JPH07103133B2 - Dispersant - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel dispersant, and more specifically, it relates to a dispersion processed product of a fine solid material such as a pigment, which is composed of a phosphate ester compound containing a polyester chain. An object of the present invention is to provide a novel dispersant useful for dispersing or flushing pigments or the like during production.

(Prior Art) Conventionally, a dispersant for dispersing a pigment in a paint vehicle or a printing ink varnish or flushing an aqueous filter cake into an oil vehicle or an oil varnish in the production of a paint or a printing ink, or As a flushing agent,
For example, the phospholipid lecithin has been used.

(Problems to be solved by the invention) However, since lecithin is a natural phospholipid, it is susceptible to oxidation and rancidity, and may be deteriorated or spoiled. Therefore, lecithin is stable and superior to these lecithins. There is a need for a dispersant or flushing agent having the desired properties.

In view of the above defects of the conventional dispersant or flushing agent, the present inventors have various studies on compounds having affinity for various vehicles and varnishes, and also for pigments, The inventors have found that a phosphoric acid ester compound having a polyester chain containing an alicyclic dicarboxylic acid having 8 or more carbon atoms exhibits excellent properties and effects as a dispersant for a pigment, and completed the present invention.

(Means for Solving Problems) That is, the present invention is represented by the following general formula, R _{1 to} R ₃ are all polyester chain groups formed by condensing at least one alicyclic dicarboxylic acid having 8 or more carbon atoms with an alkylene glycol having at least 2 or more carbon atoms and optionally having a branch Or one or two of R _{1 to} R ₃ is a group of the above polyester chain, and the remaining is a group in which two or more benzene rings are linked,
A monoalcohol residue having a cyclic group selected from an alicyclic hydrocarbon group having 8 or more carbon atoms and a heterocyclic compound having 8 or more carbon atoms, a phosphoric acid ester compound which is a hydrogen atom or a cation Is a dispersant.

Explaining the present invention in more detail, the phosphoric acid ester compound used in the present invention can be obtained by various methods, but it is preferable that 3 mol, 2 mol or 1 mol of the hydroxyl group terminal is present per 1 mol of the ester-forming phosphorus compound. Further, it is preferably obtained by reacting a polyester compound composed of an alicyclic dicarboxylic acid having at least 8 carbon atoms according to a conventionally known reaction method.

When 1 mol of the ester-forming phosphorus compound is reacted with 3 mol of the hydroxy-terminated polyester compound in the above reaction, R _{1 to} R _{3 in} the general formula are all phosphorus groups which are groups of the polyester chain. An acid ester compound is obtained.

In the above reaction, if 1 mol of the ester-forming phosphorus compound is reacted with 2 mol or 1 mol of the hydroxy-terminated polyester compound, R ₁
A phosphoric ester compound in which one or two of R ₃ to R ₃ are the groups of the polyester chain is obtained. The remaining 2 to 1 of R _{1 to} R ₃ are preferably a monoalcohol residue having a ring structure, a hydrogen atom, a cation and the like.

As the ester-forming phosphorus compound, conventionally known phosphorus oxychloride, phosphorus pentoxide, phosphorus trichloride, phosphoric anhydride, fucetyl phosphoric acid and the like are used. Most preferred is phosphorus oxychloride.

The reaction between the above ester-forming phosphorus compound and the above hydroxy-terminated polyester compound is inert to these raw materials and products, and an organic solvent in which these raw materials and the like are dissolved, such as octane and petroleum ether. , Ligroin, mineral spirits, saturated aliphatic hydrocarbons such as kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated aliphatic hydrocarbons such as trichloroethane and tetrachloroethane, o-dichlorobenzene, trichlor Like chlorinated aromatic hydrocarbons such as benzene,
It is preferably carried out in the organic solvent used for the phosphoric acid esterification reaction.

When a halogenated phosphoric acid compound such as phosphorus oxychloride is used as the ester-forming phosphorus compound, for example, tertiary amines such as triethylamine, pyridine,
Of organic bases such as 2,6-lutidine and 1,8-diaza-bicyclo (5,4,0) undecene-7, oxides, hydroxides, carbonates and organic acid salts of alkali metals and alkaline earth metals It is preferable to use an explicit or latent inorganic base or the like as a catalyst.

When one or two of R _{1 to} R ₃ in the above general formula is a hydrogen atom or a cation as described below, an ester-forming phosphorus compound and 1 mol or 2 mol of the hydroxy-terminated polyester After the reaction with the compound is substantially completed and, if necessary, after hydrolysis (when a halogenated phosphoric acid compound is used as the ester-forming phosphorus compound), a cation source as described below is added to the reaction mixture to form a salt. Should be formed. In addition, such a cation source is added by R ₁
To R ₃ in which one or two have a residue of a hydroxyl-terminated polyester compound and the rest are hydrogen ions, before obtaining a dispersion such as a pigment using the phosphoric ester compound of the above general formula, Alternatively, it may be performed after manufacturing.

