JPS6351391A - Phosphoric ester compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (at least one of three R groups is polyester chain group consisting of 4-30C hydrocarbon group containing ester linkage of a polycarboxylic acid with a polyalcohol as a chief linkage). USE:A dispersing agent and flashing agent for producing coating or printing ink. PREPARATION:For example, methyl nadic anhydride, etc., is reacted with butylene glycol and ethylene glycol mono(2-naphthoxy acetic acid)ester in a solvent such as toluene, etc., in the presence of an acid catalyst to provide a polyester, which is then reacted with phosphorus oxychloride in dripping into a solvent such as benzene, etc., in the presence of triethyl amine, etc., to provide the compound expressed by the formula.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel phosphoric acid ester compound, more specifically, it is a phosphoric acid ester compound containing a polyester chain, which is useful for dispersion processing of fine solid materials such as pigments. The purpose of the present invention is to provide a new nisder phosphate compound that can be used as a dispersing agent or flushing agent in the production of products.

(Prior art) Conventionally, in the production of paints and printing inks, dispersants have been used to disperse pigments into paint vehicles and printing ink faces, and when flushing from aqueous filter cakes into oil vehicles and oil faces. Alternatively, for example, lecithin, which is a phospholipid, has been used as a flushing agent.

(Problem 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 spoilage. There is a need for a dispersant or flushing agent with similar properties.

In view of the deficiencies of the conventional dispersants or flushing agents described above, the present inventors have conducted various studies on compounds that have an affinity for various vehicles and festivals, and also have an affinity for pigments. The present invention was completed based on the discovery that a phosphoric acid ester compound having a polyester chain exhibits excellent properties and effects as a pigment dispersant.

(Means for solving the problems) That is, the present invention is a phosphoric acid ester compound represented by the following general formula.

R-0-P-0-R (2) However, at least one of the three Rs in the formula is a group of a polyester chain whose main bond is an ester bond between a polycarboxylic acid and a polyalcohol.

To explain the present invention in more detail, the phosphoric acid ester compound of the present invention can be obtained by various methods, but 3 mol, 2 mol or 1 mol of the hydroxyl group-terminated polyester compound is added to 1 mol of the ester-forming phosphorus compound. It is preferable to obtain it by reacting according to a conventionally known reaction method.

In the above, per mol of ester-forming phosphorus compound,
If 3 moles of a hydroxy-terminated polyester compound are reacted, a phosphoric acid ester compound in which all three R's in the above general formula are polyester chain groups is obtained.

In addition, if 2 mol or 1 mol of the doxy-terminated polyester compound is reacted with 1 mol of the ester-forming phosphorus compound in the above formula, one or two of the three R's are polyester chains. A phosphoric acid ester compound which is a group of is obtained. The remaining two to one R are preferably a residue of a hydroxycarboxylic acid or an alcohol ester thereof, a hydrocarbon group, a hydrogen atom, a cation, or the like.

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

The reaction between the above ester-forming phosphorus compound and the hydroxy-terminated polyester compound can be carried out using an organic solvent that is inert to these raw materials and products and that dissolves these raw materials, such as octane, petroleum ether, and ligroin. , mineral spirit, aliphatic saturated hydrocarbons such as kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aliphatic hydrocarbons such as trichloroethane and tetrachloroethane, 0-dichlorobenzene, trichloroenzene, etc. It is preferable to carry out the reaction in an organic solvent used in the phosphoric acid esterification reaction, such as a chlorinated aromatic hydrocarbon.

In addition, when using a halogenated phosphoric acid compound such as phosphorus oxychloride as the ester-forming phosphorus compound, for example, tertiary amines such as triethylamine, pyridine,
2,6-lutidine, 1,8-diaza-bicyclo(5,4
, O) Organic bases such as undecene-7, oxides, hydroxides, carbonates of alkali metals, alkaline earth metals, manifest or latent inorganic bases of organic acid salts, etc. are preferably used as catalysts.

