JPH0357134B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel phosphoric acid ester compound,
More specifically, it is a phosphoric acid ester compound containing one or two polyester chains, and is used in paints,
The purpose of the present invention is to provide a novel phosphoric acid ester compound that can be used as a dispersion aid, a lashing aid, etc. in the production of coloring materials such as printing inks and colorants for synthetic resins. (Prior Art) Conventionally, in the production of paints and printing inks, dispersion aids have been used for dispersing pigments in paint vehicles and printing ink varnishes, and for flushing pigments from aqueous filter cakes into oil vehicles and oil-based varnishes. For example, the phospholipid lecithin has been used as a flushing agent or 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. There is a need for compounds that can be used as agents or flushing aids. In view of the above-mentioned defects in dispersion aids or flushing aids for pigments, the present inventor has conducted various studies on compounds that have an affinity for various vehicles and varnishes, and also have an affinity for pigments. As a result, one of the polyester chains with hydroxyl groups
The present invention was completed based on the discovery that a di- or monoester obtained by reacting one or two of these with phosphoric acid exhibits excellent properties and effects. (Means for solving the problems) That is, the present invention is a phosphoric acid ester compound represented by the following general formula. However, R1 in the formula is a self-condensed polyester of hydroxycarboxylic acid, and its terminal is a carboxyl group or an ester group with alcohol,
R2 is a hydrogen atom or a cation, and R3 is
R1, R2 or a hydrocarbon group. To explain the present invention in detail, the phosphoric acid ester compound of the present invention can be obtained by reacting 1 mole or 2 moles of a polyester alcohol component with 1 mole of a phosphorylating agent according to a conventionally known reaction method. It will be done. 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 the 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, the pressure of the reaction apparatus may be reduced to remove the generated hydrogen chloride. It will be done. It is also preferable to heat the reaction to complete the reaction. After the reaction is completed, unreacted chloride groups are washed with hot water, hot water, cold water, etc. and hydrolyzed. In addition, when a halogenated phosphorus compound is used, a basic catalyst may be used, for example, tertiary amines such as triethylamine, pyridine, 2,6-lutidine, 1,8-diaza-bicyclo(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 are used, and after the reaction, filtration is performed. It is preferable to remove halides, salts, bases and other impurities by filtering, neutralizing, washing with water, etc. The alcohol component to be reacted is selected and used in various ways depending on the purpose of the product. The phosphoric acid ester compound of the present invention can be obtained by directly reacting a polyester alcohol component, etc. that matches the target compound with a phosphorylating agent, or by reacting it with, for example, methyl ester of 12-hydroxystearic acid in advance. , synthesize a di- or monoester such as a methyl ester at the end, and then hydrolyze the methyl ester, or
It can also be obtained by a method such as condensation with 12-hydroxystearic acid or its polyester or other alcohols by demethanol reaction to synthesize a phosphoric acid di- or monoester compound of the polyester. The polyester alcohol components used are conventionally known hydroxyl group-containing aliphatic, alicyclic and aromatic polyesters. The molecular weight of the polyester alcohol component used is not particularly limited, but
The average molecular weight is 10,000 or less, preferably between 500 and 5,000. As such polyester alcohol,
For example, the following are used. (A) Self-condensing polyesters of hydroxycarboxylic acids, preferably polyesters of hydroxycarboxylic acids containing hydrocarbon chains having from 4 to 30 carbon atoms. For example, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, ε-hydroxycaproic acid, p-hydroxyethyloxybenzoic acid, 2-hydroxynaphthalene-6-carboxylic acid. It is one or more self-condensing polyesters selected from hydroxycarboxylic acids such as. (B) An esterified product of the carboxylic acid at the other end of the polyester alcohol component described in (A) above. These are esters with aliphatic, alicyclic or aromatic alcohols having 1 to 30 carbon atoms,
Examples include esters of the above polyesters such as methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, and benzyl alcohol. In addition to the phosphoric acid ester compound of the polyester alcohol component described above, the phosphoric acid ester compound of the present invention includes a reaction between the polyester alcohol component and a phosphorylating agent to a monoester,
It also includes asymmetric phosphodiester compounds in which other monoester components are esterified using conventionally known hydroxycarboxylic acids, alcohol esters of hydroxycarboxylic acids, or alcohols, and can be synthesized according to conventionally known methods for synthesizing asymmetric phosphodiester compounds. are synthesized. Conventionally known alcohol components are used. For example, hydroxycarboxylic acids and alcohol esters thereof include ricinoleic acid, 12-hydroxystearic acid, γ-hydroxybutyric acid, δ-hydroxyvaleric acid, ε- Hydroxycaproic acid, p-hydroxyethyloxybenzoic acid, 2-hydroxynaphthalene-6-carboxylic acid, etc., and esters of these with alcohols having 1 to 30 carbon atoms.
