WO2013133013A1 - Dispersant including polyvinyl acetal-polyester graft copolymer, solid-particle dispersion using same, solid particle-containing composition and surface-treated solid particles - Google Patents

Dispersant including polyvinyl acetal-polyester graft copolymer, solid-particle dispersion using same, solid particle-containing composition and surface-treated solid particles Download PDF

Info

Publication number
WO2013133013A1
WO2013133013A1 PCT/JP2013/054089 JP2013054089W WO2013133013A1 WO 2013133013 A1 WO2013133013 A1 WO 2013133013A1 JP 2013054089 W JP2013054089 W JP 2013054089W WO 2013133013 A1 WO2013133013 A1 WO 2013133013A1
Authority
WO
WIPO (PCT)
Prior art keywords
graft copolymer
dispersant
solid
polyester
acid
Prior art date
Application number
PCT/JP2013/054089
Other languages
French (fr)
Japanese (ja)
Inventor
千穂 浅井
橋本　賀之
俊夫 鍵政
Original Assignee
第一工業製薬株式会社
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 第一工業製薬株式会社 filed Critical 第一工業製薬株式会社
Publication of WO2013133013A1 publication Critical patent/WO2013133013A1/en

Links

Classifications

    • 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
    • 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
    • C09D11/16—Writing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences

Definitions

  • the present invention relates to a dispersant containing a polyvinyl acetal-polyester graft copolymer, a solid particle dispersion using the same, a solid particle-containing resin composition, and surface-treated solid particles.
  • the technology for dispersing solid particles in non-aqueous liquids is used in various industrial fields.
  • pigment dispersion in the fields of paints, printing inks, copying toners, plastics, pigment printing agents, ink jet recording inks, thermal transfer recording inks, color filter resists, writing instrument inks, etc. is an important basic technology.
  • a dispersion composition When manufacturing such a dispersion composition, there exists a problem that a solid particle tends to aggregate. It is known that when agglomeration occurs, undesired phenomena such as a decrease in stability, a gloss of a final product, a coloring power, a decrease in gloss, and a color separation occur.
  • a dispersant is used to prevent such aggregation and improve dispersibility.
  • a reaction product of polyester and polyamine is known.
  • a reaction product of a hydroxystearic acid condensate and polyethyleneimine, a reaction product of a polycaprolactone-based polyester compound and polyallylamine, and the like are disclosed (Patent Documents 1 to 3).
  • Dispersants having a polyamine as an adsorbing group as described above are widely known, but having an amine skeleton has a problem of causing yellowing at a high temperature.
  • Patent Document 4 polyvinyl acetal-polyester graft polymer has excellent performance as a non-aqueous dispersant. Although this has the advantage of being excellent in heat-resistant yellowing compared with the dispersing agent containing nitrogen, there existed a tendency for the viscosity of a dispersion to become high.
  • the present invention has been made in view of the above, and when dispersing solid particles in various non-aqueous liquids, it is extremely effective in preventing aggregation of solid particles in the dispersion and forming a stable dispersion. Furthermore, it aims at providing the dispersing agent excellent in heat resistance. Another object of the present invention is to provide a solid particle dispersion, a solid particle-containing resin composition, and surface-treated solid particles having the above characteristics using the same.
  • the dispersant of the present invention contains a polyvinyl acetal-polyester graft copolymer, and contains a polyvinyl acetate-polyester graft copolymer and / or a polyvinyl alcohol-polyester graft copolymer. It shall contain.
  • the dispersant of the present invention contains 1 to 50 parts by mass of polyvinyl acetate-polyester graft copolymer and / or polyvinyl alcohol-polyester graft copolymer with respect to 100 parts by mass of polyvinyl acetal-polyester graft copolymer. It is preferable to do.
  • the solid particles are dispersed in a non-aqueous liquid using the solid particle dispersion of the present invention and the dispersant of the present invention.
  • the solid particle-containing resin composition of the present invention contains the above-described dispersant, resin, and solid particles of the present invention.
  • the solid particle-containing resin composition can be used as, for example, a coating composition or an ink composition.
  • the surface-treated solid particles of the present invention are treated with the dispersant of the present invention.
  • the present invention when dispersing solid particles in various non-aqueous liquids, it is possible to obtain a very effective dispersant for preventing aggregation of the solid particles in the dispersion and forming a stable dispersion.
  • the present dispersant is excellent in dispersibility, fluidity, storage stability, and compatibility with the dispersion medium. Moreover, since it does not have an amine skeleton, the effect that it is excellent in heat resistance is also acquired.
  • the dispersion of the dispersion can be obtained by using the polyvinyl acetate-polyester graft copolymer and / or the polyvinyl alcohol-polyester graft copolymer together. Viscosity can be reduced. By reducing the viscosity of the dispersion, effects such as improved workability during coating can be obtained.
  • the dispersant of the present invention is mainly composed of a polyvinyl acetal-polyester graft copolymer, and one or both of a polyvinyl acetate-polyester graft copolymer and a polyvinyl alcohol-polyester graft copolymer are used in combination. It is a thing.
  • Polyvinyl acetal can be obtained by acetalizing polyvinyl alcohol with aldehyde.
  • aldehydes used include formaldehyde, acetaldehyde, propanal, butanal, isobutanal, pentanal, hexanal, heptanal, octanal, nonanal, isononanal, decanal, benzaldehyde and mixtures thereof.
  • the average molecular weight of the polyvinyl acetal is preferably 100 to 100,000, more preferably 1,000 to 50,000. When the weight average molecular weight is less than 100, performance degradation such as a decrease in dispersibility is observed. When the weight average molecular weight exceeds 100,000, the viscosity increases during use as a dispersant, making it difficult to handle.
  • the weight average molecular weight of the polyvinyl acetate is preferably 100 to 100,000, more preferably 1,000 to 50,000. When the weight average molecular weight is less than 100, performance degradation such as a decrease in dispersibility is observed. When the weight average molecular weight exceeds 100,000, the viscosity increases during use as a dispersant, making it difficult to handle.
  • the polyvinyl alcohol can be obtained by saponifying polyvinyl acetate, and the degree of saponification is not limited, and any of more than 0% to 100% can be used.
  • the weight average molecular weight of polyvinyl acetate is preferably 100 to 100,000, more preferably 1,000 to 50,000. When the weight average molecular weight is less than 100, performance degradation such as a decrease in dispersibility is observed. When the weight average molecular weight exceeds 100,000, the viscosity increases during use as a dispersant, making it difficult to handle.
  • the polyester used in the present invention can be obtained by known means such as a ring-opening polymerization reaction of a lactone compound, a polycondensation reaction of a polycarboxylic acid and a polyhydric alcohol, a polycondensation reaction of a hydroxycarboxylic acid.
  • lactone compound examples include ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -propiolactone, ⁇ -butyrolactone, 2-methylcaprolactone, 4-methylcaprolactone, and nonanolactone. A mixture of two or more of these can also be used.
  • the ring-opening polymerization reaction of the lactone compound can be performed by a known method.
  • a compound having an alcohol or an amine can be used as an initiator, and a lactone compound can be subjected to ring-opening polymerization.
  • Examples of the alcohol used as the initiator include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, and 4-methylpen Tanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanal, isononanal, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, oleyl Aliphatic monoalcohols such as alcohol, 2-octyldecanol, 2-octyldodecanol, 2-hexyldecanol, and behenyl alcohol, benzyl alcohol, phenylethyl alcohol Aromatic monoalcohol
  • amines used for the initiator include methylamine, dimethylamine, ethylamine, diethylamine, triethylamine, methylethylamine, propylamine, dipropylamine, cyclohexylamine, phenylamine, benzylamine, pyrrolidine, morpholine, methylenediamine, and ethylenediamine.
  • Tetraethylenediamine Tetraethylenediamine, hexaethylenediamine, propylenediamine, diphenyldiaminomethane, paraphenylenediamine, hexamethylenediamine, isophoronediamine, ethanolamine, diethylenetriamine, diethylaminopropylamine, piperazine, triethylenetetramine and the like.
  • the ring-opening polymerization reaction of the lactone compound proceeds by adding an initiator and a catalyst to the lactone compound and heating.
  • the reaction temperature is 100 ° C to 220 ° C, preferably 140 ° C to 210 ° C.
  • the catalyst tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, organic tin compounds such as dioctyltin neodecanate, stannous oxide, tin compounds such as stannous chloride, tetrabutyl titanate, Titanium compounds such as tetraethyl titanate and tetrapropyl titanate, and other known esterification catalysts can be used.
  • the amount of the catalyst used is preferably from 0.1 ppm to 1000 ppm, more preferably from 1 ppm to 100 ppm.
  • polylactone polyols can also be used as the ring-opening polymer of the lactone compound. Examples thereof include “Placcel” series manufactured by Daicel Chemical Industries, Ltd.
  • the polyester used in the present invention can also be obtained by a polycondensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol.
  • polyvalent carboxylic acid examples include phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexa
  • polyhydric alcohol examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl -1,3-propanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1, 4-cyclohexanedimethanol, 1,4-benzenedimethanol, 2,2-bis- (4-hydroxyethoxyphenyl) propane, 1,4-bis (2-hydroxyethyl) benzene, 1,6-bis (2- Hydroxyethoxy) hexa , Butanediol, neopentyl glycol, 1,4-hexanediol glycerin,
  • the polycondensation reaction between the polyvalent carboxylic acid and the polyhydric alcohol can be performed by adding a catalyst and heating.
  • the reaction temperature is preferably from 100 ° C to 220 ° C, more preferably from 140 ° C to 210 ° C.
  • Catalysts include, but are not limited to, organotin compounds such as tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, dioctyltin neodecanate, stannous oxide, stannous chloride Tin compounds such as tin, titanium compounds such as tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate, and other known esterification catalysts can be used.
  • the amount of the catalyst used is preferably from 0.1 ppm to 1000 ppm, more preferably from 1 ppm to 100 ppm.
  • the polyester used in the present invention can also be obtained by polycondensation reaction of hydroxycarboxylic acid.
  • hydroxycarboxylic acid aliphatic, aromatic or unsaturated hydroxycarboxylic acid can be used.
  • examples include ricinoleic acid, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, ⁇ -hydroxyvaleric acid, lactic acid, glycolic acid, hydroxyisophthalic acid, hydroxypivalic acid, 4-hydroxyisophthalic acid, salicylic acid 11-oxyhexadodecanoic acid, 2-oxidedecanoic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, 2,2-dimethylolpentanoic acid, malic acid, Examples thereof include tartaric acid, gluconic acid, 4,4-bis (hydroxyphenyl) butyric acid, glucuronic
  • the polycondensation reaction of the hydroxycarboxylic acid can be performed by adding a catalyst and heating.
  • the reaction temperature is preferably in the range of 100 ° C. to 220 ° C., more preferably 140 ° C. to 210 ° C.
  • tin octylate dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, organic tin compounds such as dioctyltin neodecanate, stannous oxide, tin compounds such as stannous chloride, tetrabutyl titanate, Titanium compounds such as tetraethyl titanate and tetrapropyl titanate, and other known esterification catalysts can be used.
  • the amount of the catalyst used is preferably from 0.1 ppm to 1000 ppm, more preferably from 1 ppm to 100 ppm.
  • inert gas atmosphere such as nitrogen
  • the weight average molecular weight of the polyester used in the present invention is preferably from 100 to 50,000, more preferably from 1,000 to 10,000. When the weight average molecular weight is less than 100, performance deterioration such as a decrease in dispersibility is observed. When the weight average molecular weight exceeds 50,000, the viscosity becomes high when used as a dispersant, and it becomes difficult to handle.
  • the method for producing the graft copolymer used in the present invention is not particularly limited, but a method of directly reacting a polyester monomer with polyvinyl acetal, polyvinyl acetate and polyvinyl alcohol, a hydroxyl group of polyvinyl acetal, polyvinyl acetate and polyvinyl alcohol. And a method of dehydrating and condensing the polyester with a carboxylic acid, and a method of transesterifying the polyester with a hydroxyl group or ester group of polyvinyl acetal, polyvinyl acetate and polyvinyl alcohol.
  • a polyvinyl acetal-polyester graft copolymer, a polyvinyl acetate-polyester copolymer and / or a polyvinyl alcohol-polyester copolymer may be produced, and these may be mixed when used as a dispersant. It is also possible to combine the polyester chains after previously mixing polyvinyl acetal with polyvinyl acetate and / or polyvinyl alcohol.
  • the hydroxyl group or ester group of polyvinyl acetal, polyvinyl acetate or polyvinyl alcohol preferably forms a graft bond with the polyester in the range of 1 to 95 mol%. More preferably, 2 to 50 mol% of the hydroxyl group or ester group forms a graft bond with the polyester. In any case, unreacted polyester may remain.
  • the amount of the polyvinyl acetate-graft copolymer and / or polyvinyl alcohol-polyester graft copolymer used relative to the polyvinyl acetal-polyester graft copolymer is as follows.
  • the total amount of the graft copolymer and / or polyvinyl alcohol-polyester graft copolymer is preferably 1 to 50 parts by mass.
  • Dispersant of the present invention is effective for dispersing various inorganic and organic solid particles. Specifically, in dispersion media commonly used in various fields such as paint, printing ink, copying toner, plastic, pigment printing agent, ink jet recording ink, thermal transfer recording ink, color filter resist, writing tool ink, etc.
  • the solid particles can be dispersed with high concentration and stability.
  • polyvinyl acetal-polyester graft copolymer is mixed with polyvinyl acetate-polyester graft copolymer and / or polyvinyl alcohol-polyester graft copolymer to form a dispersant.
  • the viscosity of the dispersion can be significantly reduced. By reducing the viscosity of the dispersion, advantages such as improved workability during coating are obtained, and the use of the dispersion is further expanded.
  • Solid particles dispersed by the dispersant of the present invention are not particularly limited, but examples of inorganic particles include kaolin, aluminum silicate, clay, talc, mica, calcium silicate, bentonite, magnesium silicate, asbestos, calcium carbonate. , Magnesium carbonate, barium carbonate, dolomite, calcium sulfate, barium sulfate, aluminum sulfate, zirconia, magnesia, alumina, antimony trioxide, titanium oxide, diatomaceous earth, iron oxide, zinc oxide, aluminum hydroxide, iron hydroxide, silicon carbide, Examples thereof include silicon nitride, boron nitride, barium titanate, carbon black, graphite, iron powder, silver powder, aluminum powder, copper powder, nickel powder, and gold powder.
  • organic particles examples include azo, diazo, condensed azo, thioindigo, indanthrone, quinacridone, anthraquinone, benzimidazolone, perylene, phthalocyanine, anthrapyridine, dioxazine, etc.
  • Organic pigment, starch, polyethylene resin, urethane resin, melamine resin, polystyrene resin, polylactic acid, solid paraffin and the like can be mentioned.
  • Dispersion media include toluene, xylene, aromatic hydrocarbon solvents, hydrocarbon solvents such as n-hexane, cyclohexane, n-heptane, halogenated hydrocarbon solvents such as methylene chloride, chloroform, dichloroethane, dioxane, tetrahydrofuran , Ether solvents such as butyl ether, butyl ethyl ether and diglyme, ketone solvents such as methyl isobutyl ketone, cyclohexanone and isophorone, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate Methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, alcohol
  • the amount of the dispersant of the present invention is not particularly limited depending on the type of solid particles to be dispersed, but is usually preferably about 1 to 300% by mass with respect to the solid particles.
  • the dispersion method is not particularly limited, and the dispersion can be performed by a known method using a pulverizer such as a ball mill, a bead mill, or a sand mill.
  • a pulverizer such as a ball mill, a bead mill, or a sand mill.
  • a solid particle-containing resin composition containing solid particles and resin, and further containing a solvent or the like as necessary can be prepared.
  • This solid particle-containing resin composition can be used in, for example, a coating composition or an ink composition.
  • the resin contained in the solid particle-containing resin composition includes acrylic resin, urethane resin, epoxy resin, polyester resin, alkyd resin, silicone resin, fluororesin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, phenol resin,
  • a wide range of resins such as, but not limited to, vinyl chloride, polyethylene resin, and polyvinyl acetal resin are included.
  • a solid particle-containing resin composition can be directly prepared by kneading the dispersant of the present invention with solid particles, a resin, a solvent, and other additives.
  • a resin may be added thereto to obtain a solid particle-containing resin composition.
  • the dispersant of the present invention and solid particles, monomers or oligomers having reactive groups can be kneaded and dispersed, and then polymerized to prepare a solid particle-containing resin composition.
  • the surface treatment of the solid particles can be performed with the dispersant of the present invention.
  • a treatment method a dry method in which a dispersant is added and mixed while stirring solid particles using a Henschel mixer, a ball mill, an atomizer colloid mill, a Banbury mixer, etc., or a wet method in which the solvent is removed after treatment in a solvent is used. be able to.
  • the dispersibility of the solid particles can be improved and aggregation can be prevented.
  • polyvinyl acetal manufactured by Sekisui Chemical Co., Ltd., trade name “ESREC BX-L”, average molecular weight of about 20000, hydroxyl group 37 ⁇ 3 mol%, Acetyl group 3 mol% or less, degree of acetalization about 61 mol%) 4.1 parts, 129.0 parts of polyester as the above reaction product, 0.05 parts of dioctyltin neodecanate, were charged at 200 ° C. in a nitrogen atmosphere. And heated for 6 hours. The reaction product was a yellow viscous liquid, the weight average molecular weight was 95,000, and the acid value was 3.3 mgKOH / g.
  • Polyvinyl acetate manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “Denkasacnol SN-04T”, degree of polymerization 500 to 700 12.3 in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a reflux tube, and a sample tube Part, 64.2 parts of polyester as the above reaction product and 0.05 part of dioctyltin neodecanate were charged, heated to 200 ° C. in a nitrogen atmosphere, and heated for 6 hours.
  • the reaction product was a yellow viscous liquid, the weight average molecular weight was 65,000, and the acid value was 8.8 mgKOH / g.
  • polyvinyl alcohol manufactured by Kuraray Co., Ltd., trade name “Kuraray Poval PVA-102”, degree of saponification 98.0 to 99.0%, degree of polymerization 200
  • degree of saponification 98.0 to 99.0% degree of polymerization 200
  • dioctyltin neodecanate was charged, heated to 200 ° C. in a nitrogen atmosphere, and heated for 6 hours.
  • the reaction product was a yellow viscous liquid, and the weight average molecular weight was 85,500.
  • Comparative product 1 Ajinomoto Fine Techno Co., Ltd., trade name “Ajisper PB-822”, polymer pigment dispersant, amine value 17 mgKOH / g, acid value 14 mgKOH / g
  • Comparative product 2 manufactured by Sekisui Chemical Co., Ltd., trade name “ESREC BL-1”, polyvinyl butyral, average molecular weight of about 19000, hydroxyl group of about 36 mol%, acetyl group of 3 mol% or less, degree of butyralization of 63 ⁇ 3 mol%
  • Color difference 0.5 mg of the dispersant was dissolved in 20 mL of methylene chloride, mixed with 10 g of silica gel, and dried at room temperature. Half of the obtained silica gel was heat-treated at 200 ° C. for 1 hour, and the color difference before and after the treatment was measured. Heat resistance: Judged according to the following criteria. ⁇ : Color difference ( ⁇ E) 0 or more and 5 or less ⁇ : Color difference ( ⁇ E) 5 to less than 10 ⁇ : Color difference ( ⁇ E) 10 or more
  • the photosensitive colored resin composition was spin-coated on a glass substrate and pre-baked in a clean oven at 70 ° C. for 20 minutes to prepare a dry coating film.
  • the substrate was cooled to room temperature, and then exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a 0.04% aqueous potassium hydroxide solution, washed with ion-exchanged water, and air-dried. Thereafter, post-baking was performed at 230 ° C. for 30 minutes in a clean oven.
  • the dried coating film was a uniform and smooth coating film within ⁇ 0.5 ⁇ m, and the light transmittance (average of 380 to 780 nm) was 98%.
  • the dispersant of the present invention is solid in non-aqueous liquids in the fields of paints, printing inks, copying toners, plastics, pigment printing agents, ink jet recording inks, thermal transfer recording inks, color filter resists, writing instrument inks, etc. It is extremely effective for dispersing the particles.