In addition, in the case where one or two of the three R's in the Tateki general formula is a hydrogen atom or a cation as described below, an ester-forming phosphorus compound and 1 or 2 moles of a doxy-terminated polyester compound After the reaction with is substantially complete, optionally after hydrolysis (if 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. All you have to do is form it. Further, the addition of such a cation source can be carried out by using a phosphoric acid ester compound having one or two hydroxyl-terminated polyester compound residues and the remaining R being a hydrogen ion. It may be carried out before, during, or after the production of a dispersion of pigment or the like.

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

Such hydroxyl group-terminated polyester compounds are
Polyesters can be produced by condensation polymerization using aliphatic, alicyclic, aromatic or heterocyclic polycarboxylic acid components and polyalcohol components, or further hydroxycarboxylic acid components, which are the raw materials used to synthesize conventionally known polyesters. This compound is synthesized and has a hydroxyl group at the end.

Examples of the polycarboxylic acids used include adipic acid, azelaic acid, sebacic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3,6-nindomethylene-tetrahydrophthalic anhydride (nadic anhydride).
, methyl-3,6-endomethylene-tetrahydrophthalic anhydride (methylnadic anhydride), hexachlorendomethylenetetrahydrophthalic anhydride (hettonic anhydride)
, dodecenyl succinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic anhydride, polymerized rosin, rosin-maleic anhydride adduct, unsaturated fatty acid-maleic anhydride adduct Things, etc. Also, as a polyalcohol to use.

Examples include butane 1,3-glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, octamethylene glycol, dihydroxymethylcyclodecane, dihydroxybenzene, tris(hydroxyethyl)isocyanurate, and the like.

Hydroxycarboxylic acids that may be used in combination include, for example, wasillic acid, 12-hydroxystearic acid,
and mustard oil fatty acids, hydrogenated bean oil fatty acids, gamma-hydroxyvaleric acid, ε-hydroxycaproic acid, P-hydroxyethyloxybenzoic acid, and the like.

The esterification reaction using the above components can be carried out according to conventionally known methods, for example, in a solvent-free system or a solvent solution, without a catalyst or using a catalyst, in a reduced pressure system or a normal pressure system, in air or The reaction is carried out by selecting preferred reaction conditions, such as under a nitrogen atmosphere.

The phosphoric acid ester compound of the present invention obtained as described above may have a free carboxyl group or hydroxyl group at the end of the polyester chain; At the time or after synthesis, or after forming the phosphoric acid ester compound, it may be esterified with a monoalcohol or monocarboxylic acid as necessary.

For example, monoalcohols used in such esterification include methyl, ethyl, pro-, butyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, tetracosyl, hexacosyl, octadecenyl, cyclohexyl, benzyl
Monoalcohols such as alcohol, and monocarboxylic acids include acetic acid, propionic acid, acetic acid, caproic acid, lauric acid, valmitic acid, stearic acid, oleic acid, linoleic acid, liluic acid, behenic acid, tricyclo These are monocarboxylic acids such as decanecarboxylic acid, benzoic acid, rosin, and hydrogenated rosin.

Furthermore, when the phosphoric acid ester compound of the present invention has a cyclic group having a large number of carbon atoms, it exhibits even more excellent properties as a pigment dispersant. .

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

These groups are introduced into the phosphoric acid ester compound by impregnating the hydroxyl-terminated polyester compound as a raw material component, or by directly reacting it as an alcohol component or phenol component. Reactive compounds for introducing aromatic hydrocarbon groups, alicyclic hydrocarbon groups, or heterocyclic compound groups include mono- or polyalcohols, mono- or polyphenols, mono- or polycarboxylic acids, and acid anhydrides having those groups. It is an acid chloride compound, or a compound having two or more of these reactive groups.

