TW201402202A - Dispersant including polyvinyl acetal-polyester graft copolymer, solid-particle dispersion using same, solid particle-containing composition and surface-treated solid particles - Google Patents

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

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

The present invention relates to a dispersant containing a polyvinyl acetal-polyester graft copolymer, a solid particle dispersion using the same, a composition containing solid particles, and surface-treated solid particles.

The technique of dispersing solid particles in a non-aqueous liquid is applied to various industrial fields such as paints, printing inks, toners for photocopying, plastics, pigment printing agents, inks for inkjet recording, inks for thermal transfer recording, and color. In the fields of photoresists for filters, inks for note-taking tools, and the like, dispersion of pigments is an important basic technology. When such a dispersed composition is produced, there is a problem that solid particles are easily aggregated. It is known that if agglomeration occurs, there is a problem that the stability is lowered, the gloss of the final product, the coloring power, the gloss is lowered, and the spots are caused. In order to prevent such agglomeration and improve dispersibility, a dispersing agent is used.

Conventionally, as a nonaqueous dispersant, a reaction product of a polyester and a polyamine has been known. For example, Patent Documents 1 to 3 disclose a reaction product of a hydroxystearic acid condensate and a polyethyleneimine, a reaction product of a polycaprolactone-based polyester compound and a polyallylamine, and the like. Like these dispersing agents with polyamines as adsorption groups In order to know, if it has an amine skeleton, there is a problem that yellowing occurs at a high temperature.

On the other hand, Patent Document 4 discloses a polyvinyl acetal-polyester graft copolymer as a nonaqueous dispersant which has excellent properties. Compared with the dispersant containing nitrogen, it has the advantage of being excellent in heat-resistant yellowing property, but the viscosity of the dispersion tends to increase.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 09-176511

Patent Document 2: Japanese Laid-Open Patent Publication No. 07-207012

Patent Document 3: Japanese Laid-Open Patent Publication No. 09-169821

Patent Document 4: WO2011/067889A1

The present invention has been made in view of the above problems, and it is an object of the invention to provide a dispersing agent which can effectively prevent agglomeration of solid particles in a dispersion liquid when dispersed in various nonaqueous liquids, thereby forming a stable dispersion liquid and having excellent heat resistance. . Further, an object of the present invention is to provide a solid particle dispersion having the above characteristics, a resin composition containing solid particles, and surface-treated solid particles.

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.

The above dispersant of the present invention is preferably: relative to polyethylene acetal - 100 parts by mass of the polyester graft copolymer contains 1 to 50 parts by mass of a polyvinyl acetate-polyester graft copolymer and/or a polyvinyl alcohol-polyester graft copolymer.

The solid particle dispersion of the present invention is obtained by dispersing solid particles in a non-aqueous liquid by the above-described 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 resin composition containing the above solid particles can be used, for example, as a coating composition or an ink composition.

The surface-treated solid particles of the present invention are treated by the above-described dispersant of the present invention.

1. Preparation of dispersing agent

The dispersing agent of the present invention comprises a polyvinyl acetal-polyester graft copolymer as a main component, and one of a polyvinyl acetate-polyester graft copolymer and a polyvinyl alcohol-polyester graft copolymer. Or both.

Polyvinyl acetal is obtained by acetalizing polyvinyl alcohol with an aldehyde. Examples of the aldehyde to be used include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, hexanal, heptaldehyde, octanal, furfural, isodecanoaldehyde, furfural, benzaldehyde, and the like. mixture. The average molecular weight of the polyvinyl acetal is preferably from 100 to 100,000, more preferably from 1,000 to 50,000. When the weight average molecular weight is less than 100, a decrease in performance such as a decrease in dispersibility is observed, and when it exceeds 100,000, the viscosity is increased when used as a dispersant, and it is difficult to handle.

The weight average molecular weight of the above polyvinyl acetate is preferably from 100 to 100,000, more preferably from 1,000 to 50,000. If the weight average molecular weight is not full At 100, a decrease in performance such as a decrease in dispersibility was observed, and when it was more than 100,000, the viscosity was increased when used as a dispersant, and it was difficult to handle.

