JPH0523307B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel flushing method for pigments, and more specifically, the present invention relates to a novel flushing method for pigments, and more specifically, the present invention relates to a method for flushing pigments, and more specifically, a phosphoric acid ester compound containing a hydrocarbon chain having an ester group, a carboxyl group, or a salt group thereof is used as a flushing aid. The purpose of the present invention is to provide a pigment composition useful as a coloring agent for paints, printing inks, synthetic resins, etc. (Prior Art) Conventionally, in the production of paints and printing inks, dispersants or For example, the phospholipid lecithin has been used as a flushing aid. (Problems to be solved by the invention) However, since lecithin is a natural phospholipid, it is susceptible to oxidation and rancidity, and there is a risk of deterioration and putrefaction.However, lecithin is a dispersing agent that has stable and excellent properties. There is also a need for a compound that can be used as a flushing aid. In view of the above-mentioned deficiencies in pigment dispersants or flushing aids, the present inventors have conducted various studies on compounds that have an affinity for various vehicles and varnishes, and also have an affinity for pigments. , discovered that a phosphoric acid ester compound obtained by reacting a hydrocarbon having an ester group or a carboxyl group and at the same time a hydroxyl group with phosphoric acid exhibits excellent properties and effects as a flushing aid,
This completes the present invention. (Means for Solving the Problems) That is, the present invention involves kneading a mixture containing an aqueous slurry of pigment, a flushing aid, and optionally a hydrophobic organic solvent to transfer the pigment to an organic phase. In the flushing method for pigments, the flushing aid is a phosphoric acid ester compound represented by the following general formula or an ammonium salt thereof, primary to
This is a method for flushing a pigment characterized by using a tertiary organic amine salt, an organic quaternary ammonium salt, or a mono- to trivalent metal salt. [However, R ₁ is a hydrocarbon group having 4 to 30 carbon atoms that is not a polymer. _R2 is _R3OOC - _R1- , a hydrogen atom, or a hydrocarbon group having 1 to 30 carbon atoms. R ₃ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (Preferred Embodiment) To explain the present invention in detail, the flushing aid used in the present invention and which mainly characterizes the present invention is a specific phosphoric acid ester compound as defined above. The phosphoric acid ester compound used in the flushing method of the present invention is obtained by reacting 1 mole of the phosphorylating agent with 1 mole or 2 moles of an alcohol component having an ester group or carboxyl group as an essential component according to a conventionally known method. obtained by As the phosphorylating agent, conventionally known phosphorus oxychloride, phosphorus pentoxide, phosphorus trichloride, phosphoric anhydride, acetyl phosphoric acid, etc. are used. Phosphorous oxychloride is the most preferred phosphorylating agent. Regarding reaction conditions, in the case of phosphorus oxychloride, the initial esterification reaction is intense, so it is preferable to carry out the reaction at a low temperature.To accelerate the reaction, it is also possible to reduce the pressure in the reactor to remove the generated hydrogen chloride. . It is also preferable to heat the reaction to complete the reaction. After the reaction is complete, remove unreacted chloride with hot water,
Wash with cold water and hydrolyze. In addition, when a halogenated phosphorus compound is used, it is also preferable to use a basic catalyst, for example, tertiary amines such as triethylamine, pyridine, 2,6-lutidine, 1,8-diazabicyclo(5 , 4, 0) Organic bases such as undecene-7, manifest or latent inorganic bases such as oxides, hydroxides, carbonates, and organic acid salts of alkali metals and alkaline earth metals can be used, and organic bases such as undecene-7 can be used. Afterwards, it is preferable to remove halides, salts, bases, and other impurities by filtration, neutralization, washing with water, or the like. The alcohol component to be reacted is selected and used depending on the purpose of the product. The phosphoric acid ester compound used in the flushing method of the present invention can be prepared by directly reacting an alcohol component, etc. that matches the target compound with a phosphorylating agent, or by preliminarily preparing, for example, methyl ester of 12-hydroxystearic acid, etc. to synthesize a di- or monophosphoric acid ester with a terminal terminal such as a methyl ester, and then hydrolyze the methyl ester and transesterify it with other alcohols to form other phosphoric acid di- or monoester compounds. It can also be obtained by methods such as synthesis. The alcohol component used is a conventionally known aliphatic, alicyclic or aromatic carboxylic acid having a hydroxyl group or an ester thereof. As such alcohol components, for example, the following are used. (A) A hydroxycarboxylic acid containing a hydrocarbon chain having 1 to 30 carbon atoms, preferably a hydroxycarboxylic acid containing a hydrocarbon chain having 4 to 30 carbon atoms. For example, ricinoleic acid, ricinoleic acid, 12