For example, diphenylmethanecarboxylic acid, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylpropane, 4,4'-dioxydiphenylsulfone and their phenols and ethylene oxide,
Propylene oxide, reaction product with epichlorohydrin; diphenylcarboxylic acid, diphenyldicarboxylic acid, oxybiphenyl and its reaction product with ethylene oxide, propylene oxide, reaction product with epichlorohydrin, naphthol, dihydroxynaphthalene, methyl 2-hydroxynaphthoate and their ethylene oxide, propylene oxide, reaction product with epichlorohydrin, naphthalenecarboxylic acid, naphthalenedicarboxylic acid, 3-oxy-anthracene-2-carboxylic acid, anthracene-carboxylic acid, anthraquinonecarboxylic acid, anthraquinone-dicarboxylic acid.

Fluorene alcohol, fluorene carboxylic acid, aminofluorene; phenanthrene carboxylic acid, acenaphthene carboxylic acid; abietic acid, di- or tetrahydroabietic acid, polymerized rosin, rosin-maleic anhydride adduct, coumaron carboxylic acid, quinoline carboxylic acid, quinoline Examples include dicarboxylic acid, 2-oxydibenzofuran-3-carboxylic acid, 2-oxycarbazole-gocarboxylic acid, and the like.

By introducing a cyclic group having a large number of carbon atoms into the phosphoric acid ester compound as described above, the phosphoric acid ester compound of the present invention is imparted with hydrophobicity or lipophilicity and has a marked affinity with pigments, especially organic pigments. can be increased.

Therefore, when such a phosphoric acid ester compound is used to treat a pigment, the surface of the pigment can be easily made hydrophobic or lipophilic, and the affinity of the treated pigment to an oily medium can be significantly improved.

The phosphoric acid ester compound of the present invention can be obtained by reacting 3 to 1 mole of a hydroxyl-terminated polyester compound as described above with 1 mole of the Nisder-forming phosphorus compound, and is obtained by reacting 3 to 1 mole of a hydroxyl-terminated polyester compound such as (c) When the above hydroxyl group-terminated polyester compound is reacted at a ratio of 1 mole or 2 moles, the remaining one or two R in the general formula that is not a polyester chain group is preferably a group other than the above polyester, For example, it can be a residue of another alcohol compound, a hydrogen atom, an inorganic cation or an organic cation.

Examples of inorganic cations include alkali metals such as sodium and potassium, polyvalent metals containing two or more atoms such as magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, zinc, aluminum, and tin, and ammonium. Examples of organic cations include methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl,
Octadecyl, oleyl, diethyl, diptyl,
Distearyl, triethyl, tributyl, dimethyloleyl, dimethyldecyl, dimethyldodecyl
, dimethyltetradecyl-, dimethylhexadecyl-,
Dimethyloctadecyl, dimethyloleyl, dilaurylmonomethyl, trioctylamine, dimethylaniline: primary, secondary, and secondary carbon atoms having 1 to 30 carbon atoms such as ethylenediamine, propylenediamine, hexamethylenediamine, stearylpropylpylenediamine, etc. Tertiary mono- and polyamines, quaternary ammoniums such as octadecyltrimethylammonium, dioctadecyldimethylammonium; and ethanolamine, jetanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, propatoolamine, dibrobanol Examples include cations such as amines and alkanolamines obtained by adding ethylene oxide to the above-mentioned higher aliphatic amines. These amines can be used singly or in mixtures.

Furthermore, when using higher aliphatic amines obtained from natural fats and oils and their ammoniums, mixtures of amines having different carbon numbers or degrees of saturation resulting from the natural fats and oils used as raw materials may also be used as they are.

In the phosphoric acid ester compound of the present invention as described in -1- below, a phosphoric acid ester compound in which all three R's are residues of a hydroxyl group-terminated polyester compound, a hydroxyl group-terminated polyester compound among the three R's; Those in which the group other than the residue is a residue of another alcohol, and those in which one or two of the three R's are higher amine cations are relatively hydrophobic dispersants, and organic It is preferably used as a solution in a solvent.