The polyvinyl alcohol is obtained by alkalizing polyvinyl acetate, and the degree of alkalinity is not limited, and any degree of alkalinity of more than 0% to 100% can be used.

The polyester used in the present invention can be obtained by a ring-opening polymerization reaction of a lactone compound, a condensation polymerization reaction of a polyvalent carboxylic acid with a polyvalent alcohol, and a condensation polymerization reaction of a hydroxycarboxylic acid.

The above lactone compound may, for example, be ε-caprolactone, δ-caprolactone, β-methyl-δ-valerolactone, β-propiolactone, γ-butyrolactone, 2-methylhexene. As the ester, 4-methylcaprolactone, azlactone or the like, a mixture of two or more of these may be used.

The ring-opening polymerization of the above lactone compound can be carried out by a conventional method. For example, a compound having an alcohol or an amine can be used as a starter to ring-open the polymerization of the lactone compound.

The alcohol used for the above initiator may, for example, be methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, foreign alcohol, 1 -hexanol, cyclohexanol, 4-methylpentanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isodecyl alcohol, 1-nonanol, 1-undecanol, 1-tetradecanol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, oleyl alcohol, 2-octyl decyl alcohol, 2-octylundecyl alcohol, 2-hexyl decyl alcohol An aromatic monoalcohol such as octaethylene glycol, an aromatic monoalcohol such as benzyl alcohol or phenethyl alcohol, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, etc. Acrylate, 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, propane Alcohol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethyl 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, triethyl 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 monohexyl 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, tetraethyl Glycol mono-2-ethylhexyl 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 , alkyl diol monoalkyl ether such as tetraethylene glycol monomethyl ether, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butane Alcohol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethyl Glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, 2,2-bis-(4-hydroxyethoxyphenyl) a divalent alcohol such as propane, 1,4-bis(2-hydroxyethyl)benzene, 1,6-bis(2-hydroxyethoxy)hexane or the like, butanediol, neopentyl glycol, 1,4 - hexanediol glycerol, trimethylolethane, trimethylolpropane, ginseng (2-hydroxyethyl)isocyanate, pentaerythritol, ditrihydroxypropane, dipentaerythritol, A polyvalent alcohol such as mannitol or sorbitol.

As the amine used for the above initiator, for example, methylamine and dimethyl are mentioned. Amine, ethylamine, diethylamine, triethylamine, methylethylamine, propylamine, dipropylamine, cyclohexylamine, aniline, benzylamine, pyrrolidine, morpholine, methylenediamine, ethylidene diamine, tetra Ethyldiamine, hexaethylidene diamine, propyldiamine, diphenyldiaminomethane, p-phenylenediamine, hexamethylenediamine, isophoronediamine, ethanolamine, diethylene Triamine, diethylaminopropylamine, piperazine, tri-ethyltetramine, and the like.

The ring-opening polymerization of the lactone compound is carried out by adding a starter and a catalyst to the lactone compound by heating. The reaction temperature is in the range of 100 ° C to 220 ° C, preferably 140 ° C to 210 ° C. As the catalyst, tin compounds such as an organic tin compound such as tin octylate, dibutyltin laurate, monobutyl hydroxybutyl tin oxide, dioctyltin neodecanoate, stannous oxide or stannous chloride can be used. A titanium compound such as tetrabutyl titanate, tetraethyl titanate or tetrapropyl titanate, and other conventional esterification catalysts. The amount of the catalyst used is preferably from 0.1 ppm to 1000 ppm, more preferably from 1 ppm to 100 ppm. Further, in order to prevent coloring, it is preferred to carry out the reaction in an inert gas atmosphere such as nitrogen.

As the ring-opening polymer of the lactone compound, a commercially available polylactone polyol can be used. For example, it is a "Placcel" series manufactured by Daicel Chemical Industry Co., Ltd.

The polyester used in the present invention can be obtained by a condensation polymerization reaction of a polyvalent carboxylic acid and a polyvalent alcohol.