~30 alcohols, such as 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 above-mentioned phosphoric acid esterification reaction of the alcohol component mainly composed of polyester alcohol of the present invention, it is necessary to use a material that is inert to these raw materials and products and that dissolves these raw materials. It is also preferred to use organic solvents that 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, are used. The phosphoric acid di- or monoester of 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,
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 may be used alone or in combination. Further, as higher aliphatic amines and ammoniums, mixtures of amines having different carbon numbers or degrees of saturation derived from natural oils and fats used as raw materials may 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 water, lower alkanolamine salts, etc. exhibit hydrophilicity and are water-soluble or water-dispersible.
When used, it can be used in an aqueous solution or aqueous dispersion. In addition, polyvalent metal salts of divalent or higher valence, higher amine salts, etc. are hydrophobic and lipophilic, and can be used alone or as a solvent solution as agents for making the surface of base materials such as pigments hydrophobic or oily. You can also do it. 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 or a higher amine compound is reacted to form the latter hydrophobic compound or oily compound. It is also used to treat substrates such as pigments. (Function/Effect) The phosphoric acid ester compound bonded with polyester chains obtained by the present invention can be found in the natural phospholipid lecithin described above in the field of coloring materials such as pigments, paints, printing inks, and plastic colorants. It has no fear of deterioration or decomposition due to oxidation or rancidity, and is highly stable and has excellent effects on surface modification, dispersion in media, etc. The phosphoric acid di- or monoester compound bonded with polyester chains of the present invention may be used alone as it is, or may be added to a dispersion medium such as a solvent, paint vehicle, printing ink varnish, or plasticizer, or may be used further therein. It is used in the form of an oil-in-water emulsion, and the surface of pigments etc. becomes philophilic, especially lipophilic, due to the effects of the phosphate ester bonds, the charge adsorption properties of the ester bonds, and the philophilic properties of the hydrocarbon chains. treated to improve dispersibility in the dispersion medium. Therefore, it is useful as a dispersion aid when dispersing using a dispersion or kneading machine, or as a flushing aid for pigment from an aqueous paste or filter cake into an oily dispersion medium. In addition, the phosphoric acid ester compound of the present invention can also be used in magnetic recording materials that are similar fine solid materials, metal fibers,
It is also useful as an additive such as a dispersion aid for conductive materials such as high structure carbon black and carbon fiber, electromagnetic shielding materials, and ceramic materials. Next, the present invention will be specifically explained with reference to Examples. Note that parts and percentages in the text are based on weight. Example 1 (1) Synthesis of self-condensing polyester of 12-hydroxystearic acid and its methyl esterification reaction. A four-necked glass reactor with a stirrer, a thermometer, a backflow condenser with a moisture meter, and an inlet and an oil bath were prepared. 100 parts of 12-hydroxystearic acid and 100 parts of toluene were charged therein and dissolved by stirring. After dissolution, the temperature was raised, and 1.0 part of p-toluenesulfonic acid was added as a condensation catalyst. reaction solution
The temperature was raised to 120°C to advance the self-condensation polyesterification reaction of 12-hydroxystearic acid.
The progress of the reaction was checked at 60 minutes, 120 minutes, and 180 minutes by the amount of distilled water and the infrared absorption spectrum of the reactant, and the polyesterification reaction was completed by cooling at 200 minutes. Next, when the temperature reached 63℃, methanol was added at 50℃.
100 parts of methyl acetate and 0.5 parts of p-toluenesulfonic acid were added thereto, and the temperature was raised to 110°C to proceed with the methyl esterification reaction while distilling off the solvent.
When 150 parts were distilled, the temperature was lowered to 63°C, 200 parts of methanol was added, the temperature was raised to 110°C, and the solvent was distilled off. The amount distilled off was 245 parts. The methyl esterification reaction required about 5 hours. After the reaction, 300 parts of water was added to extract the water-soluble component, and the oil layer separated into two layers was taken out. To dehydrate, add 150 parts of toluene and 200 parts of methanol to the oil layer, and boil to 130 parts while blowing nitrogen gas.
The temperature was raised to ℃ and the solvent was distilled off. The distillate amount was 345 parts. The reaction product obtained is an amber liquid, and it is confirmed by infrared absorption spectrum and gel permeation chromatography analysis data that it is a methyl ester of self-condensed polyester of 12-hydroxystearic acid. did. Measurement of the acid value of the reaction product confirmed that the methyl esterification reaction of the polymer was almost complete. Furthermore, the measured value of hydroxylation of the reaction product was 40.8. From this, this 12
- 1 gram equivalent of the methyl ester of the self-condensing polyester of hydroxystearic acid is 1375, from which the average degree of condensation polymerization is approximately 5