-Hydroxystearic acid, castor oil fatty acid,
Hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid,
Examples include one or more hydroxycarboxylic acids such as ε-hydroxycaproic acid, p-hydroxyethyloxybenzoic acid, and 2-hydroxynaphthalene-6-carboxylic acid. (B) An esterified product of the carboxylic acid at the other end of the alcohol component described in (A) above. These are esters with aliphatic, alicyclic, or aromatic alcohols having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, and octyl of the above-mentioned hydroxycarboxylic acids. -, dodecyl-, hexadecyl-, octadecyl-, cyclohexyl-, benzyl-alcohol and other esters. The phosphoric acid ester compound used in the flushing method of the present invention includes, in addition to the above-mentioned phosphoric diester compound of the alcohol component, the reaction between the alcohol component and the phosphorylating agent is limited to a monoester, and other monoester components are conventionally known. It also includes an asymmetric phosphodiester compound esterified using an alcohol, and can be synthesized according to a conventionally known method for synthesizing an asymmetric phosphodiester compound. Conventionally known alcohol components are used as these alcohol components, such as alcohols having 1 to 30 carbon atoms,
For example, methyl alcohol, ethyl alcohol,
Propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, hexadecyl alcohol, octadecyl alcohol, tetracosyl alcohol, hexacosyl alcohol, octadecenyl alcohol, cyclohexyl alcohol, benzyl alcohol etc. In the phosphoric acid esterification reaction of the alcohol component, which is an essential component of the alcohol having a carboxyl group or ester group, used in the present invention, it is necessary to use an alcohol that is inert to these raw materials and products and It is also preferable to use an organic solvent that dissolves the raw materials and the like. For example, aliphatic saturated hydrocarbons such as octane, petroleum ether, ligroin, mineral spirits, kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated aliphatic hydrocarbons such as trichloroethane, tetrachloroethane, etc. - Solvents conventionally used in these reactions, such as chlorinated aromatic hydrocarbons such as dichlorobenzene and trichlorobenzene, can be used. The phosphoric acid di- or monoester compound used in the present invention naturally has an acidic radical, which includes hydrogen ions as acids, alkali metal salts such as sodium and potassium in the form of salts, magnesium, calcium, etc.
Salts of divalent or higher polyvalent metals such as strontium, barium, manganese, iron, cobalt, nickel, zinc, aluminum, tin; ammonium salts; methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl -, octadecyl-,
Oleyl, diethyl, dibutyl, distearyl, triethyl, tributyl, dimethyloctyl, dimethyldecyl, dimethyldodecyl, dimethyltetradecyl, dimethylhexadecyl, dimethyloctadecyl, dimethyloleyl, Lauryl monomethyl, trioctylamine, dimethylaniline; carbon number 1 such as ethylene diamine, propylene diamine, hexamethylene diamine, stearyl propylene diamine, etc.
~30 primary, secondary, and tertiary mono- and polyamine salts, quaternary ammonium salts such as octadecyltrimethylammonium, dioctadecyldimethylammonium, and ethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, Examples include alkanolamine salts such as diethylethanolamine, propanolamine, dipropanolamine, and alkanolamines obtained by adding ethylene oxide to the above-mentioned higher aliphatic amines, which can be used alone or in combination. Further, as the higher aliphatic amines and ammoniums, amines which are mixtures of amines having different carbon numbers or degrees of saturation derived from the natural oils and fats used as raw materials can also be used as they are. Depending on the balance with the hydrophobic group, among the above salts, alkali metal salts, ammonium salts, lower amine salts, lower alkanolamine salts, etc. exhibit hydrophilicity and are water-soluble to water-dispersible, and are used. In this case, it can be used in a water-soluble to aqueous dispersion. In addition, polyvalent metal salts of divalent or higher valence, higher amine salts, and the like are hydrophobic and lipophilic, and can be used alone or as a solvent solution in the flushing method of the present invention. Also, of course, after treating a base material such as a pigment in advance with an acid form or an aqueous solution or dispersion of the former, a polyvalent metal compound, a higher amine compound, etc. are reacted to form a hydrophobic compound or an oily compound of