Abstract

Provided is a dispersant with which when solid particles are dispersed in various non-aqueous liquids agglomeration of the solid particles in a dispersion liquid is inhibited, the dispersant being extremely effective in forming a stable dispersion liquid, having excellent thermal resistance and lowering the viscosity of a dispersion to be lower than that in the past thereby improving the workability. The dispersant comprises a polyvinyl acetal-polyester graft copolymer and a vinyl acetate-polyester graft copolymer and/or a polyvinyl alcohol-polyester graft copolymer.

Description

ポリビニルアセタール－ポリエステルグラフト共重合体を含有する分散剤、これを用いた固体粒子分散体、固体粒子含有組成物、及び表面処理固体粒子Dispersant containing polyvinyl acetal-polyester graft copolymer, solid particle dispersion using the same, solid particle-containing composition, and surface-treated solid particles
　本発明は、ポリビニルアセタール－ポリエステルグラフト共重合体を含有する分散剤、並びにこれを用いた固体粒子分散体、固体粒子含有樹脂組成物、及び表面処理固体粒子に関する。 The present invention relates to a dispersant containing a polyvinyl acetal-polyester graft copolymer, a solid particle dispersion using the same, a solid particle-containing resin composition, and surface-treated solid particles.
　非水系液体に固体粒子を分散する技術は、様々な産業分野で利用されている。例えば、塗料、印刷インキ、複写用トナー、プラスチック、顔料捺染剤、インクジェット記録用インキ、熱転写記録用インキ、カラーフィルター用レジスト、筆記具用インキ等の分野での顔料の分散は重要な基礎技術である。このような分散組成物を製造する際、固体粒子が凝集しやすいという問題点がある。凝集が起こると安定性の低下、最終製品の光沢、着色力、グロスの低下、色分かれなど好ましくない現象を生じることが知られている。このような凝集を防止し、分散性を向上させるため、分散剤が使用される。 The technology for dispersing solid particles in non-aqueous liquids is used in various industrial fields. For example, pigment dispersion in the fields of paints, printing inks, copying toners, plastics, pigment printing agents, ink jet recording inks, thermal transfer recording inks, color filter resists, writing instrument inks, etc. is an important basic technology. . When manufacturing such a dispersion composition, there exists a problem that a solid particle tends to aggregate. It is known that when agglomeration occurs, undesired phenomena such as a decrease in stability, a gloss of a final product, a coloring power, a decrease in gloss, and a color separation occur. A dispersant is used to prevent such aggregation and improve dispersibility.
　従来の非水系分散剤としては、ポリエステルとポリアミンの反応生成物が知られている。例えば、ヒドロキシステアリン酸縮合物とポリエチレンイミンとの反応生成物、ポリカプロラクトン系ポリエステル化合物とポリアリルアミンとの反応生成物などが開示されている（特許文献１～３）。これらのように吸着基としてポリアミンを持つ分散剤が広く知られているが、アミン骨格を持つと、高温下で黄変を起こすという問題があった。 As a conventional non-aqueous dispersant, a reaction product of polyester and polyamine is known. For example, a reaction product of a hydroxystearic acid condensate and polyethyleneimine, a reaction product of a polycaprolactone-based polyester compound and polyallylamine, and the like are disclosed (Patent Documents 1 to 3). Dispersants having a polyamine as an adsorbing group as described above are widely known, but having an amine skeleton has a problem of causing yellowing at a high temperature.
　一方、ポリビニルアセタール－ポリエステルグラフトポリマーが非水系分散剤として優れた性能を有することが開示されている（特許文献４）。これは窒素を含有する分散剤と比較して耐熱黄変性に優れるという利点があるが、分散体の粘度が高くなる傾向があった。 On the other hand, it has been disclosed that polyvinyl acetal-polyester graft polymer has excellent performance as a non-aqueous dispersant (Patent Document 4). Although this has the advantage of being excellent in heat-resistant yellowing compared with the dispersing agent containing nitrogen, there existed a tendency for the viscosity of a dispersion to become high.
特開平０９－１７６５１１号公報Japanese Patent Laid-Open No. 09-176511 特開平０７－２０７０１２号公報Japanese Patent Laid-Open No. 07-207012 特開平０９－１６９８２１号公報Japanese Patent Application Laid-Open No. 09-169821 ＷＯ２０１１／０６７８８９Ａ１WO2011 / 067889A1
　本発明は上記に鑑みてなされたものであり、各種の非水系液体中に固体粒子を分散させる際に、分散液中における固体粒子の凝集を防ぎ、安定な分散液を形成するのに極めて有効であり、さらに、耐熱性に優れた分散剤を提供することを目的とする。また、これを用いた上記のような特性を有する固体粒子分散体、固体粒子含有樹脂組成物、表面処理固体粒子を提供することを目的とする。 The present invention has been made in view of the above, and when dispersing solid particles in various non-aqueous liquids, it is extremely effective in preventing aggregation of solid particles in the dispersion and forming a stable dispersion. Furthermore, it aims at providing the dispersing agent excellent in heat resistance. Another object of the present invention is to provide a solid particle dispersion, a solid particle-containing resin composition, and surface-treated solid particles having the above characteristics using the same.
　本発明の分散剤は、上記の課題を解決するために、ポリビニルアセタール－ポリエステルグラフト共重合体を含有し、かつポリ酢酸ビニル－ポリエステルグラフト共重合体及び／又はポリビニルアルコール－ポリエステルグラフト共重合体を含有するものとする。 In order to solve the above problems, the dispersant of the present invention contains a polyvinyl acetal-polyester graft copolymer, and contains a polyvinyl acetate-polyester graft copolymer and / or a polyvinyl alcohol-polyester graft copolymer. It shall contain.
　上記本発明の分散剤は、ポリビニルアセタール－ポリエステルグラフト共重合体１００質量部に対して、ポリ酢酸ビニル－ポリエステルグラフト共重合体及び／又はポリビニルアルコール－ポリエステルグラフト共重合体を１～５０質量部含有することが好ましい。 The dispersant of the present invention contains 1 to 50 parts by mass of polyvinyl acetate-polyester graft copolymer and / or polyvinyl alcohol-polyester graft copolymer with respect to 100 parts by mass of polyvinyl acetal-polyester graft copolymer. It is preferable to do.
　本発明の固体粒子分散体、上記本発明の分散剤により固体粒子を非水系液体に分散させたものとする。 Suppose that the solid particles are dispersed in a non-aqueous liquid using the solid particle dispersion of the present invention and the dispersant of the present invention.
　本発明の固体粒子含有樹脂組成物は、上記本発明の分散剤、樹脂、及び固体粒子を含有するものとする。 The solid particle-containing resin composition of the present invention contains the above-described dispersant, resin, and solid particles of the present invention.
　上記固体粒子含有樹脂組成物は、例えば塗料組成物又はインキ組成物として用いることができる。 The solid particle-containing resin composition can be used as, for example, a coating composition or an ink composition.
　本発明の表面処理固体粒子は、上記本発明の分散剤で処理したものとする。 The surface-treated solid particles of the present invention are treated with the dispersant of the present invention.
　本発明によれば、各種の非水系液体中に固体粒子を分散させる際、分散液中における固体粒子の凝集を防ぎ、安定な分散液を形成するのに極めて有効な分散剤が得られる。本分散剤は、分散性、流動性、保存安定性に優れ、また分散媒との相溶性に優れている。また、アミン骨格を有しないため耐熱性に優れるという効果も得られる。 According to the present invention, when dispersing solid particles in various non-aqueous liquids, it is possible to obtain a very effective dispersant for preventing aggregation of the solid particles in the dispersion and forming a stable dispersion. The present dispersant is excellent in dispersibility, fluidity, storage stability, and compatibility with the dispersion medium. Moreover, since it does not have an amine skeleton, the effect that it is excellent in heat resistance is also acquired.
　さらに、ポリビニルアセタール－ポリエステルグラフト共重合体を単独で使用するときと比較して、ポリ酢酸ビニル－ポリエステルグラフト共重合体及び／又はポリビニルアルコール－ポリエステルグラフト共重合体を併用することにより、分散体の粘度を低下させることができる。分散体の粘度が低下することにより、塗装時の作業性が向上する等の効果が得られる。 Further, compared with the case where the polyvinyl acetal-polyester graft copolymer is used alone, the dispersion of the dispersion can be obtained by using the polyvinyl acetate-polyester graft copolymer and / or the polyvinyl alcohol-polyester graft copolymer together. Viscosity can be reduced. By reducing the viscosity of the dispersion, effects such as improved workability during coating can be obtained.
１．分散剤の調製
　本発明の分散剤は、ポリビニルアセタール－ポリエステルグラフト共重合体を主成分とし、ポリ酢酸ビニル－ポリエステルグラフト共重合体とポリビニルアルコール－ポリエステルグラフト共重合体のうちの一方又は双方を併用したものである。 1. Preparation of Dispersant The dispersant of the present invention is mainly composed of a polyvinyl acetal-polyester graft copolymer, and one or both of a polyvinyl acetate-polyester graft copolymer and a polyvinyl alcohol-polyester graft copolymer are used in combination. It is a thing.
　ポリビニルアセタールは、ポリビニルアルコールをアルデヒドでアセタール化することにより得られる。使用するアルデヒドの例としては、ホルムアルデヒド、アセトアルデヒド、プロパナール、ブタナール、イソブタナール、ペンタナール、ヘキサナール、ヘプタナール、オクタナール、ノナナール、イソノナナール、デカナール、ベンズアルデヒドおよびこれらの混合物が挙げられる。ポリビニルアセタールの平均分子量は１００～１００，０００が好ましく、より好ましくは１，０００～５０，０００である。その重量平均分子量が１００未満であると分散性が低下する等の性能低下が見られ、１００，０００を超えると分散剤としての使用時に粘度が高くなり、扱いにくくなる。 Polyvinyl acetal can be obtained by acetalizing polyvinyl alcohol with aldehyde. Examples of aldehydes used include formaldehyde, acetaldehyde, propanal, butanal, isobutanal, pentanal, hexanal, heptanal, octanal, nonanal, isononanal, decanal, benzaldehyde and mixtures thereof. The average molecular weight of the polyvinyl acetal is preferably 100 to 100,000, more preferably 1,000 to 50,000. When the weight average molecular weight is less than 100, performance degradation such as a decrease in dispersibility is observed. When the weight average molecular weight exceeds 100,000, the viscosity increases during use as a dispersant, making it difficult to handle.
　上記ポリ酢酸ビニルの重量平均分子量は１００～１００，０００が好ましく、より好ましくは１，０００～５０，０００である。その重量平均分子量が１００未満であると分散性が低下する等の性能低下が見られ、１００，０００を超えると分散剤としての使用時に粘度が高くなり、扱いにくくなる。 The weight average molecular weight of the polyvinyl acetate is preferably 100 to 100,000, more preferably 1,000 to 50,000. When the weight average molecular weight is less than 100, performance degradation such as a decrease in dispersibility is observed. When the weight average molecular weight exceeds 100,000, the viscosity increases during use as a dispersant, making it difficult to handle.
　上記ポリビニルアルコールはポリ酢酸ビニルを鹸化することで得られ、その鹸化度は限定されず、０％超～１００％のいずれのものも使用することができる。ポリ酢酸ビニルの重量平均分子量は１００～１００，０００が好ましく、より好ましくは１，０００～５０，０００である。その重量平均分子量が１００未満であると分散性が低下する等の性能低下が見られ、１００，０００を超えると分散剤としての使用時に粘度が高くなり、扱いにくくなる。 The polyvinyl alcohol can be obtained by saponifying polyvinyl acetate, and the degree of saponification is not limited, and any of more than 0% to 100% can be used. The weight average molecular weight of polyvinyl acetate is preferably 100 to 100,000, more preferably 1,000 to 50,000. When the weight average molecular weight is less than 100, performance degradation such as a decrease in dispersibility is observed. When the weight average molecular weight exceeds 100,000, the viscosity increases during use as a dispersant, making it difficult to handle.