On the other hand, the compound of the above general formula, which is a cation consisting of one or two of the three R's, an alkali metal, ammonium, lower amine, or lower alkanolamine, is a relatively hydrophilic dispersant, and can be used in an aqueous solution or It is suitably used as a dispersion in water.

The fine solid material to which the phosphoric acid ester compound of the present invention is applied may be any material, but the most suitable materials are various pigments, such as conventionally known organic pigments, inorganic pigments, extender pigments, etc. .

For example, organic pigments include phthalocyanine, azo, condensed azo, anthraquinone, perinone/perylene, indigo/thioindigo, isoindolinone,
Azomethine azo series, dioxazine series, quinacridone series,
These include aniline black, triphenylmethane, and carbon black, and inorganic pigments include titanium oxide, iron oxide, iron hydroxide, chromium oxide, spinel fired pigments, lead chromate, and chromium. Extender pigments include acid vermilion type, navy blue type, aluminum powder, bronze powder, etc. Extender pigments include calcium carbonate type, FA acid barium type,
Silicon oxide type, aluminum hydroxide type, etc.

These pigments are used in the form of dry fine powders as well as aqueous filter cakes or aqueous suspensions.

The phosphoric acid ester compound of the present invention was added to the pigment 100 as described above.
About 1 to 300 parts by weight, preferably about 3 to 300 parts by weight
By blending in a proportion of about 150 parts by weight, a pigment composition having excellent dispersibility, 2-dispersion stability, etc. can be obtained.

Of course, when mixing these two components, conventionally known suitable organic solvents, binder resins such as oil-based paint vehicles, oil-based printing ink faces, oil-based coding agent vehicles, thermoplastic resins, thermosetting resins, etc. A resin, a boat-enabling agent, a crosslinking agent, a catalyst, etc. can be added at the same time, and the composition can be used as it is as a paint, printing ink, etc.

The pigment composition may be obtained by mixing the components of the stiff powder using any conventionally known method, such as a ball mill, a sand mill, an attritor, a horizontal continuous media dispersion machine, a Miki roll, a Miki roll, and a pressure kneader. , panbari mixer,
A typical method is mixing, kneading, and grinding using a conventionally known dispersing machine such as an extruder.

In particular, when using a pigment in the form of an aqueous filtration gel or an aqueous suspension, the phosphoric acid ester compound of the present invention may be used alone, preferably in a solution of a hydrophobic organic solvent (these organic solvents are The pigment can be transferred from the aqueous phase to the organic solvent phase to form a pigment composition by adding it to the pigment (which may contain a binder for printing inks or coatings) and mixing it (flushing).

Pigment compositions obtained using the phosphoric acid ester compound of the present invention include the following embodiments.

(1) A composition containing a pigment at a high concentration and useful as a coloring agent for printing inks, paints, coating agents, synthetic resins, etc.

In this embodiment, the concentration of the pigment is between 20 and 95%, and the concentration of the phosphoric acid ester compound of the invention is between 1 and 300% by weight of the pigment.

(2) A composition useful as a paint, etc., which also contains a paint, a dispersant, a solvent necessary as a coating agent, a binder resin, etc. In these compositions the pigment concentration is between 0.1 and 20% by weight.
The concentration of the phosphoric acid ester compound is 1 to 30% of the pigment.
It is 0% by weight.

Paints include all conventionally known paints that use pigments, such as automotive paints, architectural paints, wood paints, vehicle and equipment paints, household paints, plastic paints, and pre-coated metal paints. paint, can paint,
Marine paint, anti-corrosion paint, light curing paint, electron beam curing paint,
These include electrostatic powder paints and vinyl sol paints.

The printing ink includes all conventionally known printing inks, such as letterpress ink, lithographic ink, intaglio gravure ink, screen ink, newspaper ink, flexographic ink, and the like.