The molecular weight of the hydroxyl group-terminated polyester compound used in the above reaction is not particularly limited, but is a dimer to an average molecular weight of 10,000 or less, preferably about 500.
~ 5,000.

Such a hydroxyl group-terminated polyester compound contains an alicyclic dicarboxylic acid having 8 or more carbon atoms, which is a raw material used for synthesizing a conventionally known polyester, as an essential component,
In addition, an aromatic or heterocyclic dicarboxylic acid component and a glycol component, or a hydroxycarboxylic acid component is used to synthesize the polyester compound by polycondensation, and has a hydroxyl group at the terminal.

Examples of the alicyclic dicarboxylic acid having 8 or more carbon atoms to be used include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3,6-endo-methylene-tetrahydrophthalic anhydride (nadic acid anhydride), methyl- Examples thereof include 3,6-endomethylene-tetrahydrophthalic acid (methyl nadic acid) and its anhydride (methyl nadic acid anhydride), hexachloroendomethylene tetrahydrophthalic acid anhydride (het anhydride), and the like. Particularly preferred is methyl nadic acid or its anhydride.

Examples of other dicarboxylic acids include aliphatic dicarboxylic acids such as dodecenyl succinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, isophthalic acid, terephthalic acid, and other aromatic dicarboxylic acids, adipic acid, azelaic acid, sebacic acid. , Unsaturated fatty acids-maleic anhydride adducts and other aliphatic dicarboxylic acids, polymerized rosins, and rosin-maleic anhydride adducts.

When the alicyclic dicarboxylic acid having 8 or more carbon atoms is used in combination with other dicarboxylic acid, the total amount of dicarboxylic acid components is 20%.
It is preferably used in a proportion of ˜100% by weight.

As the glycol to be used, for example, ethylene glycol, butylene glycol, butane 1,3-glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, octamethylene glycol or the like has a branch having 2 or more carbon atoms. Alkylene glycol which may be mentioned is mentioned.

Examples of the hydroxylcarboxylic acid that may be used in combination include, for example, ricinoleic acid, 12-hydroxystearic acid,
Castor oil aliphatics, hydrogenated castor oil fatty acids, aliphatic hydroxycarboxylic acids such as gamma-hydroxyvaleric acid and ε-hydroxycaproic acid, and aromatic hydroxycarboxylic acids such as p-hydroxyethyloxybenzoic acid. Hydroxycarboxylic acid or its ester can also be used as an alcohol residue-forming substance of a phosphoric acid ester compound.

The esterification reaction using the above components is carried out according to a conventionally known method, for example, in a solvent-free system or a solvent solution, in a reduced pressure system or a normal pressure system using a catalyst-free system or a catalyst, in air or It is carried out by selecting preferable reaction conditions such as under a nitrogen atmosphere.

The phosphoric acid ester compound, which is the dispersant of the present invention obtained as described above, may have a free carboxyl group or hydroxyl group at the end of the polyester chain, and these groups are the hydroxyl groups of the raw material. At the time of or after the synthesis of the polyester compound having the above, or as a phosphoric acid ester compound, it may be esterified with a monoalcohol or a monocarboxylic acid, if necessary.

For example, monoalcohols used for such esterification include methyl-, ethyl-, propyl-, butyl-, hexyl-, octyl-, dodecyl-, hexadecyl-, octadecyl-, tetracosyl-, hexacosyl-, octadecenyl-. , Cyclohexyl-, benzyl-
Monoalcohols such as alcohol, and as the monocarboxylic acid, acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linoleic acid, behenic acid, tricyclo acid. Monocarboxylic acids such as decanecarboxylic acid, benzoic acid, rosin and hydrogenated rosin. Further, esterification with an alcohol or a carboxylic acid having a cyclic group having a large number of carbon atoms described below is preferable in order to enhance dispersibility.

Further, when the phosphoric acid ester compound dispersant in the present invention has a cyclic group having a large number of carbon atoms, it exhibits excellent pigment dispersibility.

The above-mentioned cyclic group having a large number of carbon atoms is a group in which two or more benzene rings are linked, an alicyclic hydrocarbon group having 8 or more carbon atoms, a group of a heterocyclic compound having 8 or more carbon atoms, and the like. For example, diphenylmethane, diphenylethane, diphenylpropane, diphenyl ether, diphenylmethyl ether, diphenyl sulfone, styrylbenzene, biphenyl, naphthalene, fluorene, anthracene, acenaphthene, polyhydronaphthalene, polyhydrophenanthrene, coumarin, quinoline, diphenylene oxide, It is a group derived from carbazole, benzcarbazole and the like.