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, and cis. Butylene diacid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, pyromellitic acid, and the like.

The above polyvalent alcohol may, for example, be ethylene glycol, 1,2-propanediol or 1,3-propane Alcohol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 1,10-anthracene Glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, 2,2-bis-(4-hydroxyethylphenyl)propane, 1,4-bis(2-hydroxyethyl)benzene, 1,6-bis(2-hydroxyethyl)benzene, butanediol, new Pentyl glycol, 1,4-hexanediol glycerol, trimethylolethane, trimethylolpropane, ginseng (2-hydroxyethyl)isocyanate, neopentyl alcohol, ditrihydroxymethyl Propane, dipentaerythritol, mannitol, sorbitol, and the like.

The condensation polymerization of the above polyvalent carboxylic acid with a polyvalent alcohol can be carried out by adding a catalyst and heating. The reaction temperature is preferably in the range of from 100 ° C to 220 ° C, more preferably from 140 ° C to 210 ° C. The catalyst is not limited to the following, and an organotin compound such as tin octylate, dibutyltin oxide, dibutyltin laurate, monobutylhydroxybutyltin oxide, dioctyltin neodecanoate, stannous oxide or stannous chloride can be used. A titanium compound such as a tin compound, tetrabutyl titanate, tetraethyl titanate or tetrapropyl titanate, or other conventional esterification catalyst. The amount of the catalyst used is preferably from 0.1 ppm to 1000 ppm, more preferably from 1 ppm to 100 ppm. Further, in order to prevent coloring, it is preferred to carry out the reaction in an inert gas atmosphere such as nitrogen.

The polyester used in the present invention can be obtained by a condensation polymerization reaction of a hydroxycarboxylic acid, and as the hydroxycarboxylic acid, an aliphatic, aromatic or unsaturated hydroxycarboxylic acid can be used. For example, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil, acid, 6-hydroxyvaleric acid, lactic acid, glycolic acid, hydroxyisophthalic acid, hydroxy-t-valeric acid, 4-hydroxyl Phthalic acid, salicylic acid, 11-oxyhexadecanoic acid, 2-oxydodecanoic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-di Hydroxymethyl valeric acid, 2,2-dimethylol valeric acid, frequency fruit acid, tartar As the acid, gluconic acid, 4,4-bis(hydroxyphenyl)butyric acid, glucuronic acid or 3-hydroxybutyric acid, a mixture of two or more of these may also be used.

The condensation polymerization of the above hydroxycarboxylic acid can be carried out by adding a catalyst and heating. The reaction temperature is preferably in the range of from 100 ° C to 220 ° C, more preferably from 140 ° C to 210 ° C. As the catalyst, tin such as an organic tin compound such as tin octylate, dibutyltin oxidate, dibutyltin laurate, monobutylhydroxybutyltin oxide or dioctyltin neodecanoate, stannous oxide or stannous chloride can be used. a compound; a titanium compound such as tetrabutyl titanate, tetraethyl titanate or tetrapropyl titanate; and other conventional esterification catalysts. The amount of the catalyst used is preferably from 0.1 ppm to 1000 ppm, more preferably from 1 ppm to 100 ppm. Further, in order to prevent coloring, it is preferred to carry out the reaction in an 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, a decrease in performance such as a decrease in dispersibility is observed, and when it exceeds 50,000, the viscosity is increased when used as a dispersant, and it is difficult to handle.

The method for producing the graft copolymer used in the present invention is not particularly limited, and examples thereof include a method in which a polyester acetal, a polyvinyl acetate, and a polyvinyl alcohol are directly reacted with a polyester monomer; and a polyvinyl acetal, a method for dehydrating polymerization of a carboxylic acid having a polyvinyl acetate and a polyvinyl alcohol and a carboxylic acid; and a polyester having a hydroxy or ester group of a polyvinyl acetal, a polyvinyl acetate, and a polyvinyl alcohol; The method of transesterification reaction, and the like.