the latter. and can be used in the flushing method of the present invention. Next, the method for flushing pigments of the present invention will be explained in more detail. As the pigments used in the present invention, all conventionally known organic pigments, inorganic pigments, extender pigments, etc. can be used. For example, organic pigments include phthalocyanine, azo, condensed azo, anthraquinone, penolin/perylene, indigo/thioindigo, isoindolinone, azomethine azo, dioxazine, quinacridone, aniline black, and trifluoride. Inorganic pigments include titanium oxide, iron oxide, iron hydroxide, chromium oxide, spinel fired pigments, lead chromate, vermilion chromate, and navy blue. Examples of extender pigments include calcium carbonate, barium sulfate, silicon oxide, and aluminum hydroxide. In the present invention, these pigments can also be used in the form of an aqueous filter cake or an aqueous suspension. The phosphoric acid ester compound used in the flushing method of the present invention may be used alone or in some cases with a conventionally known suitable organic solvent, a fixing agent resin such as a vehicle for paint, a varnish for printing ink, a vehicle for a coding agent, etc. , thermoplastic resins, thermosetting resins, plasticizers, crosslinking agents, catalysts, etc. The pigment flushing method of the present invention involves flushing an aqueous pigment slurry and a phosphoric acid ester compound as a flushing aid alone or together with a hydrophobic solvent or the above-mentioned fixing agent resin in a kneader, flusher, etc. It can be easily and efficiently transferred from the aqueous phase to the oil phase medium phase. The amount of phosphoric acid ester compound used in the flushing method of the present invention is approximately 1 per 100 parts by weight of pigment.
~300 parts by weight, preferably about 3 to about 150 parts by weight. The pigment composition obtained by the flushing method of the present invention can be used as a coloring agent for various purposes such as paints, printing inks, colored coating agents, and resin colorants, as well as containing pigments in high concentrations. It can also be used as a high pigment dispersion. Paints include all paints that use conventionally known pigments, such as automotive paints, architectural paints, wood paints, vehicle and equipment paints, household paints, plastic paints, pre-coated metal paints, Examples include can paints, marine paints, anticorrosion paints, photo-curable paints, electron beam-curable paints, electrostatic powder paints, vinyl sol paints, and the like. The printing ink includes all conventionally known printing inks, such as letterpress ink, lithographic ink, gravure ink for intaglio, screen ink for stencil printing, newspaper ink, and flexo ink. While the pigment content in paints, printing inks, colored coating agents, etc. is approximately 0.1 to 20% by weight,
In the case of high pigment content dispersions, it is produced and used in the range of about 20 to 70% by weight, and in the case of easily dispersible pigments treated with a solvent and then dried, in the range of about 60 to 95% by weight. be done. As mentioned above, in the flushing method of the present invention, conventionally known materials are used in conjunction with each application, but hydrophobic organic solvents are used as the flushing medium, and these organic solvents include aliphatic Hydrocarbons, alicyclics, aromatic hydrocarbons, halogenated hydrocarbons, esters, ketones, glycol ethers, hydrophobic alcohols, etc. are used, and are not particularly limited. Furthermore, as the paint vehicle, printing ink varnish, coating agent vehicle, etc., conventionally known oil-based vehicle materials can be used depending on the purpose. For example, alkyd resins with long oil length, medium oil length, and short oil length, modified alkyd resins such as phenol-modified and styrenated alkyds, amino alkyd resins, oil-free alkyd resins, acrylic resins for baking, acrylic lacquer resins, and acrylic polyol resins. , polyester resin, epoxy resin, butylated melamine resin, methylated melamine resin, urea-melamine resin, phenolic resin, rosin-modified phenolic resin, rosin-modified maleic acid resin, phenol-modified maleic acid resin, polyurethane resin, styrene resin, styrene acrylic Modified resins such as resins, styrene-diene copolymers, vinyl chloride copolymers, vinyl acetate resins, vinyl acetate copolymers, ethylene-vinyl acetate resins, butyral resins, petroleum resins, rosin esters, maleated rosin esters, etc. , drying oil, boiling oil, etc. Thermoplastic resins include polyvinyl chloride resin,
Styrene resin, acrylonitrile-styrene resin, acrylic resin, methacryl-styrene resin,