The introduction of these groups into the phosphoric acid ester compound is carried out by incorporating them into the above-mentioned hydroxyl group-terminated polyester compound as a raw material component or by directly reacting them as a monoalcohol component or a phenol component.
As the reactive compound for introducing an aromatic hydrocarbon group, an alicyclic hydrocarbon group having 8 or more carbon atoms, or a heterocyclic compound group,
It is a mono- or polyalcohol having these groups, a mono- or polyphenol, a mono- or polycarboxylic acid and an acid anhydride, an acid chloride compound, or a compound having two or more kinds of these reactive groups.

For example, diphenylmethane carboxylic acid, diphenyl carboxylic acid, diphenyl dicarboxylic acid; 4,4'-dihitroxydiphenyl methane, 4,4'-dihydroxydiphenyl propane; 4,4'-dioxydiphenyl sulfone and their phenols and ethylene oxide, Reaction products with propylene oxide and epichlorohydrin; Oxybiphenyl and its reaction products with ethylene oxide, propylene oxide and epichlorohydrin; Naphthol, dihydroxynaphthalene, methyl 2-hydroxynaphthoate and their ethylene oxides, propylene oxide and epichlorohydrin Reaction product; naphthalenecarboxylic acid, naphthalenedicarboxylic acid, 3-oxy-anthracene-2-carboxylic acid, anthracene-carboxylic acid, anthraquino Carboxylic acid, anthraquinone-dicarboxylic acid; fluorene alcohol, fluorenecarboxylic acid, aminofluorene; phenanthrenecarboxylic acid, acenaphthenecarboxylic acid; abietic acid, di- or tetrahydroabietic acid, polymerized rosin, rosin-maleic anhydride addition product, coumarone Carboxylic acid, quinolinecarboxylic acid, quinolinedicarboxylic acid, 2-oxydibenzofuran-3-carboxylic acid, 2-oxycarbazole-3-
Examples thereof include carboxylic acid.

As described above, by introducing a cyclic group having a large number of carbon atoms into the phosphoric acid ester compound, the phosphoric acid ester compound of the present invention is imparted with hydrophobicity or lipophilicity, and at the same time, the affinity with a pigment, particularly an organic pigment, is significantly increased. Can be raised.

Therefore, when such a phosphoric acid ester compound is used for treating a pigment, the surface of the pigment can be easily rendered hydrophobic or lipophilic, and the affinity of the treated pigment for an oil medium can be significantly improved.

The dispersant composed of the phosphoric acid ester compound of the present invention is a hydroxyl group-terminated polyester compound having a concentration of 3 to 1 as described above.
It can be obtained by reacting the above-mentioned ester-forming phosphorus compound in a molar ratio of 1 mol. When the above-mentioned hydroxyl group-terminated polyester compound is reacted in a ratio of 1 mol or 2 mol per 1 mol of the phosphorus compound, the above-mentioned general The remaining one or two of R _{1 to} R ₃ which are not the above-mentioned polyester chain groups in the formula are preferably groups other than the above polyester, for example, residues of other alcohol compounds, hydrogen atoms and inorganic groups. It can be a cation or an organic cation.

Examples of the inorganic cation include alkali metals such as sodium and potassium, divalent or higher polyvalent metals such as magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, zinc, aluminum and tin, and ammonium. Examples of cations and organic cations include methyl-, ethyl-, propyl-, butyl-, hexyl-, octyl-, dodecyl-,
Octadecyl-, oleyl-, diethyl, dibutyl-,
Distearyl-, triethyl-, tributyl-, dimethyloctyl-, dimethyldecyl-, dimethyldodecyl-, dimethyltetradecyl-, dimethylhexadecyl-, dimethyloctadecyl-, dimethyloleyl-, dilaurylmonomethyl-, trioctyl-amine, dimethyl. Aniline; ethylenediamine, propylenediamine,
Hexamethylene diamine, stearyl propyl pyrenediamine, etc., primary, secondary, and tertiary mono- and polyamines having 1 to 30 carbon atoms, quaternary ammonium such as octadecyl trimethyl ammonium, dioctadecyl dimethyl ammonium; and ethanol. Amine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, propanolamine,
Examples of the cation include dipropanolamine and alkanolamine obtained by adding ethylene oxide to the above-mentioned higher aliphatic amine. These amines can be used alone or as a mixture.

When a higher aliphatic amine obtained from natural fats and oils or their ammoniums is used, a mixture of amines having different carbon numbers or different degrees of saturation due to the natural fats and oils used as raw materials is also used.