Further, the polyvinyl acetal-polyester graft copolymer, the polyvinyl acetate-polyester copolymer, and/or the polyvinyl alcohol-polyester copolymer may be separately produced, and these may be mixed as a dispersing agent, or may be used. Polyvinyl acetal with polyvinyl acetate and / Or polyvinyl alcohol is pre-mixed and then bonded to the polyester chain.

The hydroxy or ester group of the polyvinyl acetal or polyvinyl acetate or polyvinyl alcohol preferably has a graft bond with the polyester in the range of from 1 to 95 mol%. More preferably, 2 to 50 mole % of the hydroxyl or ester group forms a graft bond with the polyester. In either case, unreacted polyester may remain.

The amount of the polyvinyl acetate-polyester graft copolymer and/or the polyvinyl alcohol-polyester graft copolymer relative to the polyvinyl acetal-polyester graft copolymer is preferably reduced relative to the polyethylene. The total amount of the aldehyde-polyester graft copolymer is 100 parts by mass, and the total amount of the polyvinyl acetate-polyester graft copolymer and/or the polyvinyl alcohol-polyester graft copolymer is 1 to 50 parts by mass.

2. Use of dispersant

The above-mentioned dispersant of the present invention is effective for dispersion of various inorganic and organic solid examples. Specifically, it is generally used in the fields of paints, printing inks, toners for photocopying, plastics, pigment printing agents, inks for inkjet recording, inks for thermal transfer recording, photoresists for color filters, inks for note-taking tools, and the like. In the dispersion medium to be used, the solid particles can be dispersed at a high concentration and in a stable manner.

Particularly in the present invention, a polyvinyl acetate-polyester graft copolymer and/or a polyvinyl alcohol-polyester graft copolymer is mixed as a dispersing agent for a polyvinyl acetal-polyester graft copolymer. Compared with the case where a polyvinyl acetal-polyester graft copolymer is used alone as a dispersing agent, the viscosity of the dispersion can be remarkably lowered. By reducing the viscosity of the dispersion, the workability at the time of coating can be improved, and the use of the dispersant is more extensive.

The solid particles to be dispersed by the dispersant of the present invention are not particularly limited, and examples of the inorganic particles include kaolinite, aluminum silicate, clay, and talc. Mica, calcium citrate, bentonite, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, dolomite, calcium sulfate, barium sulfate, aluminum sulfate, zirconium dioxide, magnesium oxide, aluminum oxide, antimony trioxide, Titanium dioxide, diatomaceous earth, iron oxide, zinc oxide, aluminum hydroxide, iron hydroxide, tantalum carbide, tantalum nitride, boron nitride, barium titanate, carbon black, graphite, iron powder, silver powder, aluminum powder, copper powder , nickel powder, gold powder, etc. Examples of the organic particles include an azo-based, a diazo-based, a condensed azo-based, a thioindole-based, an anthraquinone-based, a quinophthalone-based, an anthraquinone-based, a benzimidazole-based, an anthraquinone-based, and a phthalocyanine-based. An organic pigment such as an anthracene pyridine or a dioxazine, a starch, a polyethylene resin, an amine ester resin, a melamine resin, a polystyrene resin, a polylactic acid, a solid paraffin or the like.

Examples of the dispersion medium include toluene, xylene, an aromatic hydrocarbon solvent, a hydrocarbon solvent such as n-hexane, cyclohexane or n-heptane, and a halogenated hydrocarbon solvent such as dichloromethane, chloroform or dichloroethane. An ether solvent such as dioxane, tetrahydrofuran, dibutyl ether, diethyl ether or diethylene glycol dimethyl ether; a ketone solvent such as methyl isobutyl ketone, cyclohexanone or isophorone; ethyl acetate , an ester solvent such as butyl acetate, ethylene glycol monoethyl ether, propylene glycol monomethyl ether ethyl ester, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, Alcohol solvent such as pentanol, n-hexanol, n-heptanol, 2-ethylhexyl alcohol, lauryl alcohol, stearyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, p-tert-butylbenzyl alcohol, etc. a monoether solvent of an alkyl diol such as alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or propylene glycol monobutyl ether, and other examples such as dimethyl hydrazine These may be used singly or in combination of two or more kinds thereof, such as an amine or a melamine-based solvent such as dimethylformamide.