　本発明で使用するポリエステルは、ラクトン化合物の開環重合反応、多価カルボン酸と多価アルコールの重縮合反応、ヒドロキシカルボン酸の重縮合反応等の公知の手段によって得られる。 The polyester used in the present invention can be obtained by known means such as a ring-opening polymerization reaction of a lactone compound, a polycondensation reaction of a polycarboxylic acid and a polyhydric alcohol, a polycondensation reaction of a hydroxycarboxylic acid.
　上記ラクトン化合物の例としては、ε－カプロラクトン、δ－バレロラクトン、β－メチル－δ－バレロラクトン、β－プロピオラクトン、γ－ブチロラクトン、２－メチルカプロラクトン、４－メチルカプロラクトン、ノナノラクトン等が挙げられ、これらの２種以上の混合物も使用可能である。 Examples of the lactone compound include ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, β-propiolactone, γ-butyrolactone, 2-methylcaprolactone, 4-methylcaprolactone, and nonanolactone. A mixture of two or more of these can also be used.
　上記ラクトン化合物の開環重合反応は公知の方法で行うことができる。例えば、アルコール又はアミンを有する化合物を開始剤として使用し、ラクトン化合物を開環重合させることができる。 The ring-opening polymerization reaction of the lactone compound can be performed by a known method. For example, a compound having an alcohol or an amine can be used as an initiator, and a lactone compound can be subjected to ring-opening polymerization.
　上記開始剤に用いるアルコールとしては、メタノール、エタノール、１－プロパノール、イソプロパノール、１－ブタノール、イソブタノール、ｔｅｒｔ－ブタノール、１－ペンタノール、イソペンタノール、１－ヘキサノール、シクロヘキサノール、４－メチルペンタノール、１－ヘプタノール、１－オクタノール、イソオクタノール、２－エチルヘキサノール、１－ノナナール、イソノナナール、１－デカノール、１－ドデカノール、１－ミリスチルアルコール、セチルアルコール、１－ステアリルアルコール、イソステアリルアルコール、オレイルアルコール、２－オクチルデカノール、２－オクチルドデカノール、２－ヘキシルデカノール、ベヘニルアルコール等の脂肪族モノアルコール、ベンジルアルコール、フェニルエチルアルコール等の芳香族モノアルコール、アクリル酸－２－ヒドロキシエチル、メタクリル酸－２－ヒドロキシエチル等のヒドロキシル基含有（メタ）アクリル酸エステル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノ－２－エチルヘキシルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノヘキシルエーテル、プロピレングリコールモノ－２－エチルヘキシルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールモノ－２－エチルヘキシルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、ジプロピレングリコールモノヘキシルエーテル、ジプロピレングリコールモノ－２－エチルヘキシルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノプロピルエーテル、トリエチレングリコールモノブチルエーテル、トリエチレングリコールモノヘキシルエーテル、トリエチレングリコールモノ－２－エチルヘキシルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノプロピルエーテル、トリプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノヘキシルエーテル、トリプロピレングリコールモノ－２－エチルヘキシルエーテル、テトラエチレングリコールモノメチルエーテル、テトラエチレングリコールモノエチルエーテル、テトラエチレングリコールモノプロピルエーテル、テトラエチレングリコールモノブチルエーテル、テトラエチレングリコールモノヘキシルエーテル、テトラエチレングリコールモノ－２－エチルヘキシルエーテル、テトラプロピレングリコールモノメチルエーテル、テトラプロピレングリコールモノエチルエーテル、テトラプロピレングリコールモノプロピルエーテル、テトラプロピレングリコールモノブチルエーテル、テトラプロピレングリコールモノヘキシルエーテル、テトラプロピレングリコールモノ－２－エチルヘキシルエーテル、テトラジエチレングリコールモノメチルエーテル等のアルキレングリコールモノアルキルエーテル、エチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２－メチル－１，３－プロパンジオール、１，６－ヘキサンジオール、１，１０－デカンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール、１，４－シクロヘキサンジメタノール、１，４－ベンゼンジメタノール、２，２－ビス－（４－ヒドロキシエトキシフェニル）プロパン、１，４－ビス（２－ヒドロキシエチル）ベンゼン、１，６－ビス（２－ヒドロキシエトキシ）ヘキサン等の二価アルコール、ブタンジオール、ネオペンチルグリコール、１,４－ヘキサンジオールグリセリン、トリメチロールエタン、トリメチロールプロパン、トリス（２－ヒドロキシエチル）イソシアヌレート、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール、マトール、ソルビトール等の多価アルコールを挙げることができる。 Examples of the alcohol used as the initiator include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, and 4-methylpen Tanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanal, isononanal, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, oleyl Aliphatic monoalcohols such as alcohol, 2-octyldecanol, 2-octyldodecanol, 2-hexyldecanol, and behenyl alcohol, benzyl alcohol, phenylethyl alcohol Aromatic monoalcohols such as coal, hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, Propylene glycol mono-2-ethylhexyl ether, diethylene Recall monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol Monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol mono Hexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono -2-ethyl Xyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, tetradiethylene glycol monomethyl ether Alkylene glycol monoalkyl ether such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl- 1,3-propanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, Liethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, 2,2-bis- (4-hydroxyethoxy Phenyl) propane, 1,4-bis (2-hydroxyethyl) benzene, 1,6-bis (2-hydroxyethoxy) hexane and other dihydric alcohols, butanediol, neopentyl glycol, 1,4-hexanediol glycerin, Multivalent alcohols such as trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, ditrimethylolpropane, dipentaerythritol, maltol, sorbitol Mention may be made of Le.
　上記開始剤に用いるアミンの例としては、メチルアミン、ジメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、メチルエチルアミン、プロピルアミン、ジプロピルアミン、シクロヘキシルアミン、フェニルアミン、ベンジルアミン、ピロリジン、モルホリン、メチレンジアミン、エチレンジアミン、テトラエチレンジアミン、ヘキサエチレンジアミン、プロピレンジアミン、ジフェニルジアミノメタン、パラフェニレンジアミン、ヘキサメチレンジアミン、イソホロンジアミン、エタノールアミン、ジエチレントリアミン、ジエチルアミノプロピルアミン、ピペラジン、トリエチレンテトラミン等が挙げられる。 Examples of amines used for the initiator include methylamine, dimethylamine, ethylamine, diethylamine, triethylamine, methylethylamine, propylamine, dipropylamine, cyclohexylamine, phenylamine, benzylamine, pyrrolidine, morpholine, methylenediamine, and ethylenediamine. , Tetraethylenediamine, hexaethylenediamine, propylenediamine, diphenyldiaminomethane, paraphenylenediamine, hexamethylenediamine, isophoronediamine, ethanolamine, diethylenetriamine, diethylaminopropylamine, piperazine, triethylenetetramine and the like.
　ラクトン化合物の開環重合反応は、ラクトン化合物に開始剤と触媒を加え加熱することで進行する。反応温度は１００℃～２２０℃、好ましくは１４０℃～２１０℃の範囲で行う。触媒としては、オクチル酸スズ、ジブチルスズオキシド、ジブチルスズラウレート、モノブチルスズヒドロキシブチルオキシド、ジオクチルスズネオデカネート等の有機スズ化合物、酸化第一スズ、塩化第一スズ等のスズ化合物、テトラブチルチタネート、テトラエチルチタネート、テトラプロピルチタネート等のチタン化合物、その他公知のエステル化触媒が利用できる。触媒の使用量は０．１ｐｐｍ～１０００ｐｐｍが好ましく、より好ましくは１ｐｐｍ～１００ｐｐｍである。また、着色を防ぐため窒素等の不活性ガス雰囲気下で反応を行うことが好ましい。 The ring-opening polymerization reaction of the lactone compound proceeds by adding an initiator and a catalyst to the lactone compound and heating. The reaction temperature is 100 ° C to 220 ° C, preferably 140 ° C to 210 ° C. As the catalyst, tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, organic tin compounds such as dioctyltin neodecanate, stannous oxide, tin compounds such as stannous chloride, tetrabutyl titanate, Titanium compounds such as tetraethyl titanate and tetrapropyl titanate, and other known esterification catalysts can be used. The amount of the catalyst used is preferably from 0.1 ppm to 1000 ppm, more preferably from 1 ppm to 100 ppm. Moreover, it is preferable to react in inert gas atmosphere, such as nitrogen, in order to prevent coloring.
　ラクトン化合物の開環重合物としては、市販のポリラクトンポリオールを使用することもできる。その例としては、ダイセル化学工業株式会社製「プラクセル」シリーズが挙げられる。 Commercially available polylactone polyols can also be used as the ring-opening polymer of the lactone compound. Examples thereof include “Placcel” series manufactured by Daicel Chemical Industries, Ltd.
　本発明に使用するポリエステルは、多価カルボン酸と多価アルコールの重縮合反応によっても得ることができる。 The polyester used in the present invention can also be obtained by a polycondensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol.
　上記多価カルボン酸の例としては、フタル酸、イソフタル酸、テレフタル酸、２，６－ナフタレンジカルボン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、マレイン酸、フマル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、トリメリット酸、ピロメリット酸などが挙げられる。 Examples of the polyvalent carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexa Examples include hydrophthalic acid, trimellitic acid, and pyromellitic acid.
　上記多価アルコールの例としては、エチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２－メチル－１，３－プロパンジオール、１，６－ヘキサンジオール、１，１０－デカンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール、１，４－シクロヘキサンジメタノール、１，４－ベンゼンジメタノール、２，２－ビス－（４－ヒドロキシエトキシフェニル）プロパン、１，４－ビス（２－ヒドロキシエチル）ベンゼン、１，６－ビス（２－ヒドロキシエトキシ）ヘキサン、ブタンジオール、ネオペンチルグリコール、１，４－ヘキサンジオールグリセリン、トリメチロールエタン、トリメチロールプロパン、トリス（２－ヒドロキシエチル）イソシアヌレート、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール、マンニトール、ソルビトール等が挙げられる。 Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl -1,3-propanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1, 4-cyclohexanedimethanol, 1,4-benzenedimethanol, 2,2-bis- (4-hydroxyethoxyphenyl) propane, 1,4-bis (2-hydroxyethyl) benzene, 1,6-bis (2- Hydroxyethoxy) hexa , Butanediol, neopentyl glycol, 1,4-hexanediol glycerin, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, ditrimethylolpropane, dipentaerythritol, mannitol, sorbitol, etc. Can be mentioned.
　上記多価カルボン酸と多価アルコールとの重縮合反応は、触媒を加えて加熱することで行うことができる。反応温度は１００℃～２２０℃が好ましく、より好ましくは１４０℃～２１０℃の範囲で行う。触媒としては、これらに限定されるものではないが、オクチル酸スズ、ジブチルスズオキシド、ジブチルスズラウレート、モノブチルスズヒドロキシブチルオキシド、ジオクチルスズネオデカネート等の有機スズ化合物、酸化第一スズ、塩化第一スズ等のスズ化合物、テトラブチルチタネート、テトラエチルチタネート、テトラプロピルチタネート等のチタン化合物、その他公知のエステル化触媒が利用できる。触媒の使用量は０．１ｐｐｍ～１０００ｐｐｍが好ましく、より好ましくは１ｐｐｍ～１００ｐｐｍである。また、着色を防ぐため窒素等の不活性ガス雰囲気下で反応を行うことが好ましい。 The polycondensation reaction between the polyvalent carboxylic acid and the polyhydric alcohol can be performed by adding a catalyst and heating. The reaction temperature is preferably from 100 ° C to 220 ° C, more preferably from 140 ° C to 210 ° C. Catalysts include, but are not limited to, organotin compounds such as tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, dioctyltin neodecanate, stannous oxide, stannous chloride Tin compounds such as tin, titanium compounds such as tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate, and other known esterification catalysts can be used. The amount of the catalyst used is preferably from 0.1 ppm to 1000 ppm, more preferably from 1 ppm to 100 ppm. Moreover, it is preferable to react in inert gas atmosphere, such as nitrogen, in order to prevent coloring.
　本発明に使用するポリエステルは、ヒドロキシカルボン酸の重縮合反応によっても得ることができる。ヒドロキシカルボン酸としては、脂肪族、芳香族、不飽和のヒドロキシカルボン酸を使用することができる。例としては、リシノレイン酸、リシノール酸、１２－ヒドロキシステアリン酸、ひまし油脂肪酸、水添ひまし油脂肪酸、δ－ヒドロキシ吉草酸、乳酸、グリコール酸、ヒドロキシイソフタル酸、ヒドロキシピバリン酸、４－ヒドロキシイソフタル酸、サリチル酸、１１－オキシヘキサドデカン酸、２－オキシドデカン酸、２，２－ジメチロールプロピオン酸、２，２－ジメチロール酪酸、２，２－ジメチロール吉草酸、２，２－ジメチロールペンタン酸、リンゴ酸、酒石酸、グルコン酸、４，４－ビス（ヒドロキシフェニル）酪酸、グルクロン酸、３－ヒドロキシブタン酸が挙げられ、これらの２種以上の混合物も使用できる。 The polyester used in the present invention can also be obtained by polycondensation reaction of hydroxycarboxylic acid. As the hydroxycarboxylic acid, aliphatic, aromatic or unsaturated hydroxycarboxylic acid can be used. Examples include ricinoleic acid, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, lactic acid, glycolic acid, hydroxyisophthalic acid, hydroxypivalic acid, 4-hydroxyisophthalic acid, salicylic acid 11-oxyhexadodecanoic acid, 2-oxidedecanoic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, 2,2-dimethylolpentanoic acid, malic acid, Examples thereof include tartaric acid, gluconic acid, 4,4-bis (hydroxyphenyl) butyric acid, glucuronic acid and 3-hydroxybutanoic acid, and a mixture of two or more of these can also be used.