The dispersant of the present invention as described above is a phosphoric acid ester compound, in which all of R _{1 to} R ₃ are phosphoric acid ester compounds, which are residues of a hydroxyl group-terminated polyester compound, R _{1 to} R _3.
Of the groups that are not residues of the hydroxyl group-terminated polyester compound, those that are residues of other alcohols, and R ₁ to
A compound in which one or two of R ₃ is a cation of a higher amine is a relatively hydrophobic dispersant and is preferably used as a solution of an organic solvent.

On the other hand, the compound of the above general formula in which one or two of R _{1 to} R ₃ is a cation composed of an alkali metal, ammonium, a lower amine and a lower alkanolamine is a relatively hydrophilic dispersant, and an aqueous solution. Alternatively, it is preferably used as a dispersion in water.

The fine solid material to which the dispersant of the present invention is applied may be any material, but the most suitable material is various pigments such as conventionally known organic pigments, inorganic pigments and extender pigments.

For example, organic pigments include phthalocyanine-based, azo-based, condensed azo-based, anthraquinone-based, perinone-perylene-based, indigo-thioindigo-based, isoindolinone-based, azomethineazo-based, dioxazine-based, quinacridone-based, aniline black-based, tri-based Phenylmethane-based, and carbon black and the like, as the inorganic pigment-based, titanium oxide-based, iron oxide-based, iron hydroxide-based, chromium oxide-based, spinel-type calcined pigment, lead chromate-based, vermilion chromate-based, Extenders such as navy blue, aluminum powder, bronze powder, calcium carbonate, barium sulfate,
Examples thereof include silicon oxide type and aluminum hydroxide type.

These pigments are used not only in the form of dry fine powder, but also in the form of an aqueous filter cake or an aqueous suspension.

By adding the dispersant of the present invention to the pigment as described above in an amount of about 1 to 300 parts by weight, preferably about 3 to about 150 parts by weight, excellent dispersibility, dispersion stability and the like can be obtained. A pigment composition having is obtained. Of course, when mixing these two components, a conventionally known suitable organic solvent, a vehicle for an oil-based paint, a varnish for an oil-based printing ink, a binder resin for a vehicle for an oil-based coating agent, a thermoplastic resin, a thermosetting resin, etc. A resin, a plasticizer, a cross-linking agent, a catalyst and the like can be mixed at the same time, and can be directly used as a paint or printing ink.

The method for obtaining the pigment composition by mixing these components may be any conventionally known method, for example, a ball mill, a sand mill, an attritor, a horizontal continuous medium disperser, a two-roll, a three-roll, a pressure kneader. , Ban Bali mixer,
A typical method is mixing and kneading with a conventionally known disperser such as an extruder. In particular, when the pigment in the form of an aqueous filter cake or an aqueous suspension is used as the pigment, the dispersant of the present invention alone is used, preferably a solution of a hydrophobic organic solvent (these organic solvents are printing inks). (Or a binder for paint) may be added to the pigment and mixed (flushing) to prepare a pigment composition by transferring the pigment from the aqueous phase to the organic solvent phase.

The pigment composition obtained by using the dispersant of the present invention includes the following aspects.

(1) A composition containing a high concentration of a pigment and useful as a colorant for printing inks, paints, coating agents, synthetic resins and the like.
In this embodiment, the concentration of the pigment is 20 to 95%, and the concentration of the phosphoric acid ester compound of the present invention is 1 to 300% by weight of the pigment.

(2) A composition useful as a paint or the like, which also contains a solvent, a binder resin and the like necessary for a paint, a dispersant, a coating agent. In these compositions, the concentration of the pigment is 0.1 to 20% by weight, and the concentration of the phosphoric acid ester compound is 1 to 300% by weight of the pigment. Some paints include all paints that use conventionally known pigments, such as automotive paints, architectural paints, wood paints, vehicle / equipment paints, household paints, plastic paints, and pre-coated metal. Paints, paints for cans, paints for ships, anticorrosion paints, photocurable paints, electron beam curable paints, electrostatic powder paints, vinyl sol paints and the like.

The paint includes all paints in which conventionally known pigments are used, and for example, as automotive paints, architectural paints, wood paints, vehicle / equipment paints, household paints, conventionally known pigments. Include all paints used, such as automotive paints, architectural paints, wood paints, vehicle / equipment paints, household paints, plastic paints, pre-coated metal paints, can paints, marine paints. Paints, anticorrosion paints, photocurable paints, electron beam curable paints, electrostatic powder paints, vinyl sol paints and the like.

The printing ink includes all conventionally known printing inks, and examples thereof include letterpress ink, planographic ink, intaglio gravure ink, screen ink, newspaper ink and flexo ink.

