JPS6270418A - phosphate ester compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel phosphoric acid ester compound, more specifically a phosphoric acid ester compound containing one or two polyester chains, which can be used in coatings, printing, etc. 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 inks and colorants for synthetic resins.

(Prior Art) Conventionally, in the production of paints and printing inks, dispersion aids have been used to disperse pigments into paint vehicles and printing ink varnishes, and to flush pigments from aqueous filter cakes into oil-based vehicles and oil-based varnishes. Alternatively, the phospholipid lecithin, for example, has been used as a flushing aid.

(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 that it may deteriorate or rot. There is a need for compounds that can be used as dispersing aids or flushing aids.

The present inventors: 1. In view of the deficiencies of dispersing aids or flushing aids that can be noted, various compounds have been prepared that have an affinity of 1 for various vehicles and varnishes, and an affinity of 1 for pigments. As a result of research, it was found that di- or monoesters in which one or two of the polyester chains containing 41 hydroxyl groups were reacted with phosphoric acid were superior.
The present invention has been completed based on the discovery that it exhibits excellent properties and effects.

(Means for Solving the Problems) That is, the present invention is a phosphoric acid ester compound represented by the general formula t.

Rl -0-))-0-R3 However, R1 in the formula is a self-condensed polyester of hydroxycarboxylic acid, the terminal thereof is a carboxyl group or an ester group with alcohol, and R2 is a hydrogen atom r or a cation. , [one 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 force method. .

As the phosphorylating agent, conventionally known phosphorus oxychloride, phosphorus 11 oxide, phosphorus chloride, phosphoric anhydride, acetyl phosphorus 11, etc. are used. Phosphorus oxidide is the most preferred phosphorylating agent.

The reaction conditions are oxy13! In the case of phosphorus chloride, the initial esterification reaction is intense, so it is preferable to carry out the reaction at a low temperature, and in order to accelerate the reaction, the pressure of the reactor is reduced to remove the generated hydrogen chloride. 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 jfJ group is also used, for example, E-class amines such as triethylamine, pyridine, 2,6-lutidine, ■,8-diaza- Organic bases such as bicyclo(5,4,0)undecene-7, oxides, hydroxides, carbonates, organic acid salts, etc. of alkali metals and alkaline earth metals, manifest or latent free! ! group is used, and after the reaction, the halide, 1t!, is removed by filtration, neutralization, washing with water, etc. , ifi groups and other impurities are preferably removed.

The alcohol component to be reacted can be selected depending on the purpose of the product.1. used.

The phosphoric acid ester compound of the present invention can be prepared by directly reacting a polyester alcohol component or the like that is compatible with the I heavy compound with a phosphorylating agent to obtain the desired product, or by preliminarily preparing, for example,
By reacting with methyl ester of 2-hydroxystearic acid or the like to synthesize a di- or monoester having a terminal terminal such as methyl ester, the methyl ester is then hydrolyzed, or by reacting it with 12-hydroxystearic acid or its polyester or other. It can also be obtained by a method such as condensation with an alcohol 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 acid of the polyester alcohol component used is not particularly regulated, but it is a dimer to an average amount of
,000 or less, preferably from 500 to 5,000.

As such a polyester alcohol, for example, one such as Doki is used.

(A) Self-condensing polyesters of hydroxycarboxylic acids, preferably polyesters of hydroxycarboxylic acids containing a hydrocarbon chain having 4 to 30 carbon atoms.

For example, lysyllic 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
- One or more self-condensing polyesters selected from hydroxycarboxylic acids such as carboxylic acids.

(B) An esterified product of the carboxylic acid at the other end of the polyester alcohol component described in Section 1 (A).

These are esters with aliphatic, aliphatic or aromatic alcohols having 1 to 30 carbon atoms, such as methyl-, ethyl-, propyl-, butyl-
, hexyl, octyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl alcohol and the like.

