 13に示す。 In the same manner as in Example 60, pigment dispersions were obtained according to the blending ratios (weight ratios) shown in Table 12. The evaluation was made in the same manner as in Example 60 (the lower the viscosity, the better, the closer the TI value is to 1, the better). ○, ± 1 if the rate of change in viscosity before and after storage at 50 ° C for 1 week is within ± 10% When it exceeded 0%, it was set as X. The coating weight loss is 200 after removing the coating film and solvent on the glass. C, ○ if the weight loss before and after heating for 1 hour is within 10%, and X if it exceeds 10%. The results are shown in Table 13.
[0194] [表 12] [0194] [Table 12]
Figure imgf000060_0001
Figure imgf000060_0001
[0195] [表 13] [0195] [Table 13]
粘度 (mPa · s) Viscosity (mPas)
T I値 粘度安定性 塗膜重量損失  T I value Viscosity stability Paint film weight loss
orpin 60rpm  orpin 60rpm
比較例 8 分散不可能 ― - 比較例 9 分散不可能 ―  Comparative Example 8 Dispersible--Comparative Example 9 Dispersible-
比較例 10 分散不可能 ―  Comparative Example 10 Dispersion impossible ―
比較例 11 500 200 2. 50 X  Comparative Example 11 500 200 2. 50 X
比較例 12 200 200 1. 00 〇 X  Comparative Example 12 200 200 1. 00 〇 X
比較例 13 分散不可能 ― ― 一  Comparative Example 13 Undispersible ― ― One
比較例 14 測定不能 400 ― X ―  Comparative Example 14 Unmeasurable 400 ― X ―
比較例 15 分散不可能 ― ― - 比較例 16 分散不可能 ― - 比較例 17 500 300 1. 67 X X  Comparative Example 15 Dispersible---Comparative Example 16 Dispersible--Comparative Example 17 500 300 1. 67 X X
比較例 18 400 200 2. 00 X X  Comparative Example 18 400 200 2. 00 X X
比較例 19 350 300 1. 17 〇 X  Comparative example 19 350 300 1.17 〇 X
比較例 20 400 330 1. 21 〇 X  Comparative example 20 400 330 1.21 〇 X
比較例 21 分散不可能 - ― - 比較例 22 600 400 1. 50 X X  Comparative Example 21 Undispersible---Comparative Example 22 600 400 1. 50 X X
比較例 23 測定不能 500 - X 0  Comparative Example 23 Unmeasurable 500-X 0
比較例 24 450 400 1. 13 0 X  Comparative Example 24 450 400 1. 13 0 X
[0196] 以上の評価結果カゝら明らかなように、本発明のポリエステル分散剤を使用した実施 例 60〜119の顔料分散体は、低い初期粘度で、かつ経時粘度の増加がほとんどな く良好な安定性を示している。また塗膜の耐性も高い。これに対して、比較例 8〜24 の顔料分散体では、粘度が高ぐ分散剤の使用量を多くしなければならない。また低 分子量である分散剤を多く使用するため粘度に問題がなくとも塗膜の耐性に問題が 生じていることがわ力 た。 [0196] As is apparent from the above evaluation results, the pigment dispersions of Examples 60 to 119 using the polyester dispersant of the present invention have a low initial viscosity and are excellent with little increase in viscosity over time. Stability. In addition, the coating has high resistance. On the other hand, in the pigment dispersions of Comparative Examples 8 to 24, the amount of the dispersant having a high viscosity must be increased. Also, since many dispersants with low molecular weight were used, it was obvious that there was a problem with the durability of the coating film even though there was no problem with the viscosity.
産業上の利用可能性  Industrial applicability
[0197] 本発明によるポリエステル分散剤は、塗料及び着色榭脂組成物などの分野にぉ ヽ て好適に利用することができ、具体的には、オフセットインキ、グラビアインキ、カラー フィルター用レジストインキ及びインキジェットインキなどに好適に利用することができ る。本発明のポリエステル分散剤を用いると、非集合性、流動性、保存安定性に優れ た分散体を製造することができる。 [0197] The polyester dispersant according to the present invention can be suitably used in fields such as paints and colored resin compositions, and specifically includes offset inks, gravure inks, color filter resist inks, and the like. It can be suitably used for ink jet inks. When the polyester dispersant of the present invention is used, a dispersion excellent in non-aggregability, fluidity and storage stability can be produced.