The pigment composition in the various aspects as described above may be in a solid state or a liquid state, and water or a water-hydrophilic organic solvent mixture, an organic solvent is used as a medium in the case of a liquid state, and the organic solvent is a fat. Group-based, alicyclic-based, aromatic-based hydrocarbons, halogenated hydrocarbon-based, ester-based, ketone-based, glycol ether-based, alcohol-based, etc. are used, but are not particularly limited.

As a vehicle for paint, a varnish for printing ink, a vehicle for coating agent, and the like, conventionally known oily or aqueous binder materials are used according to each application. For example, long oil length, medium oil length, short oil length alkyd resin, modified alkyd resin such as phenol-modified, styrenated alkyd, aminoalkyd resin, oil-free alkyd resin, baking acrylic resin, fucryl lacquer resin, fucryl polyol Resin, polyester resin, epoxy resin, butylated melamine resin, methylated melamine resin, urea-melamine resin, phenol resin, rosin-modified phenol resin, rosin-modified maleic acid resin, phenol-modified maleic acid resin, polyurethane resin, styrene resin, styrene Modified resin such as acrylic resin, styrene-gen copolymer, vinyl chloride copolymer, vinyl acetate resin, vinyl acetate copolymer, ethylene vinyl acetate resin, butyral resin, petroleum resin, rosin ester, maleated rosin ester , Dry , It is a boiled oil, and the like.

Examples of the thermoplastic resin include polyvinyl chloride resin, styrene resin, acrylonitrile / styrene resin, acrylic resin, methacryl-styrene resin, and polyester resin.

Examples of the plasticizer include phthalic acid ester, adipic acid ester, sebacic acid ester, polyester plasticizer, epoxidized soybean oil and the like.

If necessary, a conventionally known pigment dispersant or flushing agent, for example, higher aliphatic primary, secondary, or tertiary monoamine or higher aliphatic quaternary ammonium, higher aliphatic propylenediamine or The combined use of these acetates and higher aliphatic salts does not hinder the achievement of the present invention.

(Function / Effect) The dispersant comprising the polyester chain-bonded phosphoric acid ester compound of the present invention as described above is conventionally used as a dispersant for pigments in the field of coloring materials such as paints, printing inks, and plastic colorants. The natural phospholipids such as lecithin do not deteriorate or deteriorate due to oxidation or rancidity, have excellent stability, and have excellent effects such as surface modification of pigments or dispersion of pigments in a medium. is there.

Further, the phosphoric acid ester compound having a polyester chain bonded, which is the dispersant of the present invention, has a phosphoric acid ester bond, a charge attracting property of the ester bond, and a hydrophilic property of a hydrocarbon chain on the surface of the pigment. It improves the wettability of the pigment to the medium by adsorption, improves the dispersion of the pigment in the medium, and improves the fluidity, and also serves as a flushing agent when flushing an aqueous filter cake of the pigment. Since the surface is made lipophilic or hydrophobic, the pigment can be easily and efficiently flushed.

Furthermore, a dispersant comprising the above-mentioned phosphate ester compound of the present invention into which a group of an aromatic hydrocarbon which is a cyclic group having a large number of carbon atoms, an alicyclic hydrocarbon having 8 or more carbon atoms or a group of a heterocyclic compound is introduced is It has a high affinity with pigments, especially organic pigments, and also a high affinity with oily media, and the dispersibility and fluidity of the pigment in these media are further improved.

Although the application of the dispersant of the present invention has been described above as a representative example of application to pigments, the application of the dispersant of the present invention is not limited to pigments, and various fine solid materials such as magnetic recording materials and metal fibers can be used. , A high-structure carbon black, a conductive material such as carbon fiber, an electromagnetic wave shielding material, and a fine solid material such as a ceramic material are useful as a dispersant in a medium.

Next, the present invention will be specifically described with reference to production examples (of phosphoric acid ester compounds) and examples. In addition, in the sentence, part or%
Unless otherwise specified, the weight is based on the weight.

Production Example 1 (1) Synthesis of polyester A four-neck glass reactor having an agitator, a thermometer, a backflow condenser with a moisture meter, and a charging port, and an oil bath were prepared. Then, 534 parts of methyl nadic acid anhydride, 270 parts of butylene glycol, 246 parts of ethylene glycol mono (2-naphthoxyacetic acid) ester and 350 parts of toluene were charged and stirred to obtain a solution. After the dissolution, the temperature was raised, and 15.8 parts of p-toluenesulfonic acid was added as a condensation catalyst. The temperature of the reaction liquid was raised to 120 ° C., and the polyesterification reaction was allowed to proceed.
The progress of the reaction was examined by measuring the amount of distilled water and the infrared absorption spectrum of the reaction product, followed by cooling after 7 hours,
The reaction was completed.