The pigment compositions in the various embodiments described above may be either solid or liquid. In the case of liquid, the medium used is water, a water-hydrophilic organic solvent mixture, or an organic solvent. Group-based, alicyclic-based, aromatic hydrocarbon-based, halogenated hydrocarbon-based, ester-based, ketone-based, glycol ether-based, alcohol-based, etc. are used.
It is not particularly limited.

Further, as paint vehicles, printing ink faces, coating agent vehicles, etc., conventionally known oil-based or water-based binder materials are used depending on the purpose. For example, Nagaura long, medium length, and short length alkyd resins, modified alkyd resins such as phenol-modified and styrenated alkyds, amino alkyd resins, oil-free alkyd resins, acrylic resins for baking, acrylic lacquer resins, acrylic polyol resins, and polyesters. 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 acrylic resin, Modified resins such as 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, drying oils , boiled oil, etc.

Examples of thermoplastic resins 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, Nisder adipate, sebacic acid ester, poly Nisder plasticizer, epoxidized soybean oil, and the like.

In addition, if necessary, conventionally known pigment dispersants or flushing agents, such as higher aliphatic primary, secondary, and tertiary monoamines, higher aliphatic quaternary ammonium, higher aliphatic propylene diamine, or their acetates,
The concomitant use of higher aliphatic salts, etc. does not impede the achievement of the present invention (action/effect). In the field of coloring materials, there is no risk of deterioration or spoilage due to oxidation or rancidity, as was the case with lecithin, a natural phospholipid conventionally used as a dispersant for pigments. It has an excellent effect on dispersing pigments in a medium.

In addition, the phosphoric acid ester compound of the present invention having a polyester chain attached thereto is adsorbed onto the surface of the pigment due to its phosphoric acid ester bond, the charge-absorbing property of the ester bond, and the hydrophilic property of the hydrocarbon chain. It improves the wettability of the pigment to the medium, and improves the dispersibility and fluidity of the pigment in the medium.It is also used as a flushing agent when flushing an aqueous filter cake of the pigment, etc. to make the surface of the pigment lipophilic. There are also things that make pigments hydrophobic, making it easier and more efficient to make pigments.
Can be flushed.

Furthermore, in the case of the phosphoric acid ester compound of the present invention into which a group of aromatic hydrocarbon, alicyclic hydrocarbon or heterocyclic compound which is a cyclic group having a large number of carbon atoms as described above is introduced, a pigment,
In particular, it has a high affinity with +TmK materials and also has a high affinity with oil-based media, further improving the dispersibility, fluidity, etc. of the pigment in these media.

The uses of the phosphoric acid ester compound of the present invention have been explained above using the general example of pigments as a representative example. However, the uses of the phosphoric acid ester compound of the present invention are not limited to pigments, but are also applicable to various fine solid materials, such as magnetic recording. It is useful as a dispersant in a medium for fine solid materials such as materials, conductive materials such as metal fibers, high-stiffness carbon black, and carbon fibers, electromagnetic shielding materials, and ceramic materials.

Next, the present invention will be specifically explained with reference to Examples (manufacturing examples of phosphoric acid ester compounds) and Reference Examples (examples of use as pigment dispersion examples). In addition, in the text.

Parts or percentages are by weight unless otherwise specified.

Example 1 (1) Synthesis of polyester A four-necked glass reactor having a stirrer, a thermometer, a backflow condenser with a moisture meter, an inlet, and an oil bath were prepared. To this were added 534 parts of methylnadic anhydride, 270 parts of butylene glycol, and ethylene glycol mono(
246 parts of 2-naphthoxyacetic acid) ester and 350 parts of toluene were charged and stirred to form a solution. After dissolution, the temperature was raised, and 15.8 parts of p-toluenesulfonic acid was added as a condensation catalyst. The temperature of the reaction solution was raised to 120° C. to allow the polynisdale reaction to proceed. The progress of the reaction was checked by measuring the amount of water surfaced and the infrared absorption spectrum of the reaction product, and after 27 hours, the reaction was completed by cooling.