The amount of the dispersant used in the present invention is also based on the object to be dispersed. The type of the solid particles is not particularly limited, and is preferably from 1 to 300% by mass based on the solid particles.

The dispersion method is not particularly limited, and it can be dispersed by a conventional method using a pulverizer such as a ball mill, a bead mill, or a sand mill.

In addition, a resin composition containing solid particles and a resin, and further containing a solvent or the like as needed may be prepared by using the dispersant of the present invention. Such a resin composition containing solid particles can be used, for example, as a coating composition or an ink composition. Examples of the resin contained in the resin composition containing solid particles include an acrylic resin, an amine ester resin, an epoxy resin, a polyester resin, an alkyd resin, a oxime resin, a fluororesin, a melamine resin, a benzoguanamine resin, and the like. A wide range of resins such as urea formaldehyde resin, polyamide resin, phenol resin, vinyl chloride, polyethylene resin, and polyvinyl acetal resin are not limited thereto.

As a method for producing a resin composition containing solid particles, the dispersant of the present invention may be prepared by directly mixing a solid particle, a resin, a solvent, another additive, or the like to prepare a resin composition containing solid particles, or may be a dispersant, After solid particles and a dispersion medium are kneaded to prepare a solid particle dispersion, a resin is added thereto as a resin composition containing solid particles.

Further, the dispersant of the present invention may be obtained by dispersing and dispersing a solid particle, a monomer or an oligomer having a reactive group, and then polymerizing these to prepare a resin composition containing solid particles.

Further, the surface treatment of the solid particles can be carried out by the dispersant of the present invention. As a treatment method, a Henschel mixer, a ball mill, an Atomizer colloidal mill, a Banbury mixer can be used. A dry method in which a dispersing agent is added while stirring a solid particle, and a dry method in which it is mixed, a solvent is removed, and a solvent is removed. By performing the surface treatment by using the dispersing agent of the present invention as described above, the dispersibility of the solid particles can be improved and aggregation can be prevented.

According to the present invention, when solid particles are dispersed in various nonaqueous liquids, a dispersing agent can be obtained which can effectively prevent aggregation of solid particles in the dispersion to form a stable dispersion. The dispersant is excellent in dispersibility, fluidity, and storage stability, and is excellent in compatibility with a dispersion medium. Moreover, since it does not have an amine skeleton, the effect of being excellent in heat resistance is deliberately obtained.

Further, by using a polyvinyl acetate-polyester graft copolymer and/or a polyvinyl alcohol-polyester graft copolymer in combination with the case where a polyvinyl acetal-polyester graft copolymer is used alone, Reduce the viscosity of the dispersion. By reducing the viscosity of the dispersion, the effect of improving the workability at the time of coating can be obtained.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not particularly limited to the examples. In the following description, "parts" means "parts by mass" and "%" means "mass%" unless otherwise specified.

[Preparation of Dispersant] [Production Example 1] (Polyvinyl acetal-polyester graft copolymer)

In a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube, 50.0 parts of 12-hydroxystearic acid, 800.0 parts of ε-caprolactone, and 0.1 part of tetrabutyl titanate were placed, and the temperature was raised for 4 hours under a nitrogen atmosphere. Heat to 160 ° C and heat at 160 ° C until the residual ε-caprolactone is below 1%. The reaction product was a yellow solid, the weight average molecular weight was 7,100, and the acid value was 7.9 mg KOH/g.

A polyethylene acetal (product name "S-LEC BX-L", manufactured by Sekisui Chemical Co., Ltd., having an average molecular weight of about 20,000 and a hydroxyl group of 37 ± was placed in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube. 3 mol%, ethyl sulfonate 3 mol% or less, acetalization degree about 61 mol%) 4.1 parts, 129.0 parts of the above reaction product polyester, 0.05 parts of dioctyltin neodecanoate, in a nitrogen atmosphere The temperature was raised to 200 ° C and heated for 6 hours. The reaction product was a yellow viscous liquid having a weight average molecular weight of 95,000 and an acid value of 3.3 mgKOH/g.