　上記ヒドロキシカルボン酸の重縮合反応は、触媒を加えて加熱することにより行うことができる。反応温度は好ましくは１００℃～２２０℃、より好ましくは１４０℃～２１０℃の範囲とする。触媒としては、オクチル酸スズ、ジブチルスズオキシド、ジブチルスズラウレート、モノブチルスズヒドロキシブチルオキシド、ジオクチルスズネオデカネート等の有機スズ化合物、酸化第一スズ、塩化第一スズ等のスズ化合物、テトラブチルチタネート、テトラエチルチタネート、テトラプロピルチタネート等のチタン化合物、その他公知のエステル化触媒が利用できる。触媒の使用量は０．１ｐｐｍ～１０００ｐｐｍが好ましく、より好ましくは１ｐｐｍ～１００ｐｐｍである。また、着色を防ぐため窒素等の不活性ガス雰囲気下で反応を行うことが好ましい。 The polycondensation reaction of the hydroxycarboxylic acid can be performed by adding a catalyst and heating. The reaction temperature is preferably in the range of 100 ° C. to 220 ° C., more preferably 140 ° C. to 210 ° C. As the catalyst, tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, organic tin compounds such as dioctyltin neodecanate, stannous oxide, tin compounds such as stannous chloride, tetrabutyl titanate, Titanium compounds such as tetraethyl titanate and tetrapropyl titanate, and other known esterification catalysts can be used. The amount of the catalyst used is preferably from 0.1 ppm to 1000 ppm, more preferably from 1 ppm to 100 ppm. Moreover, it is preferable to react in inert gas atmosphere, such as nitrogen, in order to prevent coloring.
　本発明で使用するポリエステルの重量平均分子量は１００～５０，０００が好ましく、より好ましくは１，０００～１０，０００の範囲である。その重量平均分子量が１００未満であると分散性が低下するなどの性能低下が見られ、５０，０００を超えると分散剤としての使用時に粘度が高くなり、扱いにくくなる。 The weight average molecular weight of the polyester used in the present invention is preferably from 100 to 50,000, more preferably from 1,000 to 10,000. When the weight average molecular weight is less than 100, performance deterioration such as a decrease in dispersibility is observed. When the weight average molecular weight exceeds 50,000, the viscosity becomes high when used as a dispersant, and it becomes difficult to handle.
　本発明で使用するグラフト共重合体の製造方法は特に限定されないが、ポリビニルアセタール、ポリ酢酸ビニルおよびポリビニルアルコールに対して直接ポリエステルモノマーを反応させる方法、ポリビニルアセタール、ポリ酢酸ビニルおよびポリビニルアルコールが有する水酸基とポリエステルが有するカルボン酸とを脱水縮合させる方法、ポリビニルアセタール、ポリ酢酸ビニルおよびポリビニルアルコールが有する水酸基またはエステル基に対し、ポリエステルのエステル交換反応をさせる方法などが挙げられる。 The method for producing the graft copolymer used in the present invention is not particularly limited, but a method of directly reacting a polyester monomer with polyvinyl acetal, polyvinyl acetate and polyvinyl alcohol, a hydroxyl group of polyvinyl acetal, polyvinyl acetate and polyvinyl alcohol. And a method of dehydrating and condensing the polyester with a carboxylic acid, and a method of transesterifying the polyester with a hydroxyl group or ester group of polyvinyl acetal, polyvinyl acetate and polyvinyl alcohol.
　また、ポリビニルアセタール－ポリエステルグラフト共重合体と、ポリ酢酸ビニル－ポリエステル共重合体及び／又はポリビニルアルコール－ポリエステル共重合体をそれぞれ製造し、分散剤としての使用時にこれらを混合してもよいが、ポリビニルアセタールとポリ酢酸ビニル及び／又はポリビニルアルコールをあらかじめ混合してから、ポリエステル鎖を結合することもできる。 Further, a polyvinyl acetal-polyester graft copolymer, a polyvinyl acetate-polyester copolymer and / or a polyvinyl alcohol-polyester copolymer may be produced, and these may be mixed when used as a dispersant. It is also possible to combine the polyester chains after previously mixing polyvinyl acetal with polyvinyl acetate and / or polyvinyl alcohol.
　ポリビニルアセタールまたはポリ酢酸ビニルまたはポリビニルアルコールが有する水酸基またはエステル基は、１～９５モル％の範囲でポリエステルとグラフト結合を形成するのが好ましい。より好ましくは、この水酸基またはエステル基の２～５０モル％がポリエステルとグラフト結合を形成したものとする。いずれの場合も未反応のポリエステルが残存していてもよい。 The hydroxyl group or ester group of polyvinyl acetal, polyvinyl acetate or polyvinyl alcohol preferably forms a graft bond with the polyester in the range of 1 to 95 mol%. More preferably, 2 to 50 mol% of the hydroxyl group or ester group forms a graft bond with the polyester. In any case, unreacted polyester may remain.
　ポリビニルアセタール－ポリエステルグラフト共重合体に対するポリ酢酸ビニル－グラフト共重合体及び／又はポリビニルアルコール－ポリエステルグラフト共重合体の使用量は、ポリビニルアセタール－ポリエステルグラフト共重合体１００質量部に対してポリ酢酸ビニル－グラフト共重合体及び／又はポリビニルアルコール－ポリエステルグラフト共重合体の総量で１～５０質量部が好ましい。 The amount of the polyvinyl acetate-graft copolymer and / or polyvinyl alcohol-polyester graft copolymer used relative to the polyvinyl acetal-polyester graft copolymer is as follows. The total amount of the graft copolymer and / or polyvinyl alcohol-polyester graft copolymer is preferably 1 to 50 parts by mass.
２．分散剤の用途
　上記した本発明の分散剤は、無機および有機の各種固体粒子の分散に対して有効である。具体的には、塗料、印刷インキ、複写用トナー、プラスチック、顔料捺染剤、インクジェット記録用インキ、熱転写記録用インキ、カラーフィルター用レジスト、筆記具用インキ等の各分野で通常用いられる分散媒体中に、高濃度かつ安定に、固体粒子を分散させることができる。 2. Use of Dispersant The dispersant of the present invention described above is effective for dispersing various inorganic and organic solid particles. Specifically, in dispersion media commonly used in various fields such as paint, printing ink, copying toner, plastic, pigment printing agent, ink jet recording ink, thermal transfer recording ink, color filter resist, writing tool ink, etc. The solid particles can be dispersed with high concentration and stability.
　特に本発明では、ポリビニルアセタール－ポリエステルグラフト共重合体に対してポリ酢酸ビニル－ポリエステルグラフト共重合体及び／又はポリビニルアルコール－ポリエステルグラフト共重合体を混合して分散剤としたことにより、ポリビニルアセタール－ポリエステルグラフト共重合体単独で分散剤として使用した場合と比較して、分散体の粘度を顕著に低下させることができる。分散体の粘度が低下することにより、塗装時の作業性が向上する等の利点が得られ、分散体の用途がさらに広がる。 In particular, in the present invention, polyvinyl acetal-polyester graft copolymer is mixed with polyvinyl acetate-polyester graft copolymer and / or polyvinyl alcohol-polyester graft copolymer to form a dispersant. Compared to the case where the polyester graft copolymer alone is used as a dispersant, the viscosity of the dispersion can be significantly reduced. By reducing the viscosity of the dispersion, advantages such as improved workability during coating are obtained, and the use of the dispersion is further expanded.
　本発明の分散剤により分散される固体粒子は特に限定されないが、無機粒子の例としては、カオリン、ケイ酸アルミニウム、クレー、タルク、マイカ、ケイ酸カルシウム、ベントナイト、ケイ酸マグネシウム、アスベスト、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、ドロマイト、硫酸カルシウム、硫酸バリウム、硫酸アルミニウム、ジルコニア、マグネシア、アルミナ、三酸化アンチモン、酸化チタン、珪藻土、酸化鉄、酸化亜鉛、水酸化アルミニウム、水酸化鉄、炭化ケイ素、窒化ケイ素、窒化ホウ素、チタン酸バリウム、カーボンブラック、黒鉛、鉄粉、銀粉、アルミ粉、銅粉、ニッケル粉、金粉等が挙げられる。有機粒子の例としては、アゾ系、ジアゾ系、縮合アゾ系、チオインジゴ系、インダンスロン系、キナクリドン系、アントラキノン系、ベンゾイミダゾロン系、ペリレン系、フタロシアニン系、アントラピリジン系、ジオキサジン系等の有機顔料、澱粉、ポリエチレン樹脂、ウレタン樹脂、メラミン樹脂、ポリスチレン樹脂、ポリ乳酸、固体パラフィン等が挙げられる。 Solid particles dispersed by the dispersant of the present invention are not particularly limited, but examples of inorganic particles include kaolin, aluminum silicate, clay, talc, mica, calcium silicate, bentonite, magnesium silicate, asbestos, calcium carbonate. , Magnesium carbonate, barium carbonate, dolomite, calcium sulfate, barium sulfate, aluminum sulfate, zirconia, magnesia, alumina, antimony trioxide, titanium oxide, diatomaceous earth, iron oxide, zinc oxide, aluminum hydroxide, iron hydroxide, silicon carbide, Examples thereof include silicon nitride, boron nitride, barium titanate, carbon black, graphite, iron powder, silver powder, aluminum powder, copper powder, nickel powder, and gold powder. Examples of organic particles include azo, diazo, condensed azo, thioindigo, indanthrone, quinacridone, anthraquinone, benzimidazolone, perylene, phthalocyanine, anthrapyridine, dioxazine, etc. Organic pigment, starch, polyethylene resin, urethane resin, melamine resin, polystyrene resin, polylactic acid, solid paraffin and the like can be mentioned.
　分散媒としては、トルエン、キシレン、芳香族炭化水素系溶剤、ｎ－ヘキサン、シクロヘキサン、ｎ－ヘプタンなどの炭化水素系溶剤、塩化メチレン、クロロホルム、ジクロロエタンなどのハロゲン化炭化水素系溶剤、ジオキサン、テトラヒドロフラン、ブチルエーテル、ブチルエチルエーテル、ジグライムなどのエーテル系溶媒、メチルイソブチルケトン、シクロヘキサノン、イソホロンなどのケトン系溶媒、酢酸エチル、酢酸ブチル、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなどのエステル系溶剤、メチルアルコール、エチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、イソブチルアルコール、ｔ－ブチルアルコール、アミルアルコール、ｎ－ヘキシルアルコール、ｎ－ヘプチルアルコール、２－エチルヘキシルアルコール、ラウリルアルコール、ステアリルアルコール、シクロペンタノール、シクロヘキサノール、ベンジルアルコール、ｐ－ｔ－ブチルベンジルアルコールなどのアルコール系溶媒、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテルなどのアルキレングリコールのモノエーテル系溶剤の他、ジメチルアセトアミド、ジメチルホルムアミドなどのアミド系溶媒等が挙げられ、これらを単独で、または２種以上を混合して適宜使用することができる。 Dispersion media include toluene, xylene, aromatic hydrocarbon solvents, hydrocarbon solvents such as n-hexane, cyclohexane, n-heptane, halogenated hydrocarbon solvents such as methylene chloride, chloroform, dichloroethane, dioxane, tetrahydrofuran , Ether solvents such as butyl ether, butyl ethyl ether and diglyme, ketone solvents such as methyl isobutyl ketone, cyclohexanone and isophorone, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate Methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, alcohol Alcohol-based solvents such as alcohol, n-hexyl alcohol, n-heptyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, stearyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, pt-butylbenzyl alcohol, ethylene glycol monomethyl Alkylene glycol monoether solvents such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and amide solvents such as dimethylacetamide and dimethylformamide These may be used alone or in combination of two or more. It can be.
　本発明の分散剤の使用量は、分散対象となる固体粒子の種類等にもより、特に限定されないが、通常は固体粒子に対して１～３００質量％程度が好ましい。 The amount of the dispersant of the present invention is not particularly limited depending on the type of solid particles to be dispersed, but is usually preferably about 1 to 300% by mass with respect to the solid particles.
　分散方法は特に限定されず、ボールミル、ビーズミル、サンドミル等の粉砕機を用いる公知の方法で分散することができる。 The dispersion method is not particularly limited, and the dispersion can be performed by a known method using a pulverizer such as a ball mill, a bead mill, or a sand mill.