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

The reaction product obtained was an amber liquid, and according to the infrared absorption spectrum and gel vermutation chromatography analysis chart, it was found to be ethylene glycol mono(methylnarsic acid-butylene glycol polyester).
It was confirmed that the main component was an ester with 2-naphthoxyacetic acid) ester. From the results of 1 itq determination of the hydroxyl value of the reaction product, h1 per 1 gram of the produced polyester was approximately 1,000.

(2) Synthesis of phosphate ester compound Four units equipped with a stirrer, a thermometer, a dropping funnel, and a backflow condenser []
A glass reactor and water bath were prepared.

Into the reactor, 293°5 parts of the polyester obtained in (1) above,
293.5 parts of benzene and 35.6 parts of triethylamine
1 part, 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), phosphorus oxychloride, and triethylamine is 3.3:
It is 3.6.

The reaction solution is cooled while stirring, and phosphorus oxychloride is added dropwise from the dropping funnel over 60 minutes while being careful not to raise the temperature of the reaction solution above 10°C. After completing the dropwise addition,
The reaction solution was gradually heated to 80° C. over 2 hours, reacted with stirring for 2 hours, and then cooled. Next, the reaction product solution was washed with methanol to remove toluethylamine, its hydrochloric acid, and the like. Methanol was added to obtain a brown liquid reaction product. The product was confirmed to be a phosphoric triester of ethylene glycol mono(2-naphthoxyacetic acid) ester of methyl narsic acid-butylene gelicol polyester by infrared absorption spectrum and gel vermusion chromatography analysis chart. The average molecular weight of the main component of the phosphoric acid ester of the present invention was approximately 2.700 to 3,000.

Examples 2 to 13 Various phosphoric ester compounds of the present invention were prepared in the same manner as in Example 1 (2), using the materials listed in Table 1 below in place of the materials in Example 1 (2). I got it.