Then, the catalyst is neutralized with alkali, toluene is distilled off,
Methanol was added to extract and wash the neutralized catalyst, and then the methanol was distilled off.

The obtained reaction product was an amber liquid, and was analyzed by an infrared absorption spectrum and a gel permeation chromatograph analysis chart to obtain ethylene glycol mono (2) of methylnaldic acid-butylene glycol polyester.
-Naphthoxyacetic acid) ester was confirmed as the main component. From the measurement result of the hydroxyl value of the reaction product, 1 gram equivalent of the produced polyester was about 1,000.

(2) Synthesis Reaction of Phosphate Ester Compound A four-neck glass reactor having a stirrer, a thermometer, a dropping funnel and a backflow condenser and a water bath were prepared.

The reactor was charged with 293.5 parts of the polyester obtained in (1) above, 293.5 parts of benzene and 35.6 parts of triethylamine, mixed and dissolved. Separately, 15.0 parts of phosphorus oxychloride was charged into a dropping funnel and charged into the reactor.

In the above, the equivalent ratio of the polyester obtained in (1) above, phosphorus oxychloride and toluethylamine is 3: 3: 3.6.

The reaction solution is cooled with stirring, and phosphorus oxychloride is added dropwise from the dropping funnel over 60 minutes, taking care not to let the temperature of the reaction solution rise above 10 ° C. After completion of the dropwise addition, the reaction solution was gradually heated to 80 ° C. over 2 hours, stirred and reacted for 2 hours, and then cooled. Then, the reaction product solution was washed with methanol in order to gradually remove toluethylamine and its hydrochloric acid. Methanol was distilled off to obtain a brown liquid reaction product. The product was confirmed to be a phosphoric acid triester of ethylene glycol mono (2-naphthoxyacetic acid) ester of methylnaldic acid-butylene glycol polyester by infrared absorption spectrum and analysis chart of gel permeation chromatograph. The average molecular weight of the main component of the phosphoric acid ester of the present invention is 2,700.
It was ~ 3,000.

Production Examples 2 to 13 Various materials of the present invention were obtained in the same manner as in (2) of Production Example 1 using the materials described below in place of the material of (1) of Production Example 1 .

Production Example 2 Methyl nadic acid anhydride-hexahydrophthalic anhydride-
Butylene glycol-ethylene glycol-naphthyl-
1-acetic acid (2: 1: 3: 1: 1) polyester (1 gram equivalent = 940) 3 equivalents phosphorus oxychloride 3 equivalents Average molecular weight of the main component of the product 2,600 to 2,900 Production Example 3 Methyl nadic acid anhydride-anhydrous Phthalic acid-butalene glycol-tetraethylene glycol-2-naphthyl ether (2: 1: 3: 1) polyester (1 gram equivalent = 1,040) 3 equivalents phosphorus oxychloride 3 equivalents Average molecular weight of the main component of the product 2,800- 3,200 Production Example 4 Methyl nadic acid anhydride-butylene glycol-12-hydroxystearic acid-diethylene glycol-2-naphthyl ether (1: 1: 2: 1) polyester (1 gram equivalent = 1,050) 3 equivalents Phosphorus oxychloride 3 equivalents produced Average molecular weight of the main component of the product 2,800 to 3,200 Production Example 5 Methyl nadic acid anhydride-butylene glycol-dipropylene glycol-2-naphthyl ether (2: 2: 1) poly Stell (1 gram equivalent = 760) 3 equivalents Phosphorus oxychloride 3 equivalents Average molecular weight of the main component of the product 2,100 to 2,300 Production Example 6 Methyl nadic acid anhydride-butylene glycol-12-hydroxystearic acid-cyclohexyl alcohol (1: 1:
2: 1) Polyester (1 gram equivalent = 920) 3 equivalents Phosphorus oxychloride 3 equivalents Average molecular weight of the main component of the product 2,500 to 2,800 Production Example 7 Methyl nadic acid anhydride-phthalic anhydride-butylene glycol-benzyl alcohol ( 2: 1: 3: 1) Polyester (1 gram equivalent = 830) 3 equivalents Phosphorus oxychloride 3 equivalents Average molecular weight of the main component of the product 2,200 to 2,500 Production Example 8 Methyl nadic acid anhydride-butylene glycol-cyclohexyl alcohol (3 : 3: 1) Polyester (1 gram equivalent = 850) 2 equivalents Diethylene glycol-2-naphthyl ether (1 gram equivalent = 230) 1 equivalent phosphorus oxychloride 3 equivalents Average molecular weight of the main component of the product 1,800-2,000 Production Example 9 Methyl nadic acid anhydride-butylene glycol-benzyl alcohol (3: 3: 1) polyester (1 gram equivalent = 86
0) 2 equivalents diethylene glycol-2-naphthyl ether (1 gram equivalent = 230) 1 equivalent phosphorus oxychloride 3 equivalents Average molecular weight of the main component of the product 1,800 to 2,000 Production Example 10 Methyl nadic acid anhydride-butylene glycol-benzyl alcohol (3 : 3: 1) Polyester (1 gram equivalent = 86)
0) 2 equivalents Phosphorus oxychloride 3 equivalents (after reaction, neutralized with distearyldimethylamine to form a salt) Average molecular weight of the main component of the product 1,600 to 1,800 Production Example 11 Methyl nadic acid anhydride-butylene glycol-diene Propylene glycol-2-naphthyl ether (2: 2: 1) polyester (1 gram equivalent = 760) 2 equivalents phosphorus oxychloride 3 equivalents (after reaction, neutralized with distearyl dimethylamine to give a salt) Product Average molecular weight of the main component of 1,400-1,600 Production Example 12 Methyl nadic acid anhydride-butylene glycol (1: 1) polyester (1 gram equivalent = 450)
1 equivalent Diethylene glycol-2-naphthyl ether (1 gram equivalent = 230) 1 equivalent Phosphorus oxychloride 3 equivalents (after reaction, neutralized with stearyl dimethylamine to form a salt) Average molecular weight of the main component of the product 600 to 750 Production Example 13 Methyl nadic acid anhydride-butylene glycol (1: 1) polyester (1 gram equivalent = 1,020) 1 equivalent phosphorus oxychloride 3 equivalents (after reaction, neutralized with trioctylamine to give a salt) Product Average molecular weight of the main component of 1,000 to 1,100 Example 1 Copper phthalocyanine blue pigment (CI Pigment Blue 15
238) Aqueous filter cake of -3) (pigment content 42%) was charged in a flasher, and then 20 parts of the phosphoric acid ester compound as the dispersant obtained in Production Example 1 was dissolved in 58.5 parts of petroleum-based ink solvent. Then, the mixture was added to a flasher, kneaded according to a conventional method, and flushed. In this flushing, the water in the cake is easily released,
The copper phthalocyanine blue pigment migrated to the oily dispersant phase.