　また、本発明の分散剤を用い、固体粒子、樹脂を含有し、さらに必要に応じて溶剤等を含有する、固体粒子含有樹脂組成物を調製することができる。この固体粒子含有樹脂組成物は、例えば塗料組成物又はインキ組成物に使用することができる。固体粒子含有樹脂組成物に含有される樹脂としては、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、アルキッド樹脂、シリコーン樹脂、フッ素樹脂、メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂、ポリアミド樹脂、フェノール樹脂、塩化ビニル、ポリエチレン樹脂、ポリビニルアセタール樹脂等、広範囲の樹脂が挙げられるが、これらに限定されない。 Further, using the dispersant of the present invention, a solid particle-containing resin composition containing solid particles and resin, and further containing a solvent or the like as necessary can be prepared. This solid particle-containing resin composition can be used in, for example, a coating composition or an ink composition. The resin contained in the solid particle-containing resin composition includes acrylic resin, urethane resin, epoxy resin, polyester resin, alkyd resin, silicone resin, fluororesin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, phenol resin, A wide range of resins such as, but not limited to, vinyl chloride, polyethylene resin, and polyvinyl acetal resin are included.
　固体粒子含有樹脂組成物の製造方法としては、本発明の分散剤と固体粒子、樹脂、溶剤、その他添加剤などと混練して直接固体粒子含有樹脂組成物を調製することもできるが、分散剤、固体粒子、分散媒を混練して固体粒子分散体を作った後に、これに樹脂を添加して固体粒子含有樹脂組成物とすることもできる。 As a method for producing a solid particle-containing resin composition, a solid particle-containing resin composition can be directly prepared by kneading the dispersant of the present invention with solid particles, a resin, a solvent, and other additives. Alternatively, after solid particles and a dispersion medium are kneaded to form a solid particle dispersion, a resin may be added thereto to obtain a solid particle-containing resin composition.
　また、本発明の分散剤と固体粒子、モノマー又は反応性基を有するオリゴマーを混練して分散させた後、これを重合して固体粒子含有樹脂組成物を作製することもできる。 Alternatively, the dispersant of the present invention and solid particles, monomers or oligomers having reactive groups can be kneaded and dispersed, and then polymerized to prepare a solid particle-containing resin composition.
　さらに、本発明の分散剤により固体粒子の表面処理を行うことができる。処理方法としてはヘンシェルミキサー、ボールミル、アトマイザーコロイドミル、バンバリミキサー等を用いて固体粒子を攪拌しながら分散剤を添加して混合する乾式法、溶剤中で処理した後溶剤を除去する湿式法を用いることができる。このように本発明の分散剤で表面処理を行うことにより、固体粒子の分散性を向上させ、凝集を防止することができる。 Furthermore, the surface treatment of the solid particles can be performed with the dispersant of the present invention. As a treatment method, a dry method in which a dispersant is added and mixed while stirring solid particles using a Henschel mixer, a ball mill, an atomizer colloid mill, a Banbury mixer, etc., or a wet method in which the solvent is removed after treatment in a solvent is used. be able to. Thus, by performing the surface treatment with the dispersant of the present invention, the dispersibility of the solid particles can be improved and aggregation can be prevented.
　以下、実施例により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、以下の記載中、特に他に特定しない限り、「部」は「質量部」を表し、「％」は「質量％」を表す。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not particularly limited to the examples. In the following description, unless otherwise specified, “part” represents “part by mass” and “%” represents “% by mass”.
［分散剤の調製］
［製造例１］（ポリビニルアセタール－ポリエステルグラフト共重合体）
　窒素導入管、温度計、還流管を取り付けた反応容器に、１２－ヒドロキシステアリン酸５０．０部、ε－カプロラクトン８００．０部、テトラブチルチタネート０．１部を仕込み、窒素雰囲気下で１６０℃まで４時間かけて昇温し、残存するε－カプロラクトンが１％以下になるまで１６０℃で加熱を行った。反応生成物は黄色固体で、重量平均分子量は７，１００、酸価は７．９ｍｇＫＯＨ／ｇであった。 [Preparation of dispersant]
[Production Example 1] (Polyvinyl acetal-polyester graft copolymer)
A reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a reflux tube was charged with 50.0 parts of 12-hydroxystearic acid, 800.0 parts of ε-caprolactone, and 0.1 parts of tetrabutyl titanate, and 160 ° C. in a nitrogen atmosphere. Until the remaining ε-caprolactone was 1% or less. The reaction product was a yellow solid, the weight average molecular weight was 7,100, and the acid value was 7.9 mgKOH / g.
　窒素導入管、温度計、還流管、検水管を取り付けた反応容器に、ポリビニルアセタール（積水化学工業株式会社製、商品名「エスレックＢＸ－Ｌ」、平均分子量約２００００、水酸基３７±３モル％、アセチル基３モル％以下、アセタール化度約６１モル％）４．１部、上記反応生成物であるポリエステル１２９．０部、ジオクチルスズネオデカネート０．０５部を仕込み、窒素雰囲気下で２００℃まで昇温し、６時間加熱を行った。反応生成物は黄色粘調液体で、重量平均分子量は９５，０００、酸価は３．３ｍｇＫＯＨ／ｇであった。 In a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a reflux tube, and a test tube, polyvinyl acetal (manufactured by Sekisui Chemical Co., Ltd., trade name “ESREC BX-L”, average molecular weight of about 20000, hydroxyl group 37 ± 3 mol%, Acetyl group 3 mol% or less, degree of acetalization about 61 mol%) 4.1 parts, 129.0 parts of polyester as the above reaction product, 0.05 parts of dioctyltin neodecanate, were charged at 200 ° C. in a nitrogen atmosphere. And heated for 6 hours. The reaction product was a yellow viscous liquid, the weight average molecular weight was 95,000, and the acid value was 3.3 mgKOH / g.
［製造例２］（ポリ酢酸ビニル－ポリエステルグラフト共重合体）
　窒素導入管、温度計、還流管を取り付けた反応容器に、２，２－ジメチロールプロピオン酸１００．０部、ε－カプロラクトン８５０．０部、テトラブチルチタネート０．０５部を仕込み、窒素雰囲気下で１６０℃まで４時間かけて昇温し、残存するε－カプロラクトンが１％以下になるまで１６０℃で加熱を行った。反応生成物は黄色固体で、重量平均分子量は２，０００、酸価は２９．５ｍｇＫＯＨ／ｇであった。 [Production Example 2] (polyvinyl acetate-polyester graft copolymer)
A reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a reflux tube was charged with 100.0 parts of 2,2-dimethylolpropionic acid, 850.0 parts of ε-caprolactone, and 0.05 parts of tetrabutyl titanate under a nitrogen atmosphere. The temperature was raised to 160 ° C. over 4 hours, and heating was performed at 160 ° C. until the remaining ε-caprolactone was 1% or less. The reaction product was a yellow solid, the weight average molecular weight was 2,000, and the acid value was 29.5 mgKOH / g.
　窒素導入管、温度計、還流管、検水管を取り付けた反応容器に、ポリ酢酸ビニル（電気化学工業株式会社製、商品名「デンカサクノールＳＮ－０４Ｔ」、重合度５００～７００）１２．３部、上記反応生成物であるポリエステル６４．２部、ジオクチルスズネオデカネート０．０５部を仕込み、窒素雰囲気下で２００℃まで昇温し、６時間加熱を行った。反応生成物は黄色粘調液体で、重量平均分子量は６５，０００、酸価は８．８ｍｇＫＯＨ／ｇであった。 Polyvinyl acetate (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “Denkasacnol SN-04T”, degree of polymerization 500 to 700) 12.3 in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a reflux tube, and a sample tube Part, 64.2 parts of polyester as the above reaction product and 0.05 part of dioctyltin neodecanate were charged, heated to 200 ° C. in a nitrogen atmosphere, and heated for 6 hours. The reaction product was a yellow viscous liquid, the weight average molecular weight was 65,000, and the acid value was 8.8 mgKOH / g.
［製造例３］（ポリビニルアルコール－ポリエステルグラフト共重合体）
　窒素導入管、温度計、還流管を取り付けた反応容器に、メタノール１０．０部、ε－カプロラクトン８００．０部、テトラブチルチタネート０．１部を仕込み、窒素雰囲気下で１６０℃まで４時間かけて昇温し、残存するε－カプロラクトンが１％以下になるまで１６０℃で加熱を行った。反応生成物は黄色固体で、重量平均分子量は３，１００であった。 [Production Example 3] (Polyvinyl alcohol-polyester graft copolymer)
A reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a reflux tube was charged with 10.0 parts of methanol, 800.0 parts of ε-caprolactone, and 0.1 part of tetrabutyl titanate, and the temperature was increased to 160 ° C. for 4 hours under a nitrogen atmosphere. The temperature was raised and heated at 160 ° C. until the remaining ε-caprolactone was 1% or less. The reaction product was a yellow solid, and the weight average molecular weight was 3,100.
　窒素導入管、温度計、還流管を取り付けた反応容器に、ポリビニルアルコール（株式会社クラレ製、商品名「クラレポバールＰＶＡ－１０２」、鹸化度９８．０～９９．０％、重合度２００）４９．７部、上記反応生成物であるポリエステル５０．３部、ジオクチルスズネオデカネート０．０５部を仕込み、窒素雰囲気下で２００℃まで昇温し、６時間加熱を行った。反応生成物は黄色粘調液体で、重量平均分子量は８５，５００であった。 In a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a reflux tube, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name “Kuraray Poval PVA-102”, degree of saponification 98.0 to 99.0%, degree of polymerization 200) 49 .7 parts, 50.3 parts of polyester as the above reaction product, and 0.05 parts of dioctyltin neodecanate were charged, heated to 200 ° C. in a nitrogen atmosphere, and heated for 6 hours. The reaction product was a yellow viscous liquid, and the weight average molecular weight was 85,500.
［製造例４］（ポリビニルアセタール－ポリエステル共重合体とポリ酢酸ビニル－ポリエステル共重合体の混合物）
　窒素導入管、温度計、還流管を取り付けた反応容器に、ポリビニルブチラール（積水化学工業株式会社製、商品名「エスレックＢＬ－１」、平均分子量約１９，０００、水酸基約３６モル％、アセチル基３モル％以下、ブチラール化度６３±３モル％）２７．５部、ポリ酢酸ビニル（電気化学工業株式会社製、商品名「デンカサクノールＳＮ－０４Ｔ」、重合度５００～７００）３．１部、ポリカプロラクトン（ダイセル化学工業株式会社製、商品名「プラクセルＨ１Ｐ」、分子量１０，０００）５０．０部、ジオクチルスズネオデカネート０．０５部を仕込み、窒素雰囲気下で２００℃まで昇温し、６時間加熱を行った。反応生成物は黄色粘調液体で、重量平均分子量は９２，５００であった。 [Production Example 4] (Polyvinyl acetal-polyester copolymer and polyvinyl acetate-polyester copolymer mixture)
In a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a reflux tube, polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., trade name “ESREC BL-1”, average molecular weight of about 19,000, hydroxyl group of about 36 mol%, acetyl group 37.5% or less, butyralization degree 63 ± 3 mol%) 27.5 parts, polyvinyl acetate (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “Denkasacnol SN-04T”, polymerization degree 500-700) 3.1 Part, polycaprolactone (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel H1P”, molecular weight 10,000) and 0.05 part of dioctyltin neodecanate are charged, and the temperature is raised to 200 ° C. in a nitrogen atmosphere. And heated for 6 hours. The reaction product was a yellow viscous liquid, and the weight average molecular weight was 92,500.
［製造例５］（ポリビニルアセタール－ポリエステル共重合体とポリビニルアルコール－ポリエステル共重合体の混合物）
　窒素導入管、温度計、還流管を取り付けた反応容器に、ポリビニルブチラール４９．７部（積水化学工業株式会社製、商品名「エスレックＢＬ－１」、平均分子量約１９０００、水酸基約３６モル％、アセチル基３モル％以下、ブチラール化度６３±３モル％）、ポリビニルアルコール（株式会社クラレ製、商品名「クラレポバールＰＶＡ－１０２」鹸化度９８．０～９９．０％、重合度２００）６．１部、ε－カプロラクトン１１４．０部、ジオクチルスズネオデカネート０．２部を仕込み、窒素雰囲気下で、残存するε－カプロラクトンが１％以下になるまで１８０℃で加熱を行った。反応生成物は淡黄色粘調液体で、重量平均分子量は２１８，０００であった。 [Production Example 5] (Polyvinyl acetal-polyester copolymer and polyvinyl alcohol-polyester copolymer mixture)
In a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a reflux tube, 49.7 parts of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., trade name “ESREC BL-1”, average molecular weight of about 19000, hydroxyl group of about 36 mol%, 3 mol% or less of acetyl group, butyralization degree 63 ± 3 mol%), polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name “Kuraray Poval PVA-102”, saponification degree 98.0 to 99.0%, polymerization degree 200) 6 .1 part, 114.0 parts of ε-caprolactone and 0.2 part of dioctyltin neodecanate were charged and heated at 180 ° C. in a nitrogen atmosphere until the remaining ε-caprolactone was 1% or less. The reaction product was a pale yellow viscous liquid, and the weight average molecular weight was 218,000.