以上、本発明を特定の態様に沿って説明したが、当業者に自明の変形や改良は 本発明の範囲に含まれる。 As mentioned above, although this invention was demonstrated along the specific aspect, a deformation | transformation and improvement obvious to those skilled in the art are possible. It is included in the scope of the present invention.

Claims

請求の範囲 The scope of the claims
[1] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)の存在下に、ェ チレン性不飽和単量体をラジカル重合して生成され、片末端領域に 2つの水酸基を 有するビニル重合体 (a)中の水酸基と、 [1] Generated by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule. A hydroxyl group in the vinyl polymer ( a ) having,
テトラカルボン酸無水物 (b)中の酸無水物基と、  An acid anhydride group in tetracarboxylic acid anhydride (b);
を反応させて生成されるポリエステル分散剤。  Polyester dispersant produced by reacting
[2] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)の存在下に、ェ チレン性不飽和単量体をラジカル重合して生成され、片末端領域に 2つの水酸基を 有するビニル重合体 (a)中の水酸基、及び前記ビニル重合体 (a)以外のポリオール 化合物 (c)中の水酸基と、 [2] It is formed by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, and has two hydroxyl groups in one end region. A hydroxyl group in the vinyl polymer ( a ) having, and a hydroxyl group in the polyol compound (c) other than the vinyl polymer (a),
テトラカルボン酸無水物 (b)中の酸無水物基と、  An acid anhydride group in tetracarboxylic acid anhydride (b);
を反応させて生成されるポリエステル分散剤。  Polyester dispersant produced by reacting
[3] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)の存在下に、ェ チレン性不飽和単量体をラジカル重合して生成され、片末端領域に 2つの水酸基を 有するビニル重合体 (a)中の水酸基と、 [3] Generated by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule. A hydroxyl group in the vinyl polymer ( a ) having,
テトラカルボン酸無水物（b)中の酸無水物基及びトリカルボン酸無水物（d)中の酸 無水物基と、  An acid anhydride group in tetracarboxylic acid anhydride (b) and an acid anhydride group in tricarboxylic acid anhydride (d);
を反応させて生成されるポリエステル分散剤。  Polyester dispersant produced by reacting
[4] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)の存在下に、ェ チレン性不飽和単量体をラジカル重合して生成され、片末端領域に 2つの水酸基を 有するビニル重合体 (a)中の水酸基、及び前記ビニル重合体 (a)以外のポリオール 化合物 (c)中の水酸基と、 [4] Radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule. A hydroxyl group in the vinyl polymer ( a ) having, and a hydroxyl group in the polyol compound (c) other than the vinyl polymer (a),
テトラカルボン酸無水物（b)の酸無水物基及びトリカルボン酸無水物（d)中の酸無 水物基と、  An acid anhydride group of tetracarboxylic acid anhydride (b) and an acid anhydride group in tricarboxylic acid anhydride (d);
を反応させて生成されるポリエステル分散剤。  Polyester dispersant produced by reacting
[5] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)中の水酸基とテ トラカルボン酸無水物 (b)中の酸無水物基とを反応させて生成される化合物（a2)の 存在下に、エチレン性不飽和単量体をラジカル重合して生成されるポリエステル分 散剤。 [5] Compound formed by reacting a hydroxyl group in compound (al) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in tetracarboxylic anhydride (b) ( Polyester fraction produced by radical polymerization of ethylenically unsaturated monomer in the presence of a2) Powder.
[6] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)及びチオール基 を有さないポリオ一ルイ匕合物（c ' )中の水酸基とテトラカルボン酸無水物（b)中の酸 無水物基とを反応させて生成される化合物 (a3)の存在下に、エチレン性不飽和単 量体をラジカル重合して生成されるポリエステル分散剤。  [6] Hydroxyl and tetracarboxylic acid anhydride (b) in a compound (al) having two hydroxyl groups and one thiol group in the molecule (c ') and a polyoxyl compound (c') having no thiol group A polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a3) produced by reacting an acid anhydride group therein.