[Production Example 2] (polyvinyl acetate-polyester graft copolymer)

In a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube, 100.0 parts of 2,2-dimethylolpropionic acid, 850.0 parts of ε-caprolactone, and 0.05 parts of tetrabutyl titanate were placed in a nitrogen atmosphere. The temperature was raised for 4 hours to 160 ° C and heated at 160 ° C until the residual ε-caprolactone was below 1%. The reaction product was a yellow solid, and had a weight average molecular weight of 2,000 and an acid value of 29.5 mgKOH/g.

In a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube, 12.3 parts of polyvinyl acetate (manufactured by Electric Chemical Industry Co., Ltd., trade name "DENKA SAKNOHOL SN-04T", polymerization degree: 500 to 700) was placed. 64.2 parts of the polyester of the above reaction product and 0.05 parts of dioctyltin neodecanoate were heated to 200 ° C in a nitrogen atmosphere, and heated for 6 hours. The reaction product was a yellow viscous liquid having a weight average molecular weight of 65,000 and an acid value of 8.8 mgKOH/g.

[Production Example 3] (polyvinyl alcohol-polyester graft copolymer)

In a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube, 10.0 parts of methanol, 800.0 parts of ε-caprolactone, and 0.1 part of tetrabutyl titanate were placed, and the temperature was raised in a nitrogen atmosphere for 4 hours to 160 ° C, and Heating at 160 ° C until the residue The ε-caprolactone is kept below 1%. The reaction product was a yellow solid, and the weight average molecular weight was 3,100.

In a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name "KURARAY POVAL PVA-102", alkalinity: 98.0 to 99.0%, polymerization degree: 200) was placed. 49.7 parts, 50.3 parts of the polyester of the above reaction product, and 0.05 part of dioctyltin neodecanoate were heated to 200 ° C in a nitrogen atmosphere, and heated for 6 hours. The reaction product was a yellow viscous liquid having a weight average molecular weight of 85,000.

[Production Example 4] (a mixture of a polyvinyl acetal-polyester graft copolymer and a polyvinyl acetate-polyester graft copolymer)

In a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube, polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., trade name "S-LEC BL-1", having an average molecular weight of about 19,000, hydroxyl group was placed. About 36% by mole, acetonitrile 3 mole % or less, acetalization degree 63 ± 3 mole %) 27.5 parts, polyvinyl acetate (manufactured by Electric Chemical Industry Co., Ltd., trade name "DENKA SAKNOHOL SN- 04T", polymerization degree 500~700) 3.1 parts, polycaprolactone (Daicel Chemical Industry Co., Ltd., trade name "Placcel H1P", molecular weight 10,000) 50.0 parts, dioctyl neodecanoate 0.05 parts, in nitrogen The temperature was raised to 200 ° C in the environment and heated for 6 hours. The reaction product was a yellow viscous liquid having a weight average molecular weight of 92,500.

[Production Example 5] (mixture of polyvinyl acetal-polyester graft copolymer and polyvinyl alcohol-polyester graft copolymer)

49.7 parts of polyvinyl butyral (made by Sekisui Chemical Industry Co., Ltd.) was placed in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube. The trade name "S-LEC BL-1" has an average molecular weight of about 19,000, a hydroxyl group of about 36 mol%, an acetamyl group of 3 mol% or less, a degree of butyralization of 63 ± 3 mol%, and a polyvinyl alcohol (Kuraray). Co., Ltd., trade name "KURARAY POVAL PVA-102", alkalinity 98.0~99.0%, polymerization degree 200) 6.1 parts, ε-caprolactone 114.0 parts, dioctyl neodecanoate 0.2 parts, in nitrogen Under the environment, heating was carried out at 180 ° C until the residual ε-caprolactone was below 1%. The reaction product was a pale yellow viscous liquid having a weight average molecular weight of 218,000.