［製造例６］（ポリビニルアセタール－ポリエステル共重合体とポリ酢酸ビニル－ポリエステル共重合体の混合物）
　窒素導入管、温度計、還流管を取り付けた反応容器に、ポリビニルブチラール（積水化学工業株式会社製、商品名「エスレックＢＬ－１」、平均分子量約１９，０００、水酸基約３６モル％、アセチル基３モル％以下、ブチラール化度６３±３モル％）２４．４部、ポリ酢酸ビニル（電気化学工業株式会社製、商品名「デンカサクノールＳＮ－０４Ｔ」、重合度５００～７００）６．２部、ポリカプロラクトン（ダイセル化学工業株式会社製、商品名「プラクセルＨ１Ｐ」、分子量１０，０００）４９．０部、ポリエステルポリオール（株式会社クラレ製、商品名「クラレポリオールＰ－６０１０」、アジピン酸と３－メチル－１，５－ペンタンジオールのポリエステルポリオ－ル、平均分子量約６，０００）１．０部、ジオクチルスズネオデカネート０．０５部を仕込み、窒素雰囲気下で２００℃まで昇温し、６時間加熱を行った。反応生成物は黄色粘調液体で、重量平均分子量は１０１，１００であった。 [Production Example 6] (Polyvinyl acetal-polyester copolymer and polyvinyl acetate-polyester copolymer mixture)
In a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a reflux tube, polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., trade name “ESREC BL-1”, average molecular weight of about 19,000, hydroxyl group of about 36 mol%, acetyl group 34.4% or less, degree of butyral 63 ± 3 mol%) 24.4 parts, polyvinyl acetate (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “Denkasacnol SN-04T”, degree of polymerization 500-700) 6.2 Part, polycaprolactone (Daicel Chemical Industries, Ltd., trade name “Placcel H1P”, molecular weight 10,000) 49.0 parts, polyester polyol (Kuraray Co., Ltd., trade name “Kuraray Polyol P-6010”, adipic acid and Polyester polyol of 3-methyl-1,5-pentanediol, average molecular weight of about 6,000) 1.0 part, dioctyltin neo They were charged Kaneto 0.05 parts, the temperature was raised to 200 ° C. under a nitrogen atmosphere, was heated for 6 hours. The reaction product was a yellow viscous liquid, and the weight average molecular weight was 101,100.
［比較製造例１］
　窒素導入管、温度計、還流管、検水管を取り付けた反応容器に、ポリエチレンイミン（ＢＡＳＦ社製、商品名「Ｌｕｐａｓｏｌ　ＰＲ８５１５」、分子量２０００）８．１部、製造例１のポリエステル９１．９部、テトラブチルチタネート０．０５部を仕込み、窒素雰囲気下で２００℃まで昇温し、６時間加熱を行った。反応生成物は茶褐色固体で、アミン価は４５．５ｍｇＫＯＨ／ｇ、酸価は１．１ｍｇＫＯＨ／ｇであった。 [Comparative Production Example 1]
In a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a reflux tube, and a test tube, 8.1 parts of polyethyleneimine (BASF, trade name “Lupasol PR8515”, molecular weight 2000), 91.9 parts of polyester of Production Example 1 Then, 0.05 part of tetrabutyl titanate was charged, heated to 200 ° C. under a nitrogen atmosphere, and heated for 6 hours. The reaction product was a brown solid, the amine value was 45.5 mgKOH / g, and the acid value was 1.1 mgKOH / g.
[製造例７]（表面処理顔料の製造）
　ピグメントブルー１５：６ ５０．０部、製造例６のグラフト共重合物５．０部、酢酸エチル２５０部を混合し、１時間攪拌した後、酢酸エチルを減圧留去して表面処理顔料を得た。 [Production Example 7] (Production of surface-treated pigment)
Pigment Blue 15: 6 50.0 parts, the graft copolymer of Production Example 6 5.0 parts, and ethyl acetate 250 parts were mixed and stirred for 1 hour, and then ethyl acetate was distilled off under reduced pressure to obtain a surface-treated pigment. It was.
[分散剤の調製及び耐熱性試験]
　上記製造例、比較製造例により得られた分散剤、及び次の比較品１，２につき、以下の方法により耐熱性の評価を行った。結果を表１に示す。 [Preparation of dispersant and heat resistance test]
About the dispersing agent obtained by the said manufacture example and the comparative manufacture example, and the following comparative products 1 and 2, heat resistance was evaluated with the following method. The results are shown in Table 1.
比較品１：味の素ファインテクノ株式会社製、商品名「アジスパーＰＢ－８２２」、高分子系顔料分散剤、アミン価１７ｍｇＫＯＨ／ｇ、酸価１４ｍｇＫＯＨ／ｇ
比較品２：積水化学工業株式会社製、商品名「エスレックＢＬ－１」、ポリビニルブチラール、平均分子量約１９０００、水酸基約３６モル％、アセチル基３モル％以下、ブチラール化度６３±３モル％ Comparative product 1: Ajinomoto Fine Techno Co., Ltd., trade name “Ajisper PB-822”, polymer pigment dispersant, amine value 17 mgKOH / g, acid value 14 mgKOH / g
Comparative product 2: manufactured by Sekisui Chemical Co., Ltd., trade name “ESREC BL-1”, polyvinyl butyral, average molecular weight of about 19000, hydroxyl group of about 36 mol%, acetyl group of 3 mol% or less, degree of butyralization of 63 ± 3 mol%
色差：分散剤０．５ｍｇを塩化メチレン２０ｍＬに溶解し、シリカゲル１０ｇと混合し室温で乾燥させた。得られたシリカゲルの半量を２００℃で１時間加熱処理を行い、処理前後の色差を測定した。 
耐熱性：以下の基準により判定した。 
　○：色差（ΔＥ）０以上５以下　△：色差（ΔＥ）５より大きく１０未満　×：色差（ΔＥ）１０以上 Color difference: 0.5 mg of the dispersant was dissolved in 20 mL of methylene chloride, mixed with 10 g of silica gel, and dried at room temperature. Half of the obtained silica gel was heat-treated at 200 ° C. for 1 hour, and the color difference before and after the treatment was measured.
Heat resistance: Judged according to the following criteria.
○: Color difference (ΔE) 0 or more and 5 or less Δ: Color difference (ΔE) 5 to less than 10 ×: Color difference (ΔE) 10 or more
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
[固体粒子分散体の調製及び評価]
＜分散性試験＞
　上記製造例により得られたポリビニルアセタール・ポリエステルグラフト共重合体等、及び比較対象の分散剤を表２に示した分散媒に溶解し、表２に示した固体粒子、０．３ｍｍのジルコニアビーズをそれぞれ加え、ペイントシェーカーを用いて４時間分散した。分散操作停止直後の分散性を目視にて観察し、以下の基準で評価した。実施例１６については、製造例７で得られた表面処理顔料に分散媒及び上記ジルコニアビーズを加え、さらなる分散剤の使用は行わなかった以外は同じ操作を行った。結果を表２に示す。 
　分散性：以下の基準により判定した。 
　◎：すべての粉末が液中に分散し、まったく底部に沈澱が発生していない。 
　○：ほとんどの粉末が液中に分散しているが、わずかに底部に沈澱が発生する。 
　△：半分程度の粉末が液中に沈澱する。 
　×：ほとんどの粉末が底部に沈澱する。 [Preparation and Evaluation of Solid Particle Dispersion]
<Dispersibility test>
The polyvinyl acetal / polyester graft copolymer obtained by the above production example and the dispersant for comparison are dissolved in the dispersion medium shown in Table 2, and the solid particles and 0.3 mm zirconia beads shown in Table 2 are obtained. Each was added and dispersed for 4 hours using a paint shaker. The dispersibility immediately after stopping the dispersion operation was visually observed and evaluated according to the following criteria. For Example 16, the same operation was performed except that the dispersion medium and the zirconia beads were added to the surface-treated pigment obtained in Production Example 7 and no further dispersant was used. The results are shown in Table 2.
Dispersibility: Judged according to the following criteria.
(Double-circle): All powder disperse | distributes in a liquid and precipitation does not generate | occur | produce at the bottom part at all.
○: Most of the powder is dispersed in the liquid, but precipitation occurs slightly at the bottom.
Δ: About half of the powder is precipitated in the liquid.
X: Most powders settle to the bottom.
＜粘度＞
　上記分散試験で得られた分散体の粘度をＢ型粘度計で測定した。結果を表２に示す。 <Viscosity>
The viscosity of the dispersion obtained in the dispersion test was measured with a B-type viscometer. The results are shown in Table 2.
＜塗膜状態試験＞
　分散試験後の分散体１０．０部にアクリル樹脂（三菱レイヨン（株）製、商品名「アクリペットＶＨ」）またはブチラール樹脂（積水化学工業（株）製、商品名「エスレックＢＨ－３）を０．４部添加し、攪拌して溶解させた。得られた混合液をガラス基板に平均膜厚が１．８μｍになるようにスピンコートし、１２０℃のオーブンで１時間加熱した。得られた塗膜を目視にて観察し、以下の基準により評価した。結果を表２に示す。 
　○：得られた塗膜が透明である。 
　△：得られた塗膜に曇りが見られる。 
　×：粒子が凝集し、透明性がない。 <Coating condition test>
Acrylic resin (Mitsubishi Rayon Co., Ltd., trade name “Acrypet VH”) or butyral resin (Sekisui Chemical Co., Ltd., trade name “S-Lec BH-3”) is applied to 10.0 parts of the dispersion after the dispersion test. 0.4 part was added and dissolved by stirring, and the resulting mixture was spin coated on a glass substrate to an average film thickness of 1.8 μm and heated in an oven at 120 ° C. for 1 hour. The coated film was visually observed and evaluated according to the following criteria, and the results are shown in Table 2.
○: The obtained coating film is transparent.
(Triangle | delta): Cloudiness is seen in the obtained coating film.
X: Particles aggregate and have no transparency.
＜塗膜の耐熱性試験＞
　塗膜状態試験で作製した試験板と、さらにそれを２３０℃で１時間加熱した試験板との色差を測定し、以下の基準により評価した。結果を表２に示す。 
　○：色差（ΔＥ）０以上１以下　△：色差（ΔＥ）１より大きく２．５未満　×：色差（ΔＥ）２．５以上 <Heat resistance test of coating film>
The color difference between the test plate prepared in the coating state test and the test plate heated at 230 ° C. for 1 hour was measured and evaluated according to the following criteria. The results are shown in Table 2.
○: Color difference (ΔE) 0 or more and 1 or less Δ: Color difference (ΔE) 1 or more and less than 2.5 ×: Color difference (ΔE) 2.5 or more
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［感光性着色樹脂組成物の調製及び評価］
　メタクリル酸／ベンジルメタクリレート共重合体（２５／７５質量比、重量平均分子量約３００００）４０．０部、ピグメントブルー１５：６　２３．０部、製造例６のグラフト共重合物　７．０部、ジペンタエリスリトールヘキサアクリレート　１０．０部、２，４－ビス（トリクロロメチル）－６－（２－エトキシスチリル）－ｓ－トリアジン　３．０部、ＰＧＭＥＡ　２００部を混合し、０．３ｍｍジルコニアビーズを加え、ペイントシェーカーにより分散を行い、感光性着色樹脂組成物を得た。 [Preparation and Evaluation of Photosensitive Colored Resin Composition]
Methacrylic acid / benzyl methacrylate copolymer (25/75 mass ratio, weight average molecular weight of about 30000) 40.0 parts, Pigment Blue 15: 6 23.0 parts, Graft copolymer 7.0 of Production Example 6, di Mix 10.0 parts of pentaerythritol hexaacrylate, 3.0 parts of 2,4-bis (trichloromethyl) -6- (2-ethoxystyryl) -s-triazine and 200 parts of PGMEA, and add 0.3 mm zirconia beads. Then, dispersion was performed with a paint shaker to obtain a photosensitive colored resin composition.
　ガラス基板に上記感光性着色樹脂組成物をスピンコート塗布し、７０℃のクリーンオーブン中で２０分間プリベークを行い、乾燥塗布膜を作製した。次いで、この基板を室温に冷却した後、超高圧水銀ランプを用い、紫外線を露光した。その後、この基板を０．０４％水酸化カリウム水溶液を用いてスプレー現像した後、イオン交換水で洗浄し、風乾した。その後、クリーンオーブン中で、２３０℃で３０分間ポストベークを行った。乾燥塗膜は±０．５μｍ以内の均一で平滑な塗膜であり、光透過率（３８０～７８０ｎｍの平均）は９８％であった。 The photosensitive colored resin composition was spin-coated on a glass substrate and pre-baked in a clean oven at 70 ° C. for 20 minutes to prepare a dry coating film. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a 0.04% aqueous potassium hydroxide solution, washed with ion-exchanged water, and air-dried. Thereafter, post-baking was performed at 230 ° C. for 30 minutes in a clean oven. The dried coating film was a uniform and smooth coating film within ± 0.5 μm, and the light transmittance (average of 380 to 780 nm) was 98%.
　本発明の分散剤は、塗料、印刷インキ、複写用トナー、プラスチック、顔料捺染剤、インクジェット記録用インキ、熱転写記録用インキ、カラーフィルター用レジスト、筆記具用インキ等の分野で非水系液体中に固体粒子を分散させるのに極めて有効である。 The dispersant of the present invention is solid in non-aqueous liquids in the fields of paints, printing inks, copying toners, plastics, pigment printing agents, ink jet recording inks, thermal transfer recording inks, color filter resists, writing instrument inks, etc. It is extremely effective for dispersing the particles.