[7] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)中の水酸基とテ トラカルボン酸無水物（b)中の酸無水物基及びトリカルボン酸無水物（d)中の酸無水 物基とを反応させて生成される化合物 (a4)の存在下に、エチレン性不飽和単量体を ラジカル重合して生成されるポリエステル分散剤。  [7] Hydroxyl group in compound (al) having two hydroxyl groups and one thiol group in the molecule, acid anhydride group in tetracarboxylic anhydride (b) and tricarboxylic acid anhydride (d) A polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a4) produced by reacting with an acid anhydride group.
[8] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)及びチオール基 を有さないポリオ一ルイ匕合物（c ' )中の水酸基とテトラカルボン酸無水物（b)中の酸 無水物基及びトリカルボン酸無水物（d)中の酸無水物基とを反応させて生成される 化合物（a5)の存在下に、エチレン性不飽和単量体をラジカル重合して生成されるポ リエステル分散剤。  [8] Hydroxyl and tetracarboxylic acid anhydride (b) in a compound (al) having two hydroxyl groups and one thiol group in the molecule (polyol-free compound (c ′) having no thiol group) Produced by radical polymerization of ethylenically unsaturated monomer in the presence of compound (a5) produced by reaction of acid anhydride group in acid and acid anhydride group in tricarboxylic acid anhydride (d) Polyester dispersant.
[9] 重量平均分子量が 2000〜35000であり、かつ、酸価が 5〜200である請求項 1〜 [9] The weight average molecular weight is 2000 to 35000, and the acid value is 5 to 200.
8の 、ずれか一項に記載のポリエステル分散剤。 8. The polyester dispersant according to any one of items 1 to 3.
[10] テトラカルボン酸無水物 (b)が、下記一般式（1)又は一般式 (2)で表されることを特 徴とする請求項 1〜9のいずれか一項に記載のポリエステル分散剤。 [10] The polyester dispersion according to any one of claims 1 to 9, wherein the tetracarboxylic acid anhydride (b) is represented by the following general formula (1) or general formula (2): Agent.
一般式 (1)  General formula (1)
[化 1]  [Chemical 1]
Figure imgf000064_0001
Figure imgf000064_0001
[一般式（1)中、 kは 1又は 2である。 ]  [In the general formula (1), k is 1 or 2. ]
一般式 (2)  General formula (2)
[化 2] [Chemical 2]
Figure imgf000065_0001
Figure imgf000065_0001
Figure imgf000065_0002
Figure imgf000065_0002
Figure imgf000065_0003
Figure imgf000065_0003
で表される基である。 ]  It is group represented by these. ]
[11] エチレン性不飽和単量体をラジカル重合してなるビニル重合体部分の重量平均分 子量が、 1000〜10000である請求項 1〜10のいずれか一項に記載のポリエステル 分散剤。  [11] The polyester dispersant according to any one of [1] to [10], wherein the vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer has a weight average molecular weight of 1,000 to 10,000.
[12] エチレン性不飽和単量体をラジカル重合してなるビュル重合体部分のガラス転移 温度が、 50〜70°Cである請求項 1〜： L1のいずれか一項に記載のポリエステル分 散剤。 [12] The polyester dispersant according to any one of L1 to L1, wherein the glass transition temperature of the bulle polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer is 50 to 70 ° C. .
[13] エチレン性不飽和単量体が、ベンジル (メタ）アタリレートを単量体全体の 20重量％ 〜70重量％含む請求項 1〜12のいずれか一項に記載のポリエステル分散剤。 [13] The polyester dispersant according to any one of [1] to [12], wherein the ethylenically unsaturated monomer contains 20% by weight to 70% by weight of benzyl (meth) acrylate.
[14] エチレン性不飽和単量体が、下記一般式 (3)で表わされる単量体を含むことを特 徴とする請求項 1〜13のいずれか一項に記載のポリエステル分散剤。  [14] The polyester dispersant according to any one of [1] to [13], wherein the ethylenically unsaturated monomer includes a monomer represented by the following general formula (3).
一般式 (3)  General formula (3)
[化 5]
Figure imgf000066_0001
[Chemical 5]
Figure imgf000066_0001
[一般式 (3)中、 Rは、炭素原子数 1〜4の直鎖状若しくは分岐状のアルキル基であ る。]  [In the general formula (3), R represents a linear or branched alkyl group having 1 to 4 carbon atoms. ]
[15] 請求項 1〜14のいずれか一項に記載のポリエステル分散剤と、顔料とを含有する 顔料組成物。  [15] A pigment composition comprising the polyester dispersant according to any one of claims 1 to 14 and a pigment.