Examples include polyester resins. Examples of the plasticizer include phthalate ester, adipate ester, sebacate ester, polyester plasticizer, and epoxidized water soybean oil. Further, if necessary, conventionally known pigment dispersants or flushing aids may be added and used in combination without hindering the achievement of the object of the present invention. Examples include higher aliphatic monoamines, higher aliphatic diamines, acetates and higher aliphatic salts thereof. (Functions/Effects) The phosphoric acid ester compound used in the flushing method of the present invention is used in the field of coloring materials such as pigments, paints, printing inks, and plastic colorants to prevent oxidation and oxidation as seen in the natural phospholipid lecithin described above. It has excellent effects on surface modification of pigments with excellent stability and redispersion into media without the risk of deterioration or decay due to rancidity. The phosphoric acid ester compound used in the flushing method of the present invention is adsorbed onto the surface of the pigment due to the charge-absorbing property of the phosphoric acid ester bond or ester bond, the hydrophilic property of the hydrocarbon chain, etc., and is absorbed into the medium. It improves wettability, improves dispersibility and fluidity in a medium as a dispersant, makes the surface of a pigment lipophilic or hydrophobic, and enables easy and efficient flushing. (Reference Examples/Examples) Next, the present invention will be described in more detail with reference to Reference Examples (manufacturing examples of phosphoric acid di- or monoester compounds) and Examples. In the text, parts or percentages are based on weight unless otherwise specified. Reference Example 1 A four-necked glass reactor equipped with a stirrer, a thermometer, a dropping funnel, and a backflow condenser, and a water bath were prepared. A glass tube for removing generated hydrochloric acid gas was attached to the backflow condenser, which was connected to a safety bottle and a hydrochloric acid gas absorption bottle, and further connected to a mercury pressure gauge and a vacuum pump. Thirty parts of phosphorus oxychloride was charged to the reactor. Separately, mixed ester of 12-hydroxystearic acid with dodecyl alcohol and tridecyl alcohol (gram equivalent calculated from hydroxyl value is 505)
98.8 parts of the solution and 98.8 parts of benzene were mixed and dissolved, charged into a dropping funnel, and loaded into a reactor. While the reactor was externally cooled with ice and water, the benzene solution of the alkyl ester of 12-hydroxystearic acid was heated at 5 to 10°C, especially at a temperature of 10°C.
Drop while being careful not to let it rise above the level. After the addition is complete, stir at 10°C for 1 hour, gradually reduce the pressure inside the reactor while increasing the reaction temperature, and absorb the hydrochloric acid gas produced by the reaction into the aqueous sodium hydroxide solution in the absorption bottle. It takes about 5 hours to bring the temperature to about 40°C and the degree of vacuum to 100 mmHg, and then cool it down after the generation of hydrochloric acid gas is no longer observed. In this state, phosphoric acid (alkyl ester of 12-hydroxystearic acid) monoester dichloride is generated. Next, 98.8 parts of the above alkyl ester of 12-hydroxystearic acid, 98.8 parts of benzene, and 19.8 parts of triethylamine were mixed and dissolved, charged into a dropping funnel, and reacted dropwise at 10 to 20°C over 60 minutes, and reacted for 2 hours. The mixture was stirred and heated to 40°C over a further 2 hours, stirred for 2 hours, and cooled. In the above, the equivalent ratio of 12-hydroxystearic acid alkyl ester, phosphorus oxychloride and triethylamine is 2:3:1. Next, the reaction product was washed with water, diluted sodium hydroxide solution, diluted hydrochloric acid acidified water, and water in order to dechlorinate and remove phosphoric acid ester chloride or to remove triethylamine hydrochloride. After drying the washed benzene phase with sodium sulfate, benzene was distilled off under reduced pressure to obtain a brown liquid reaction product. According to infrared absorption spectrum and gel permeation chromatography analysis charts, the above reaction product is mainly composed of a phosphoric diester compound of alkyl ester of 12-hydroxystearic acid (flushing aid 1). This was confirmed. The average molecular weight of the main components was approximately 900-1000. Reference Examples 2 to 12 Various phosphoric ester compounds were obtained in the same manner as in Reference Example 1, except that the materials listed in Table 1 below were used in place of the materials in Reference Example 1. Reference Example 13 30 parts of phosphorus oxychloride was charged into the four-necked glass reactor used in Reference Example 1, which was equipped with a stirrer, a thermometer, a dropping funnel, a backflow condenser, a pressure reduction system, and a hydrochloric acid gas absorption system. Separately a mixture of dodecyl and tridecyl esters of 12-hydroxystearic acid (gram equivalent weight 505)
98.8 parts were mixed and dissolved in 98.8 parts of benzene, charged into a dropping funnel, and reacted in the same manner as in Reference Example 1.