Claims (6)

  1. 　ポリビニルアセタール－ポリエステルグラフト共重合体を含有し、かつポリ酢酸ビニル－ポリエステルグラフト共重合体及び／又はポリビニルアルコール－ポリエステルグラフト共重合体を含有することを特徴とする分散剤。 A dispersant comprising a polyvinyl acetal-polyester graft copolymer and a polyvinyl acetate-polyester graft copolymer and / or a polyvinyl alcohol-polyester graft copolymer.
  2. 　前記ポリビニルアセタール－ポリエステルグラフト共重合体１００質量部に対して、ポリ酢酸ビニル－ポリエステルグラフト共重合体及び／又はポリビニルアルコール－ポリエステルグラフト共重合体を１～５０質量部含有することを特徴とする、請求項１の分散剤。 1 to 50 parts by mass of polyvinyl acetate-polyester graft copolymer and / or polyvinyl alcohol-polyester graft copolymer with respect to 100 parts by mass of the polyvinyl acetal-polyester graft copolymer, The dispersant of claim 1.
  3. 　請求項１又は２に記載の分散剤により固体粒子を非水系液体に分散させてなる固体粒子分散体。 A solid particle dispersion obtained by dispersing solid particles in a non-aqueous liquid using the dispersant according to claim 1.
  4. 　請求項１又は２に記載の分散剤、樹脂、及び固体粒子を含有する固体粒子含有樹脂組成物。 A solid particle-containing resin composition containing the dispersant, resin, and solid particles according to claim 1 or 2.
  5. 　塗料組成物又はインキ組成物であることを特徴とする、請求項４に記載の固体粒子含有樹脂組成物。 The solid particle-containing resin composition according to claim 4, wherein the resin composition is a paint composition or an ink composition.
  6. 　請求項１又は２に記載の分散剤で処理したことを特徴とする表面処理固体粒子。 Surface-treated solid particles characterized by being treated with the dispersant according to claim 1 or 2.
PCT/JP2013/054089 2012-03-07 2013-02-20 Dispersant including polyvinyl acetal-polyester graft copolymer, solid-particle dispersion using same, solid particle-containing composition and surface-treated solid particles WO2013133013A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-050648 2012-03-07
JP2012050648A JP5758332B2 (en) 2012-03-07 2012-03-07 Dispersant containing polyvinyl acetal-polyester graft copolymer, solid particle dispersion using the same, solid particle-containing composition, and surface-treated solid particles