Case A: Methyl nadic anhydride - hexahydrophthalic anhydride -
Butylene gelicol - ethylene glycol - naphthyl -
1-acetic acid (2:i:3:1:1) polynisder (1 gram etc. u=940) 3 equivalents phosphorus oxychloride
3 equivalents to 2.600 to 2,900 in total :1) Bossester (1 gram equivalent = 1
,040) 3 equivalent phosphorus oxychloride
3 equivalents of 2.800 to 3,200 Example A Methylnadic anhydride-butylene glycol-12-hydroxystearic acid-diethylene glycol-2-naphthyl ether (1:1:2:1) Polyester (l grams, etc. 1) = l, 050) 3 equivalents Phosphorus oxychloride 3 equivalents'
2.800-3.200 Methyl nadic anhydride-butylene gellicol-dipropylene glycol-2-naphthyl ether (2:2:1)
Polyester (1 gram equivalent = 760)
3 equivalents of phosphorus oxychloride
3 equivalents I;
1:1:2:1) polyester (1 gram equivalent = 920
) 3 equivalents of phosphorus oxychloride
3 equivalents of -゛ of -; 2, 500 to 2. 800 Example: Methylnadic anhydride-phthalic anhydride-butylene glycol-benzyl alcohol (2:1:3:1) Polyester (1 gram, etc. [=830) 3 equivalents Phosphorus oxychloride 3 equivalents
'Yono no 3-kura 61 (j[2.20
0 to 2,500 2 g 2741''ξ1 Methylnadic anhydride-butylene gellicol-cyclohexyl alcohol (3:3+1) polyester (1 gram equivalent = 850) 2 equivalents diethylene glycol-2-naphthyl ether (1 gram Current year = 230)
1 equivalent phosphorus oxychloride
3 equivalents of ξJ゛ -' of -r l, 800 to 2,000 Methylnadic anhydride-butylene glycol-benzyl alcohol (3:3:1) polyester (1 gram equivalent = 860 ) 2 equivalents diethylene glycol-2-naphthyl ether (1 gram equivalent = 230)
1 equivalent phosphorus oxychloride
- Amount of 1.800 to 2,000 x 5 plates Methyl nadic anhydride - Butylene gelicol - Benzyl alcohol (3:3:1) Polynisdel (1 gram equivalent = 860) 2 equivalents of phosphorus oxychloride
3 equivalents (after the reaction, it was neutralized with distearyldimethylamine and made into a salt) Propylene glycol-2-naphthyl ether (2:2:1)
Polyester (1 gram equivalent = 760)
2 equivalents of phosphorus oxychloride
3 equivalents (after reaction, neutralized with distearyldimethylamine to form a salt) / 2゛-dos-b-etc. 1.400-1,600 Methylnadic anhydride-butylene glycol (1:1)
Polyester (1 gram, etc. 1 = 450) 1 equivalent Diethylene glycol-2-naphthyl ether (1 gram equivalent = 230) 1 equivalent Phosphorus oxychloride 3 equivalents (After reaction, neutralized with stearyldimethylamine to form a salt) No: ' no ゛ no ゝ-;-h 600-750 Tenjo d Eguchi Methyl nadic anhydride-butylene glycol (1:1)
Polynisdel (1 gram, etc. fi = 1.020)
1 equivalent phosphorus oxychloride
3 equivalents (after the reaction, it was neutralized with trioctylamine and made into a salt) Amount of raw 1.000 to 1.100 Reference example 1 Copper phthalocyanine blue pigment (C, 1, Pigment Blue 15-3) aqueous filter cake (pigment content 42%) 2
38 parts were charged into a flasher, and then 20 parts of the phosphoric acid ester compound obtained in Example 1 was dissolved in 58.5 parts of petroleum-based ink solvent and added to the flasher.
The mixture was kneaded and flushed according to a conventional method. During this flushing, water in the cake was easily released, and the copper phthalocyanine blue pigment was transferred to the oily dispersant phase.

Furthermore, water was completely removed to obtain a flashed color containing copper phthalocyanine blue pigment. An offset lithographic printing ink was prepared using the flashed color containing the copper phthalocyanine blue pigment obtained above.

Flash color of the copper phthalocyanine blue pigment obtained above (pigment content 56%) 34.8 parts Mixed face for offset lithographic ink 63.0 parts 5% Cobalt dryer 0.2 parts 8% Manganese dryer 1.0 parts In the above The compound face 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 vent
29.5 parts aluminum mukylate 0.5
Total number of copies: 100 copies The ink obtained above was used to print on high-quality paper using an offset printing machine to obtain a clear indigo-colored printed matter.

In addition, in place of the aqueous filter cake of copper phthalocyanine blue pigment, an aqueous filter cake of disazo yellow iff material (C, 1, Pigment Yellow 12) (pigment content 27%), brilliant carmine 6Bgl:l material (C,
EXAMPLE 1 Using an aqueous filter cake (pigment content 25%) of Pigment Red 57-1), flashed colors were prepared in the same manner as above, and then yellow and red offset lithographic inks were prepared, respectively.

In the same manner, a flushed color was obtained from an aqueous MA cake of Lake Red C pigment (C, 1, Pigment Red 53-1), and a full red ink for offset lithography was obtained. Further, a flashed color was obtained from an aqueous filter cake of copper phthalocyanine green pigment (C, 1, Pigment Green 7), and a grass ink for offset lithography was obtained.

In each case, water is easily separated during flushing, the pigment shows excellent transfer to the oil phase, and the ink is easy to prepare.
61), a clear and excellent printed matter was obtained.

Further, the phosphoric ester compounds of Examples 2 to 13 were used in place of the phosphoric ester compounds used above,
Similar excellent effects as above were obtained.