In addition to the phosphoric diester compound of the polyester alcohol component described in Section L, the phosphoric acid ester compound of the present invention contains only a monoester in which the polyester alcohol component and the phosphorylating agent are reacted, and other monoester components that are conventionally known. It also includes J1 symmetric phosphodiester compounds esterified using hydroxycarboxylic acids, alcohol esters of hydroxycarboxylic acids, or alcohols, and is synthesized according to the conventional method for synthesizing J1 symmetric phosphodiester compounds. .

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-
It is an ester of carboxylic acid, etc. and an alcohol having 1 to 30 carbon atoms, and the alcohol has 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, cyclo These include hegysyl alcohol and benzyl alcohol.

In the phosphoric acid esterification reaction of the alcohol component mainly composed of the polyester alcohol of the present invention as described in -1-, it is inactive with respect to these raw materials 1 and the product, and [1] It is also preferable to use an organic solvent that dissolves these raw materials.

For example, aliphatic saturated hydrocarbons such as octane, petroleum ether, ligroin, mineral spirit, and kerosene; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as trichloroethane and tetrachloroethane; 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 acids, magnesium, calcium, strontium, barium, etc.
For polyvalent metals such as manganese, iron, cobalt, zinc, zinc, aluminum, tin; ammonium salt; methyl, ethyl, propyl, butyl, hexyl
, octyl-, dodecyl-, octadecyl-, oleyl-, diethyl-, dibutyl-, distearyl-, triethyl-, tributyl-, dimethyloctyl-, dimethyldecyl-, dimethyldodecyl-, dimethyltetradecyl-, dimethylhexadecyl- , dimethyloctadecyl-
, dimethyloleyl-, dilaurylmonomethyl-, trioctyl-amine, dimethylaniline; ethylenediamine, propylenediamine, hexamethylenediamine, stearylpropylenediamine, etc.) & element a1-30 primary, secondary, tertiary Quaternary ammonium salts such as salts and polyamine salts, octadecyltrimethylammonium, dioctadecyldimethylammonium, and ethanolamine, jetanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, propatoolamine, dibrobanolamine, Alkanolamines such as alkanolamines prepared by adding ethylene oxide to the above-mentioned higher aliphatic amines ■1!
etc., and can be used alone or in combination. Also,
Higher aliphatic amines and ammoniums include raw materials and 1.
Compounds of amines with different carbon numbers or degrees of saturation derived from natural fats and oils may also be used as they are.

Depending on the balance with hydrophobic groups, among the salts listed in L, alkali metal salts, ammonium 11! , lower amines, lower alkanolamine salts, etc. exhibit wood-philicity and are water-soluble or water-dispersible, and should be used in an aqueous solution or water! Can be used with 4tI solution.

In addition, higher amine salts for polyvalent metals of divalent or higher than -1- are hydrophobic and exhibit lipophilic P1, and can be used alone as a solvent to make the surface of a base material such as a pigment hydrophobic or as an oil + II agent. It can also be used as a solution.

Of course, after treating the base material such as face 4 in advance with an acid form or an aqueous solution or dispersion of the former, it is possible to react with a polyvalent metal compound or a higher amine compound to form the latter sacred wood compound or oil-based compound. The compound is also used to treat the base material of the face.

(Action/Effect) The phosphoric acid ester compound bonded with polyester chains obtained by the present invention can be used as a natural phospholipid lecithin in the field of coloring materials such as coloring agents, printing inks, and plastic coloring agents. It has no fear of deterioration or decomposition due to oxidation or rancidity as seen in the above, has excellent stability, and has excellent effects on surface modification and dispersion in media.

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 due to the effects of its phosphoric acid ester bonds, the charge adsorption properties of the ester bonds, and the hydrophilic properties of the hydrocarbon chains, the surface of the face is hydrophilic.
Particularly treated to be lipophilic, part #1. Improves dispersibility in media. Therefore, it can be used as a dispersion aid when dispersing using a dispersion or kneading machine, or as a flushing aid from an aqueous paste or a filter cake into an oily dispersion medium.