[16] 更に、塩基性基を有する顔料誘導体、塩基性基を有するアントラキノン誘導体、塩 基性基を有するアタリドン誘導体、及び塩基性基を有するトリァジン誘導体からなる 群から選ばれる塩基性誘導体の少なくとも一種を含有する請求項 15記載の顔料組 成物。  [16] Further, at least one of basic derivatives selected from the group consisting of pigment derivatives having basic groups, anthraquinone derivatives having basic groups, attaridone derivatives having basic groups, and triazine derivatives having basic groups 16. The pigment composition according to claim 15, comprising:
[17] 請求項 15又は 16記載の顔料組成物をワニスに分散させてなる顔料分散体。  [17] A pigment dispersion obtained by dispersing the pigment composition according to claim 15 or 16 in a varnish.
[18] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)の存在下に、ェ チレン性不飽和単量体をラジカル重合して、片末端領域に 2つの水酸基を有するビ[18] Radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule to form a bifunctional group having two hydroxyl groups in one end region.
-ル重合体 (a)を製造する工程 A1と、 A process A1 for producing a polymer ( a );
前記ビュル重合体 (a)とテトラカルボン酸無水物 (b)とを反応させる工程 B1と、 を含むポリエステル分散剤の製造方法。  A process B1 for reacting the bulle polymer (a) with the tetracarboxylic acid anhydride (b), and a method for producing a polyester dispersant.
[19] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)の存在下に、ェ チレン性不飽和単量体をラジカル重合して、片末端領域に 2つの水酸基を有するビ -ル重合体 (a)を製造する工程 A2と、 [19] Ethylene unsaturated monomer is radically polymerized in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, and a bifunctional group having two hydroxyl groups in one end region. A process A2 for producing a polymer ( a );
前記ビニル重合体 (a)とテトラカルボン酸無水物 (b)と前記ビニル重合体 (a)以外の ポリオール化合物（c)とを反応させる工程 B2と、 を含むポリエステル分散剤の製造方法。 A step B2 of reacting the vinyl polymer (a), the tetracarboxylic acid anhydride (b) and a polyol compound (c) other than the vinyl polymer (a); The manufacturing method of the polyester dispersing agent containing this.
[20] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)の存在下に、ェ チレン性不飽和単量体をラジカル重合して、片末端領域に 2つの水酸基を有するビ -ル重合体 (a)を製造する工程 A3と、 [20] Ethylene unsaturated monomer is radically polymerized in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, and a bifunctional group having two hydroxyl groups in one end region. A process A3 for producing a polymer ( a );
前記ビニル重合体 (a)とテトラカルボン酸無水物 (b)とトリカルボン酸無水物（d)とを 反応させる工程 B3と、  A step B3 of reacting the vinyl polymer (a) with a tetracarboxylic acid anhydride (b) and a tricarboxylic acid anhydride (d);
を含むポリエステル分散剤の製造方法。  The manufacturing method of the polyester dispersing agent containing this.
[21] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)の存在下に、ェ チレン性不飽和単量体をラジカル重合して、片末端領域に 2つの水酸基を有するビ -ル重合体 (a)を製造する工程 A4と、 [21] Radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule to form a bifunctional group having two hydroxyl groups in one end region. A process A4 for producing a polymer ( a );
前記ビニル重合体 (a)とテトラカルボン酸無水物 (b)と前記ビニル重合体 (a)以外の ポリオール化合物（c)とトリカルボン酸無水物（d)とを反応させる工程 B4と、 を含むポリエステル分散剤の製造方法。  A step B4 of reacting the vinyl polymer (a), a tetracarboxylic acid anhydride (b), a polyol compound (c) other than the vinyl polymer (a), and a tricarboxylic acid anhydride (d), and a polyester comprising: A method for producing a dispersant.
[22] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)中の水酸基とテ トラカルボン酸無水物 (b)中の酸無水物基とを反応させ、化合物 (a2)を製造するェ 程 B5と、 [22] The hydroxyl group in compound (al) having two hydroxyl groups and one thiol group in the molecule is reacted with the acid anhydride group in tetracarboxylic anhydride (b) to give compound (a2). Manufacturing process B5,
前記化合物（a2)の存在下に、エチレン性不飽和単量体をラジカル重合させる工程 A5と、  A step A5 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a2);
を含むポリエステル分散剤の製造方法。  The manufacturing method of the polyester dispersing agent containing this.