Further, the moisture was completely removed, and a flooded color containing a copper phthalocyanine blue pigment was obtained. An offset lithographic printing ink was prepared using the flooded color containing the copper phthalocyanine blue pigment obtained above.

Flushed de color of the copper phthalocyanine blue pigment obtained in the above (pigment content 56%) 34.8 parts offset lithographic inks formulated varnish 63.0 parts 5% cobalt drier 0.2 parts of 8% manganese drier 1.0 part isoquinolinium Solvent 1.0 parts Total 100 parts The In the above, the compounding varnish for offset lithographic ink has the following composition.

Printed on high quality paper at an offset printing machine by using the rosin-modified phenolic resin 35 parts dry oil 25 parts drying oil-modified isophthalic acid alkyd 10 parts Ink Solvent 29.5 parts Ink obtained aluminum chelate 0.5 parts Total 100 parts The, A clear indigo print was obtained.

Further, instead of the aqueous filter cake of copper phthalocyanine blue pigment, an aqueous filter cake of disazo yellow pigment (CI Pigment Yellow 12) (pigment content 27%), Brilliant Carmine 6B pigment (CI Pigment Red 57-
Using the aqueous filter cake of 1) (pigment content 25%), the same operation as above was carried out to produce a floodside color, and then yellow and crimson offset lithographic inks were prepared.

Similarly, Lake Red C pigment (CI Pigment Red
53-1) to obtain a frassid color from the aqueous filter cake,
A gold-red ink for offset lithographic printing was obtained.

In addition, a floccid color was obtained from an aqueous filter cake of copper phthalocyanine green pigment (CI Pigment Green 7) to obtain a grass ink for offset lithographic printing.

Each of them has easy water separation in the flushing, shows the transfer of the pigment to the excellent oil phase, and is easy to prepare the ink, and clear and excellent printed matter is obtained in the offset lithographic printing using these inks. Was given.

Further, the same effect as above was obtained by using the phosphoric acid ester compounds of Production Examples 2 to 13 instead of the phosphoric acid ester compound which is the dispersant used in the above.

The carbon black pigment was kneaded and dispersed with three rolls in Example 2 Carbon black pigment 20 parts manufacture EXAMPLES Example 1 phosphate ester compound 6 parts offset lithographic inks formulated varnish 69 parts Total 95 parts of formulation. The carbon black pigment dispersed very well in the varnish.

Sufficiently uniformly mixed and kneaded varnish dispersion 95 parts 5% cobalt drier 0.2 parts of 8% manganese drier 1.0 parts Ink solvent 3.8 parts Total 100 parts of carbon black pigment obtained above, to obtain a carbon black ink. Printing with an offset printing machine using this,
A black-colored printed matter with high blackness was obtained.