In addition, the phosphoric acid ester compound of the present invention can be used as a conductive material for similar fine solid materials, such as magnetic recording materials, metal fibers, high-straight carbon black, and carbon fibers, and electromagnetic wave shielding materials. 4. It is also useful as an additive such as a dispersion aid for ceramic materials and the like.

Next, the present invention will be explained in detail with reference to Examples. In addition, the words "bu" or "%" in the text are based on Jyusha standards.

Example 1 (1) Synthesis of 12-hydroxystearic acid self-condensed polyester and its methyl esterification reaction.

Four glass reactors and an oil path were prepared, each having a stirrer, a thermometer, a reverse wave condenser with a moisture meter, and an inlet.

100 fi of 12-hydroxystearic acid and 100 parts of toluene were charged therein and dissolved by stirring. After dissolving, moisten A and use P-)luenesulfonic acid 1 as a condensation catalyst.
．． 0 parts were added. The reaction solution was heated to 120°C, and 12-
The self-condensation polyesterification reaction of hydroxystearic acid was progressed.

The progress of the reaction was checked by the amount of leaked water and the infrared absorption spectrum of the reactants at 60 minutes, 120 minutes, and 180 minutes.
The polyesterification reaction was completed by cooling in 0 minutes.

Then, when the temperature reached 63°C, 50 parts of methanol, 100 parts of methyl acetate, and 0.5 parts of P-toluenesulfonic acid were added.
The temperature was raised to 110° C., and the methyl esterification reaction was proceeded while leaking the solvent. At the point where 150 parts were distilled and leaked, the temperature was lowered to 63°C, 200 parts of methanol was added, and 110 parts of methanol was added.
The temperature was raised to ℃ 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 material, and the outside of the oil layer, which was separated into two layers, was taken out. For dehydration, 150 parts of toluene and 200 parts of methanol were added to the oil layer, heated to 130°C while blowing nitrogen gas, and the solvent was distilled off. The early leakage was 345 parts.

The reaction product obtained was an amber liquid, and analytical data from infrared absorption spectra and gel permeation chromatography showed that it was a methyl ester of a self-condensing polyester of 12-hydroxystearic acid. Confirmed at.

It was confirmed that the methyl esterification reaction of the polymer was almost completed from the acid value of the reaction product, which was constant at 111. Further, the measured value of hydroxylation of the reaction product was 40.8. From this, 1 gram of methyl ester of this self-condensed polyester of 12-hydroxystearic acid is 1375, and the 4i homogeneous condensation market I11 from that is 1375.
' is approximately 5.

(2) Synthesis reaction of phosphoric diester compound of methyl ester of self-condensing polyester of 12-hydroxystearic acid.

Stirrer, thermometer, dropping funnel and backflow condenser
A fourth glass reactor and water path were prepared.

1f occurs in a backflow capacitor! A glass tube for removing acid scum was attached, and a safety bottle and a hydrochloric acid gas absorption box were connected to this tube, and a mercury pressure gauge was connected to the tube, which was connected to a vacuum pump.

7.0 parts of phosphorus oxychloride was charged to the reactor.

Separately, 62.8 parts of the self-condensed polyester methyl ester of 12-hydroxystearic acid obtained in (1) above (1 gram is 1375) and 62.8 parts of benzene were mixed and dissolved, and the mixture was charged into a dropping funnel and placed into a reactor. loaded into.