It is. (2) Synthesis reaction of phosphodiester compound of methyl ester of self-condensing polyester of 12-hydroxystearic acid. A four-necked glass reactor and water bath with stirrer, thermometer, addition funnel, and counterflow condenser was set up. 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. 7.0 parts of phosphorus oxychloride was charged to the reactor. Separately, 62.8 parts of methyl ester of self-condensed polyester of 12-hydroxystearic acid obtained in (1) above (1 gram equivalent is 1375) and benzene.
62.8 parts were mixed and dissolved, charged into a dropping funnel, and loaded into a reactor. While the reactor was externally cooled with ice and water, a benzene solution of the above polyester methyl ester of 12-hydroxystearic acid was added for 5 to 10 minutes.
Drop at ℃, being careful not to let the temperature rise above 10℃. 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 raise the temperature to about 40℃ and the degree of vacuum.
Set the temperature to 100 mmHg and cool after no longer generating hydrochloric acid gas. In this state, phosphoric acid (poly12
- methyl ester of hydroxystearic acid)
Monoester dichloride is produced. Next, 62.8 parts of the above polyester methyl ester of 12-hydroxystearic acid and benzene were added.
62.8 parts and 4.62 parts of triethylamine were mixed and dissolved, charged into a dropping funnel, and reacted dropwise over 60 minutes at 10 to 20°C, stirred for 2 hours, heated to 40°C over another 2 hours, Stir for 2 hours and cool. The equivalent ratio of the polyester having a hydroxyl group, phosphorus oxychloride and triethylamine is 2:
The ratio is 3:1. Next, water, water,
Washing was performed with dilute sodium hydroxide solution, dilute hydrochloric acid acidic solution, and water. After drying the washed benzene layer with sodium sulfate, benzene was distilled off under reduced pressure to obtain a brown liquid reaction product. The reaction product was confirmed to be mainly composed of a phosphoric diester compound of methyl ester of self-condensing polyester of 12-hydroxystearic acid by infrared absorption spectrum and gel permeation chromatography analysis charts. It was done. The approximate average molecular weight of the main component is 2500-2800
It was hot. In addition, the phosphoric acid group of the phosphoric diester of methyl ester of 12-hydroxystearic acid polyester obtained above was neutralized with rosin amine, coconut amine, beef tallow propylene diamine, and hydroxides of calcium, strontium, and aluminum, and the above-mentioned An organic amine salt and a metal salt of the phosphoric acid ester were obtained. The phosphoric diester compound of methyl ester of 12-hydroxystearic acid polyester obtained above and its organic amine salt, metal salt include copper phthalocyanine blue pigment, copper phthalocyanine green pigment, soluble azo lake pigment, insoluble azo lake pigment, carbon black pigment, etc. When dispersing pigments, it was effective in preparing high concentrations, shortening dispersion time, and improving dispersibility, and was also effective as an additive in flushing from aqueous press cakes. Examples 2 to 11 Various phosphate ester compounds were obtained 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). . Example 12 A four-necked glass reactor equipped with the stirrer, thermometer, dropping funnel, backflow condenser, pressure reduction system, and hydrochloric acid gas absorption system used in Example 1 (2) was heated to 7.0 mm.
of phosphorus oxychloride was added. Separately, poly12 synthesized in the same manner as in Example 1 (1)
- 65.8 parts of methyl ester of hydroxystearic acid (average molecular weight is 1440) and 65.8 parts of benzene
Example 1
In the same manner as (2), phosphoric acid (poly-12
methyl ester of poly-12-hydroxystearic acid (average molecular weight 600) synthesized in the same manner as in Example 1 (1).
27.4 parts of benzene and triethylamine
It was mixed and dissolved with 4.62 parts, and reacted in the same manner as in Example 1 (2). In the above, the equivalent ratio of polyester alcohol with an average molecular weight of 1440, polyester alcohol with an average molecular weight of 600, phosphorus oxychloride and triethylamine is 1:1:3:1. The cooled reaction product liquid was subjected to dechlorination reaction (hydrolysis), washing, purification, drying, and treatment in the same manner as in Example 1 (2).
Concentration and solvent removal gave a brown liquid reaction product. Analyzing in the same manner as in (2) of Example 1, it was confirmed that it was a phosphoric diester of methyl ester of poly-12-hydroxystearic acid, and the average molecular weight of its main component was approximately 1900 to 2100. . Like the phosphoric acid diester compound of Example 1, this compound was usefully used as a pigment dispersion aid, flushing aid, etc. in the form of an acid, an organic amine salt, and a metal salt. Examples 13 to 20 Various phosphoric ester compounds were obtained in the same manner as in Example 12, except that the materials listed in Table 2 below were used in place of the materials in Example 12. Like the phosphoric acid diester of Example 1, these were advantageously used as pigment dispersion aids, flushing aids, etc. in the form of acids, organic amine salts, and metal salts.

[Table] Molecular weight

【table】

【table】

Claims (1)

[Claims] 1. A phosphoric acid ester compound represented by the following general formula. [However, R1 in the formula is a self-condensed polyester of hydroxycarboxylic acid, the terminal of which is a carboxyl group or an ester group with alcohol,
R2 is a hydrogen atom or a cation, and R3 is
R1, R2 or a hydrocarbon group. 2. The phosphoric acid ester compound according to claim 1, wherein the self-condensed polyester chain of hydroxycarboxylic acid is a polyester chain of hydroxycarboxylic acid containing a hydrocarbon chain having 4 to 30 carbon atoms.