Further, the same effects as above were obtained by using the phosphate ester compounds of Production Examples 2 to 13 instead of the phosphate ester compound used in the above.

In addition, the black ink obtained above was added to the yellow ink, the red ink, and the indigo ink obtained in the above-mentioned Reference Example to obtain offset process lithographic process yellow ink, process red ink, process indigo ink, and process black ink. Color process printing was performed, and clear and beautiful multicolor printed matter was obtained.

Example 3 Flat colour of copper phthalocyanine blue pigment obtained in Production Example 1 (pigment content 56%) 9.6 parts rutile titanium white 2.0 parts quick-drying styrenated alkyd resin 72.6 parts xylol 6.6 parts mineral spirits 8.8 parts 6% naphthene sufficiently uniformly mixed and dispersed in cobalt 0.3 parts transdermal antiskinning agent 0.1 parts total 100 parts of the formulation, to obtain machine, blue quick drying enamel air drying of metallic material for a vehicle or the like. When applied, a clear and beautiful paint was applied.

Next, instead of the phosphoric acid ester compound used in Example 1, the phosphoric acid ester compound of Production Examples 2 to 13 was used, and flushing was performed in the same manner as in Example 1 to perform flushing using each phosphoric acid ester compound. Got the color.

Also, instead of the copper phthalocyanine blue pigment of Example 1,
Disazo Yellow (CI Pigment Yellow 14), 4-
Reference Example 1 using an aqueous filter cake of a fast yellow pigment obtained by diazotizing aminophthalimide and coupling it with acetoacetanilide, Watching Red (CI Pigment Red 48), Carmine FB (CI Pigment Red 3) pigment. Flushing was performed in the same manner as in (1) to obtain a flacside color of each pigment.

These were used in place of the copper phthalocyanine pigment in the above composition of the paint, and paints of each color were obtained, and clear and beautiful coated plates were obtained.

Example 4 Copper phthalocyanine blue pigment (CI Pigment Blue 15
Dispersed in a continuous horizontal medium dispersing machine at a dry phosphate esters of pulverized pigment 10 parts Preparation Example 1 Compound 2 parts of xylene 13 parts butanol 5 parts total of 30 parts of -3), xylene roll butanol mixture of copper phthalocyanine blue pigment A solvent dispersion was obtained.

Next, a paint was prepared with the following formulation.

Copper phthalocyanine blue and phosphoric acid ester compound solvent dispersion 3 parts rutile titanium white, 14 parts of thermoplastic acrylic resin 70 parts of toluene 6.8 parts xylene 3.2 parts butanol 2.2 parts cellosolve 0.8 parts Total 100 parts automobile this containing obtained above Used as an acrylic lacquer enamel for application, it gave a clear and beautiful coating.

Further, the same effects as above were obtained by using the phosphate ester compounds of Production Examples 2 to 13 instead of the phosphate ester compound used in the above.

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Takamitsu Shinoda 1170-41 Matsugasaki, Kashiwa-shi, Chiba (72) Inventor Shojiro Horiguchi 2135 Katayanagi, Omiya-shi, Saitama (56) References Japanese Patent Publication No. 43-9536 (JP, B1) ) Japanese Patent Publication Sho 49-47918 (JP, B1)

Claims (6)

[Claims] 1. Represented by the following general formula, R _{1 to} R ₃ are all polyester chain groups formed by condensing at least one alicyclic dicarboxylic acid having 8 or more carbon atoms with an alkylene glycol having at least 2 or more carbon atoms and optionally having a branch Or one or two of R _{1 to} R ₃ is a group of the above polyester chain, and the remaining is a group in which two or more benzene rings are linked,
From a monoalcohol residue having a cyclic group selected from an alicyclic hydrocarbon group having 8 or more carbon atoms and a heterocyclic compound group having 8 or more carbon atoms, a phosphate compound which is a hydrogen atom or a cation A dispersant characterized in that 2. The dispersant according to claim 1, wherein the polyester chain is a mixture with an aromatic dicarboxylic acid containing at least 20% by weight of an alicyclic dicarboxylic acid. 3. The pigment dispersant according to claim (1) or (2), wherein the alicyclic dicarboxylic acid having 8 or more carbon atoms is methyl nadic acid or its anhydride. 4. The dispersant according to claim 1, wherein the polyester chain is esterified at the terminal. 5. The dispersant according to claim (1) or (2), wherein the polyester chain is further combined with an aliphatic or aromatic hydroxycarboxylic acid. 6. The dispersant according to claim (1) or (2), wherein the cation is an inorganic or organic cation.