Phosphoric acid (alkyl ester of 12-hydroxystearic acid) monoester dichlorad is formed, followed by 68.6 parts of 12-hydroxystearic acid methyl ester (gram equivalent weight 351) and 68.6 parts of benzene.
1 part and 19.8 parts of triethylamine were mixed and dissolved, and the mixture was reacted in the same manner as in Reference Example 1. In the above, the equivalent ratio of the mixture of dodecyl and tridecyl esters of 12-hydroxystearic acid, methyl 12-hydroxystearate, phosphorus oxychloride and triethylamine is 1:1:3:1.
It is. The cooled reaction product liquid was treated in the same manner as in Reference Example 1,
A brown liquid reaction product was obtained by dechlorination, washing, purification, drying, concentration and solvent removal. Analyzed in the same manner as in Reference Example 1, it was found that the main components are phosphoric diesters of 12-hydroxystearic acid alkyl esters and methyl esters (flushing aid 13), and the average molecular weight of the main components is approximately 800 to 850. It was confirmed that. Reference Examples 14-20 Various phosphoric ester compounds were obtained in the same manner as in Reference Example 13, except that the materials listed in Table 2 below were used in place of the materials in Reference Example 13. Example 1 Copper phthalocyanine blue pigment (CI Pigment Blue 15-3) aqueous filter cake (pigment content 42
%) 238 copies were placed in a flasher. Separately,
The phosphate group of Flushing Aid 1 obtained in Reference Example 1 was neutralized with approximately the same amount of rosin amine to prepare a salt. 60 parts of this rosin amine salt was dissolved in 40 parts of petroleum-based ink solvent and added, kneaded and flushed according to a conventional method. The water content of the cake was released much more easily than conventional flushing aids, and the copper phthalocyanine blue pigment migrated into the oil-based flushing aid. Furthermore, water was completely removed to obtain a flushed color containing copper phthalocyanine blue pigment.
An offset lithography ink was prepared using the flat color containing the copper phthalocyanine blue pigment obtained above. Flatusid color of the copper phthalocyanine blue pigment obtained above (50% purity) 38.0 parts Mixed varnish for offset lithographic ink 60.0 parts 5% cobalt dryer 0.2 parts 8% manganese dryer 1.0 parts Ink solvent 0.8 parts Total 100 parts In the above The blended varnish for offset lithographic ink has the following composition. Rosin-modified phenolic resin 35 parts Drying oil 25 parts Drying oil-modified isophthalic acid alkyd 10 parts Ink solvent 29.5 parts Aluminum chelate 0.5 parts Total 100 parts The copper phthalocyanine blue pigment ink obtained above was used as an indigo ink and printed using an offset printing machine. It was printed on paper and a clear blue print was obtained. Also, instead of the aqueous filter cake of copper phthalocyanine blue pigment, disazo yellow pigment (C.
Proceed as above using an aqueous filter cake of Pigment Yellow 12) (pigment content 27%) and an aqueous filter cake of brilliant carmine 6B pigment (CI Pigment Red 57-1) (pigment content 25%). A flush color was prepared by using the inks, and then yellow and red offset lithographic inks were prepared respectively. Similarly, a flush color was obtained from an aqueous filter cake of Laked C pigment (CI Pigment Red 53-1), and a gold red ink for offset lithography was obtained. Also, a flush color was obtained from an aqueous filter cake of copper phthalocyanine green pigment (CI Pigment Green 7), and a grass ink for offset lithography was obtained. In each case, water was easily separated in flushing and showed excellent transition to an oil phase, and clear and excellent printed matter was obtained in offset lithographic printing. In addition, the flushing aid 1 used above
Flushing aid 2 - Flushing aid instead of
20, the same excellent effect as above was obtained. In addition, in place of the rosin amine that has neutralized the phosphate group of the flushing aid in the above, a salt of the flushing aid obtained by neutralizing it with coconut amine, tallow propylene diamine, or calcium, strontium, or aluminum hydroxide may be used. I used it and obtained the same excellent results as above. Example 2 Aqueous filter cake of carbon black pigment (solid content
20%) 100 parts Beef tallow propylene diamine salt of flushing aid 1 obtained in Reference Example 1 6 parts Mixed varnish for offset lithographic ink 69 parts Total 95 parts were used for flushing in the same manner as in Example 1. Obtained Tsushiyudokara. The carbon black pigment in this color was very well dispersed in the varnish. Varnish dispersion of carbon black pigment obtained above