[Manufacturing Example 6] (mixture of polyvinyl acetal-polyester graft copolymer and polyvinyl acetate-polyester graft copolymer)

In a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube, polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., trade name "S-LEC BL-1", having an average molecular weight of about 19,000, hydroxyl group was placed. About 36% by mole, acetonitrile 3 mole % or less, butyralization degree 63 ± 3 mole %) 24.4 parts, polyvinyl acetate (manufactured by Electric Chemical Industry Co., Ltd., trade name "DENKA SAKNOHOL SN- 04T", polymerization degree: 500 to 700) 6.2 parts, polycaprolactone (manufactured by Daicel Chemical Industry Co., Ltd., trade name "Placcel H1P", molecular weight 10,000) 49.0 parts, polyester polyol (Kuraray Co., Ltd., product "KURARAY Polyol P-6010", a polyester polyol of adipic acid and 3-methyl-1,5-pentanediol, an average molecular weight of about 6,000), 1.0 part, and 0.1 part of dioctyltin neodecanoate. The temperature was raised to 200 ° C under a nitrogen atmosphere, and heating was carried out for 6 hours. The reaction product was a yellow viscous liquid having a weight average molecular weight of 101,100.

[Comparative Manufacturing Example 1]

In a reaction vessel equipped with a nitrogen inlet pipe, a thermometer, and a reflux pipe, 8.1 parts of polyethyleneimine (trade name "Lupasol PR8515", manufactured by BASF Corporation, molecular weight 2000), 91.9 parts of polyester of Production Example 1, and 0.05 part of tetrabutyl titanate were added, and the temperature was raised to 200 ° C in a nitrogen atmosphere. Heating was carried out for 6 hours. The reaction product was a brown solid having an amine value of 45.5 mg KOH / g and an acid value of 1.1 mg KOH / g.

[Production Example 7] (Manufacture of surface-treated pigment)

5 parts of Pigment Blue 15:6, 5.0 parts of the graft copolymer of Production Example 6, and 250 parts of ethyl acetate were mixed and stirred for one hour, and then ethyl acetate was pressure-filtered to obtain a surface-treated pigment.

[Preparation and heat resistance test of dispersant]

The heat resistance evaluation was performed by the following method with respect to the dispersing agent obtained by the above-mentioned manufacturing example and comparative manufacturing example, and the following comparative products 1 and 2. The results are shown in Table 1.

Comparative product 1: Ajinomoto Fine-Techno Co., Ltd., trade name "Ajisper PB-822", polymer pigment dispersant, amine price 17 mgKOH/g, acid value 14 mgKOH/g. Comparative product 2: manufactured by Sekisui Chemical Co., Ltd., trade name "S-LEC BL-1", polyvinyl butyral, average molecular weight of about 19,000, hydroxyl group of about 36 mol%, ethyl sulfonate of 3 mol% or less The degree of acetalization is 63±3 mol%.

Color difference: 0.5 mg of a dispersing agent was dissolved in 20 mL of dichloromethane, and mixed with 10 g of silicone rubber, and dried at room temperature. The obtained tantalum gel was subjected to heat treatment at 200 ° C for one hour, and the color difference before and after the treatment was measured. Heat resistance: It is determined by the following criteria.

○: Color difference (ΔE) 0 or more and 5 or less

△: The color difference (ΔE) is greater than 5 and less than 10

×: color difference (ΔE) 10 or more

[Preparation and evaluation of solid particle dispersions]

<Dispersibility test>

The polyvinyl acetal-polyester graft copolymer obtained by the above production example and the dispersing agent of the comparative object were dissolved in the dispersion medium shown in Table 2, and the solid particles shown in Table 2 were added, respectively, 0.3 mm. The zirconia beads were stirred with a paint shaker for 4 hours. The dispersibility immediately after the stop of the dispersion operation was visually observed and evaluated by the following criteria. In Example 16, the dispersion medium and the above-mentioned zirconia beads were added to the surface-treated pigment obtained in Production Example 7, and the same operation was carried out except that the dispersant was not further used. The results are shown in Table 2. Dispersibility: Determined by the following criteria.