Publications (1)

Publication Number Publication Date
WO2013133013A1 true WO2013133013A1 (en) 2013-09-12

Family

ID=49116496

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/054089 WO2013133013A1 (en) 2012-03-07 2013-02-20 Dispersant including polyvinyl acetal-polyester graft copolymer, solid-particle dispersion using same, solid particle-containing composition and surface-treated solid particles

Country Status (3)

Country Link
JP (1) JP5758332B2 (en)
TW (1) TWI488689B (en)
WO (1) WO2013133013A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011038028A (en) * 2009-08-17 2011-02-24 Dai Ichi Kogyo Seiyaku Co Ltd Polyvinyl acetal-polyvinylpyrrolidone graft copolymer
WO2011067889A1 (en) * 2009-12-04 2011-06-09 第一工業製薬株式会社 Polyvinyl acetal/polyester graft copolymer, and dispersant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0881547A (en) * 1994-09-12 1996-03-26 Daicel Chem Ind Ltd Carboxylic lactone-modified polyvinyl acetal resin, its production and curable resin composition
JPH07238199A (en) * 1994-01-10 1995-09-12 Daicel Chem Ind Ltd Curable resin composition
JP4971867B2 (en) * 2007-05-07 2012-07-11 第一工業製薬株式会社 Method for producing polyvinyl alcohol-polyvinylpyrrolidone graft copolymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011038028A (en) * 2009-08-17 2011-02-24 Dai Ichi Kogyo Seiyaku Co Ltd Polyvinyl acetal-polyvinylpyrrolidone graft copolymer
WO2011067889A1 (en) * 2009-12-04 2011-06-09 第一工業製薬株式会社 Polyvinyl acetal/polyester graft copolymer, and dispersant

Also Published As

Publication number Publication date
JP5758332B2 (en) 2015-08-05
TWI488689B (en) 2015-06-21
JP2013185049A (en) 2013-09-19
TW201402202A (en) 2014-01-16

Similar Documents

Publication Publication Date Title
JP5755764B2 (en) Process for producing polyvinyl acetal / polyester graft copolymer
JP5114928B2 (en) Colored resin composition, inkjet ink, and color filter substrate
TWI791620B (en) Multi-amine polyester dispersant made via an anhydride intermediate, preparation method thereof and use thereof
TWI526244B (en) Dispersant composition
JP5125525B2 (en) Ink composition for ink jet recording and color filter substrate
JPWO2004037924A1 (en) Aqueous polyester resin dispersion and method for producing the same
TW201204781A (en) Dispersant composition
JP2009167303A (en) Inkjet ink and color filter substrate
JP5762826B2 (en) Solid particle dispersion and resin composition containing solid particles using polyvinyl acetal / polyester graft copolymer as dispersant
JP2017101170A (en) Production method for aqueous ink
JP2010053260A (en) Inkjet ink and color filter substrate
CN107207889B (en) Polyester dispersant for coloring ceramic tiles using ink-jet inks and ink-jet printers
JP5758332B2 (en) Dispersant containing polyvinyl acetal-polyester graft copolymer, solid particle dispersion using the same, solid particle-containing composition, and surface-treated solid particles
JP5951441B2 (en) Solid particle dispersant, solid particle dispersion using the same, and surface-treated solid particles
TW202045247A (en) Multi-amine polyester dispersant made via an anhydride intermediate
JP2009191251A (en) Inkjet ink and color filter substrate
JP2022500521A (en) Multiamine polyester dispersant and method of making
JP2007031509A (en) Polyester resin aqueous dispersion and method for producing the same
JP4820131B2 (en) Pigment polymer dispersant and coloring composition for color filter
JP2005232332A (en) Resin graft carbon black composition
WO2000066669A1 (en) Polyester based varnish for uv curable inks
CN113795534A (en) Polyamine dispersants prepared via anhydride intermediates
JP2009062528A (en) Inkjet ink and color filter substrate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13757636

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13757636

Country of ref document: EP

Kind code of ref document: A1