95 parts 5% cobalt dryer 0.2 parts 8% manganese dryer 1.0 parts Ink solvent 3.8 parts A total of 100 parts were thoroughly mixed and kneaded to obtain carbon black ink. This was used to print with an offset printing machine to obtain a black printed matter with a high degree of blackness. In addition, the flushing aid 1 used above
Flushing aid 2 - Flushing aid instead of
20, the same excellent effect as above was obtained. In addition, in place of the neutralized beef tallow propylene diamine in which the phosphate group of the flushing aid is used in the above, flushing obtained by neutralizing with rosin amine, coconut amine, coconut propylene diamine, or calcium, strontium, or aluminum hydroxide. Using the salt as an auxiliary agent, the same excellent effects as above were obtained. Furthermore, the black ink obtained above was added to the yellow ink, red ink, and blue ink obtained in Example 1 to obtain four process yellow inks, process red inks, process blue inks, and process black inks for offset lithography. Color process printing was performed and clear and beautiful multicolor printed matter was obtained. Example 3 Flush color of copper phthalocyanine blue pigment obtained in Example 1 (purity 50%) 10.8 parts Rutile titanium white 2.0 parts Quick-drying styrenated alkyd resin 72.6 parts Xylol 6.6 parts Mineral spirits 7.6 parts 6 % cobalt naphthenate 0.3 parts anti-skinning agent 0.1 part A total of 100 parts was thoroughly mixed and dispersed to obtain a blue quick-drying enamel that dries at room temperature for metal materials such as machinery and vehicles. When this enamel was applied to a metal plate, a clear and beautiful painting was achieved. Next, in place of the copper phthalocyanine blue pigment of Example 1, disazo yellow (CI Pigment Yellow 14), a fast yellow pigment prepared by diazotizing 4-aminophthalimide and coupling it with acetoacetanilide, and watching red ( Flushing was carried out in the same manner as in Example 1 using the aqueous filter cakes of pigments CI Pigment Red 48) and Carmine FB (CI Pigment Red 3) to obtain flush colors of each pigment. These were used in place of the copper phthalocyanine pigment in the composition of the above paint, and paints of various colors were obtained, and clear and beautiful coated plates were obtained. Example 4 Copper phthalocyanine blue pigment (CI Pigment Blue 15-3) aqueous filter cake (pigment content 40%)
25 parts 10 parts Salt obtained by neutralizing the acid radical of flushing aid 1 obtained in Reference Example 1 with approximately equal equivalent amount of triethylamine
Flushing was carried out in the same manner as in Example 1 using 2 parts xylene, 13 parts butanol, 5 parts, and a total of 30 parts to obtain a flushed color. The pigment in this color was well dispersed in the xylene butanol mixed solvent. Next, a paint was prepared using the following recipe. Copper phthalocyanine blue dispersion obtained above 3 parts Rutile titanium white 14 parts Thermoplastic acrylic resin 70 parts Toluene 6.8 parts Xylene 3.2 parts Butanol 2.2 parts Cellosolve 0.8 parts Total 100 parts This was used as an acrylic lacquer enamel for automobiles. A clear and beautiful coating was obtained. In addition, the flushing aid 1 used above
Flushing aid 2 - Flushing aid instead of
20 was used, and the same excellent paint as above was obtained. In addition, in place of triethylamine which has neutralized the phosphate group of the flushing aid in the above, it can be obtained by neutralizing it with rosin amine, coconut amine, beef tallow propylene diamine, coconut propylene diamine, or hydroxide of calcium, strontium or aluminum. The same excellent effects as above were obtained using the flushing aid salt.

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[Table] Average molecular weight

【table】

【table】

[Table] Average molecular weight

Claims (1)

[Claims] 1. An aqueous slurry of pigment, a flushing aid,
In a pigment flushing method in which the pigment is transferred to an organic phase by kneading a mixture containing a hydrophobic organic solvent if necessary, the flushing aid is a phosphate ester compound represented by the following general formula or an ammonium thereof. 1. A method for flushing a pigment, characterized in that it is a salt, a primary to tertiary organic amine salt, an organic quaternary ammonium salt, or a monovalent to trivalent metal salt. [However, R ₁ is a hydrocarbon group having 4 to 30 carbon atoms that is not a polymer. _R2 is _R3OOC - _R1- , a hydrogen atom, or a hydrocarbon group having 1 to 30 carbon atoms. R ₃ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]