◎: All the powder was dispersed in the liquid, and no precipitate was formed at the bottom.

○: Almost all of the powder was dispersed in the liquid, but a slight precipitate was formed at the bottom.

△: About half of the powder was precipitated in the liquid.

×: Almost all the powder was precipitated at the bottom.

<viscosity>

The viscosity of the dispersion obtained by the above dispersion test was measured by a type B viscosity agent. The results are shown in Table 2.

<Coating film state test>

An acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name "Acrypet VH") or butyral resin (product of Sekisui Chemical Industry Co., Ltd., trade name "S-LEC BH-" was added to 10.0 parts of the dispersion after the dispersion test. 3") 0.4 parts, stirred to dissolve. The obtained mixture was spin-coated on a glass substrate to have an average film thickness of 1.8 μm, and then heated in an oven at 120 ° C for 1 hour. The obtained coating film was visually observed and evaluated by the following criteria. The results are shown in Table 2.

○: The obtained coating film was transparent.

△: A fogging was observed in the obtained coating film.

×: The particles are aggregated and have no transparency.

<Test of heat resistance of coating film>

The color difference of the test plate prepared by the film state test and the test plate after the test plate was heated at 230 ° C for 1 hour was measured and evaluated by the following criteria. The results are shown in Table 2.

○: Color difference (ΔE) 0 or more and 1 or less

△: The color difference (ΔE) is greater than 1 and less than 2.5

×: color difference (ΔE) of 2.5 or more

【Table 2】

[Preparation and Evaluation of Photosensitive Colored Resin Composition]

40.0 parts of methacrylic acid/benzyl methacrylate copolymer (25/75 mass ratio, weight average molecular weight about 30,000), Pigment Blue 15: 6 23.0 parts, graft copolymer of Production Example 6 7.0 parts, dipentaerythritol 10.0 parts of hexaacrylate, 3.0 parts of 2,4-bis(trichloromethyl)-6-(2-ethoxystyryl)-s-triazine, 200 parts of PGMEA mixed, and 0.3 mm of zirconia added The beads were dispersed by a pigment mixer to obtain a photosensitive colored resin composition.

The photosensitive colored resin composition was spin-coated on a glass substrate, and then prebaked in a dust-free oven at 70 ° C for 20 minutes to prepare a dried coating film. Next, the substrate was cooled at room temperature, and then subjected to ultraviolet light exposure using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed with a 0.04% potassium hydroxide aqueous solution, washed with ion-exchanged water, and air-dried. Thereafter, post-baking was carried out at 230 ° C for 30 minutes in a dust-free oven. The dried coating film was an average and smooth coating film within ±0.5 μm, and the light transmittance (average of 380 to 780 nm) was 98%.

[Possibility of industrial use]

The dispersant of the present invention is used in paints, printing inks, toners for photocopying, plastics, pigment printing agents, inks for inkjet recording, inks for thermal transfer recording, photoresists for color filters, inks for note instruments, and the like. Among them, it is extremely effective to disperse solid particles in a non-aqueous liquid.

The present application is based on Japanese Patent Application No. 2012-050648, the entire contents of which is incorporated herein by reference.

Claims (6)

A dispersing agent comprising a polyvinyl acetal-polyester graft copolymer and comprising a polyvinyl acetate-polyester graft copolymer and/or a polyvinyl alcohol-polyester graft copolymer. The dispersing agent according to claim 1, wherein the polyvinyl acetate-polyester graft copolymer and/or polyvinyl alcohol-poly is contained in an amount of 100 parts by mass based on 100 parts by mass of the polyethylene acetal-polyester graft copolymer. The ester graft copolymer is 1 to 50 parts by mass. A solid particle dispersion obtained by dispersing a solid particle in a non-aqueous liquid by the dispersing agent according to claim 1 or 2. A resin composition containing solid particles, which comprises the dispersant, resin and solid particles of claim 1 or 2. The resin composition containing solid particles according to claim 4, which is a coating composition or an ink composition. A surface-treated solid particle which is treated with a dispersing agent as claimed in claim 1 or 2.