[23] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)中の水酸基及び チオール基を有さないポリオ一ルイヒ合物（ ）中の水酸基とテトラカルボン酸無水物（ b)中の酸無水物基とを反応させ、化合物 (a3)を製造する工程 B6と、 [23] Hydroxyl group in compound (al) having two hydroxyl groups and one thiol group in the molecule (al) and a polycarboxylic acid anhydride (b) having no thiol group and tetracarboxylic anhydride (b) Step B6 for producing a compound (a3) by reacting with an acid anhydride group therein,
前記化合物（a3)の存在下に、エチレン性不飽和単量体をラジカル重合させる工程 A6と、  A step A6 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a3);
を含むポリエステル分散剤の製造方法。  The manufacturing method of the polyester dispersing agent containing this.
[24] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)中の水酸基と、 テトラカルボン酸無水物（b)中の酸無水物基とトリカルボン酸無水物（d)中の酸無水 物基とを反応させ、化合物 (a4)を製造する工程 B7と、 前記化合物（a4)の存在下に、エチレン性不飽和単量体をラジカル重合させる工程 A7と、 [24] Hydroxyl group in compound (al) having two hydroxyl groups and one thiol group in the molecule, acid anhydride group in tetracarboxylic acid anhydride (b), and tricarboxylic acid anhydride (d) A step B7 for producing a compound (a4) by reacting with an acid anhydride group; A step A7 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a4);
を含むポリエステル分散剤の製造方法。  The manufacturing method of the polyester dispersing agent containing this.
[25] 分子内に 2つの水酸基と 1つのチオール基とを有する化合物（al)中の水酸基とテ トラカルボン酸無水物（b)中の酸無水物基とチオール基を有さないポリオール化合 物（c' )中の水酸基とトリカルボン酸無水物（d)中の酸無水物基とを反応させ、化合 物（a5)を製造する工程 B8と、 [25] Polyol compound having no hydroxyl group in compound (al) having two hydroxyl groups and one thiol group in the molecule, acid anhydride group in tetracarboxylic anhydride (b), and thiol group A step B8 for producing a compound (a5) by reacting a hydroxyl group in (c ′) with an acid anhydride group in tricarboxylic acid anhydride (d);
前記化合物（a5)の存在下に、エチレン性不飽和単量体をラジカル重合させる工程 A8と、  A step A8 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a5);
を含むポリエステル分散剤の製造方法。  The manufacturing method of the polyester dispersing agent containing this.
[26] テトラカルボン酸無水物 (b)が、下記一般式（1)又は一般式 (2)で表されることを特 徴とする請求項 18〜25のいずれか一項に記載のポリエステル分散剤の製造方法。 一般式 (1) [26] The polyester dispersion according to any one of claims 18 to 25, wherein the tetracarboxylic acid anhydride (b) is represented by the following general formula (1) or general formula (2): Manufacturing method. General formula (1)
[化 6]  [Chemical 6]
Figure imgf000068_0001
Figure imgf000068_0001
[一般式（2)中、 Qは、直接結合、— O—、— CO—、 -COOCH CH OCO—、 - SO―、 -C (CF ) ―、式: [In the general formula (2), Q is a direct bond, —O—, —CO—, —COOCH CH OCO—, — SO―, -C (CF) ―, formula:
2 3 2  2 3 2
[化 8]  [Chemical 8]
Figure imgf000069_0001
Figure imgf000069_0001
で表される基である。 ]  It is group represented by these. ]
[27] エチレン性不飽和単量体が、ベンジル (メタ）アタリレートを単量体全体の 20重量％ 〜70重量％含むことを特徴とする請求項 18〜26のいずれか一項に記載のポリエス テル分散剤の製造方法。  27. The ethylenically unsaturated monomer according to any one of claims 18 to 26, wherein the ethylenically unsaturated monomer contains 20% to 70% by weight of benzyl (meth) acrylate. A method for producing a polyester dispersant.