Reference example 2 Carbon black pigment 20 parts Example 1
Phosphate ester compound 6 parts Offset ink 1 Now varnish 691) Total
The carbon black pigment was kneaded and dispersed using three rolls at a blending rate of 95 parts. The Car Pump Black pigment dispersed very well 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 total 10
By sufficiently uniformly mixing and kneading at 0 parts, a carbon black ink was obtained. This was used to print with an offset printing machine to obtain a black printed matter with a high degree of blackness.

Further, the phosphoric ester compounds of Examples 2 to 13 were used in place of the phosphoric ester compounds used above,
Similar excellent effects as above were obtained.

In addition, the black ink obtained above can be added to the yellow ink, red ink, and blue ink obtained in the above reference example to produce process yellow ink, process red ink, process blue ink, and process black ink for offset lithography. Color process printing was performed and clear and beautiful multicolor printed matter was obtained.

Reference Example 3 Flushed color of the copper phthalocyanine blue pigment obtained in Reference Example 1 (pigment content 56%) 9.6 parts Rutile titanium white 2.0 parts Quick-drying styrenated alkyd resin 72.6 parts Kijirol
6.6 parts mineral spirits
8.8 parts 6% cobalt naphthenate 0.3 parts 'Ury 1) - 〇・ 1 part Total 100 parts mix and disperse thoroughly and dry at room temperature for metal materials for machinery, vehicles, etc. Obtained bright blue quick-drying enamel of the mold. When applied, the paint was clear and beautiful.

Next, flushing was carried out in the same manner as in Reference Example 1 using the phosphoric ester compounds of Examples 2 to 13 in place of the phosphoric ester compounds used in Reference Example 1. Obtained Sid color.

Further, in place of the copper phthalocyanine blue pigment of Reference Example 1, disazo yellow (C,1, Pigment Yellow 14
), fast yellow pigment made by diazotizing 4-aminophthalimide and coupling it with acetoacedoanilide, Watching Red (C,1, Pigment Red 48), Chikaramin FB (C,1, Pigmentlet 3)
Flushing was carried out in the same manner as in Reference Example 1 using the aqueous '6M filter cake of each pigment to obtain flushed 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.

Reference example 4 Copper phthalocyanine blue pigment (c, r.

Pigment Blue 15-3) dry crushed pigment 10 parts Phosphate ester compound of Example 1 2 parts Kijirol
13 parts butanol
5 parts total 30
A dispersion of copper phthalocyanine blue pigment in a mixed solvent of quidylol-butanol was obtained.

Next, a paint was prepared using the following recipe.

Solvent dispersion containing copper phthalocyanine blue and phosphate ester compound obtained above 7 & 3 parts Rutile type titanium 14 parts Thermoplastic acrylic resin 70 parts Doluol
6.8 parts pheasant roll 3
．． 2 parts Butanol 2.2 parts Cellosolve 0.8n total
100 parts of this was applied as an acrylic lacquer enamel for automobiles, and a clear and beautiful coating was obtained.

In addition, the phosphoric ester compounds of Examples 2 to 13 were used in place of the phosphoric ester compounds used in Section 2, and the same excellent effects as above were obtained.

Claims (3)

[Claims] (1) A phosphoric acid ester compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, at least one of the three Rs in the formula is a group of a polyester chain whose main bond is an ester bond between a polycarboxylic acid and a polyalcohol. ) (2) The polyester chain contains a group selected from the group consisting of an aliphatic hydrocarbon group having 4 to 30 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic compound group. A phosphoric ester compound according to claim (1). (3) Two or one of the three R's in the formula is a group of a polyester chain whose main bond is an ester bond between a polycarboxylic acid and a polyalcohol, and one or two of the remaining R's are The phosphoric acid ester compound according to claim (1), which is a group selected from the group consisting of a residue of a hydroxycarboxylic acid or an alcohol ester thereof, a hydrocarbon group, a hydrogen atom, and a cation.