[28] エチレン性不飽和単量体が、下記一般式 (3)で表わされる単量体を含むことを特 徴とする請求項 18〜27のいずれか一項に記載のポリエステル分散剤の製造方法。 一般式 (3)  [28] The production of the polyester dispersant according to any one of [18] to [27], wherein the ethylenically unsaturated monomer includes a monomer represented by the following general formula (3): Method. General formula (3)
[化 10] [Chemical 10]
Figure imgf000069_0002
Figure imgf000069_0002
[一般式 (3)中、 Rは、炭素原子数 1〜4の直鎖状若しくは分岐状のアルキル基であ る。]  [In the general formula (3), R represents a linear or branched alkyl group having 1 to 4 carbon atoms. ]
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6161623A (en) * 1984-08-31 1986-03-29 Dainippon Ink & Chem Inc Pigment dispersant
JPH01141968A (en) * 1987-11-30 1989-06-02 Nippon Oil & Fats Co Ltd Pigment dispersing agent
JPH02219866A (en) * 1989-02-22 1990-09-03 Nippon Oil & Fats Co Ltd Pigment dispersing agent
JPH09157538A (en) * 1995-12-08 1997-06-17 Daicel Chem Ind Ltd Pigment dispersant and coating mateiral or printing ink composition containing the same
JPH10500446A (en) * 1994-05-17 1998-01-13 イー・アイ・デュポン・ドゥ・ヌムール・アンド・カンパニー Comb pigment dispersant
JP2000063404A (en) * 1998-08-25 2000-02-29 Mitsubishi Chemicals Corp Preparation of photopolymerizable composition
JP2000239308A (en) * 1999-02-24 2000-09-05 Soken Chem & Eng Co Ltd Acrylic polymer, curing composition, cured product and their use
JP2000239376A (en) * 1999-02-19 2000-09-05 Dainippon Toryo Co Ltd Production of pigment dispersant for aqueous paint
JP2002226566A (en) * 2001-02-06 2002-08-14 Nippon Shokubai Co Ltd Method for producing polyether-polyester
WO2007007685A1 (en) * 2005-07-08 2007-01-18 Toyo Ink Manufacturing Co., Ltd. Dispersing agent, method for producing same, and pigment dispersion and ink containing such dispersing agent

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1053125C (en) * 1996-05-27 2000-06-07 华东理工大学 Polyester type ultra-dispersant agent and preparation method thereof
JP3588938B2 (en) * 1996-10-23 2004-11-17 東レ株式会社 Pigment dispersions, color pastes and color filters
ATE204891T1 (en) * 1997-07-25 2001-09-15 Ici America Inc DISPERSANTS AND DISPERSIONS PRODUCED THEREOF
JP4788935B2 (en) * 2000-04-27 2011-10-05 綜研化学株式会社 Acrylic polymer having a polymerizable unsaturated group at the molecular end

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6161623A (en) * 1984-08-31 1986-03-29 Dainippon Ink & Chem Inc Pigment dispersant
JPH01141968A (en) * 1987-11-30 1989-06-02 Nippon Oil & Fats Co Ltd Pigment dispersing agent
JPH02219866A (en) * 1989-02-22 1990-09-03 Nippon Oil & Fats Co Ltd Pigment dispersing agent
JPH10500446A (en) * 1994-05-17 1998-01-13 イー・アイ・デュポン・ドゥ・ヌムール・アンド・カンパニー Comb pigment dispersant
JPH09157538A (en) * 1995-12-08 1997-06-17 Daicel Chem Ind Ltd Pigment dispersant and coating mateiral or printing ink composition containing the same
JP2000063404A (en) * 1998-08-25 2000-02-29 Mitsubishi Chemicals Corp Preparation of photopolymerizable composition
JP2000239376A (en) * 1999-02-19 2000-09-05 Dainippon Toryo Co Ltd Production of pigment dispersant for aqueous paint
JP2000239308A (en) * 1999-02-24 2000-09-05 Soken Chem & Eng Co Ltd Acrylic polymer, curing composition, cured product and their use
JP2002226566A (en) * 2001-02-06 2002-08-14 Nippon Shokubai Co Ltd Method for producing polyether-polyester
WO2007007685A1 (en) * 2005-07-08 2007-01-18 Toyo Ink Manufacturing Co., Ltd. Dispersing agent, method for producing same, and pigment dispersion and ink containing such dispersing agent

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