While the reactor was externally cooled with ice and water, the benzene solution of the methyl ester of the polyester of 12-hydroxystearic acid described in -1- was heated to 5 to 10°C, taking particular care not to allow the temperature to rise above 10°C. While dripping. After the addition is complete, the mixture is stirred at 10° C. for 1 hour, and the pressure inside the reactor is gradually reduced while raising the reaction temperature, so that the hydrochloric acid gas produced by the reaction is absorbed 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 to 100■
- Hg and cool after no longer generating hydrochloric acid gas. In this state, phosphoric acid (methyl ester of poly12-hydroxystearic acid) monoester dichloride is produced. Then 62.8 parts of methyl ester of polyester of 12-hydroxystearic acid as described in 1- above,
62.8 parts of benzene and 4.62 parts of triethylamine were mixed and dissolved, and the mixture was poured into a dropping funnel and added dropwise over 60 minutes at 10 to 20°C to react, stirred for 2 hours, and then over 2 hours. The mixture was heated to 40°C for 4 hours, stirred for 2 hours, and cooled.

The ratio of the polyester having a hydroxyl group at -, phosphorus oxychloride and triethylamine is 2:3:l.

Next, in order to dechlorinate (hydrolyze) and remove phosphate ester chloride and to remove triethylamine hydrochloride from the reaction product solution, the solution was washed with water, Hanaki sodium oxide solution, diluted hydrochloric acid acid water, 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 determined by infrared absorption spectrum and gel permeation chromatography analysis chart.
It was confirmed that the main component is a phosphoric diester compound of methyl ester of self-condensed polyester of hydroxystearic acid.

The approximate average molecular value of the main components is 2,500 to 2.80
It was 0.

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, 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.

Phosphoric diester compound of methyl ester of 12-hydroxystearic acid polyester obtained above and its organic amine salt, metal ■ old copper phthalocyanine blue pigment, copper phthalocyanine green pigment, soluble azo lake face 1, insoluble azo lake pigment, When dispersing pigments such as carbon black pigment, it was effective in preparing high concentrations, shortening dispersion time, improving dispersibility, etc., and was also effective as an additive in flushing from aqueous press cake.

Example 2-11 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 The four glass reactors used in Example 1 (2), including the stirrer, thermometer, dropping funnel, reverse wave condenser, pressure reduction system, and acid gas absorption system, were installed. 7.0 parts of phosphorus oxychloride was charged.

Separately, poly-12- synthesized in the same manner as in Example 1 (1)
65.8 parts of methyl ester of hydroxystearic acid (average molecular weight is 1,440) was mixed with 65.8 parts of benzene.
Mix and dissolve in 1 part, add 1 to the funnel, and add (1) of Example 1.
2) to produce phosphoric acid (methyl ester of poly-12-hydroxystearic acid) monoester dichloride, and then poly-12-hydroxy synthesized in the same manner as in Example 1 (1). 27.4 parts of methyl stearic acid (600 to 11 parts) was mixed and dissolved with 27.4 parts of benzene and 4.62 parts of triethylamine, and the mixture was reacted in the same manner as in Example 1 (2).

[-In the equation, the equivalent ratio of 11 equal parts -f-$41.440 polyester alcohol, 1 part equal part polyester alcohol, 1 part equal phosphorus monochloride, and triethylamine is 1:1:3:1. be.

The cooled reaction product liquid was treated in the same manner as in Example 1 (2),
A brown liquid reaction product was obtained by dechlorination (hydrolysis), washing, purification, drying, concentration and solvent removal.

Analyzes were conducted in the same manner as in Example 1 (2), and it was found to be a phosphoric acid diester of methyl ester of poly-12-hydroxystearic acid, and the approximate qi ratio of its main components was approximately 1,90.
It was confirmed that it was between 0 and 2,100.

Similar to the phosphoric acid diester compound of Example 1, this compound was usefully used as a pigment dispersion aid, flushing aid, etc. in the acid form, organic amine f11, and metal In form.

Examples 13 to 20 Various phosphate 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.

These compounds were advantageously used as pigment dispersion aids, flushing aids, etc. in the acid form, for organic amines, and in the metal n1 form, similar to the ethyl phosphate in Example 1.

(Left below) Nro 201clc Co 00 00
0ON --- e't cl, 1e'p cu a
j N c') IN
e')■ -Mi Pregnancy-N -N o Oro Ro0 - 〇 ~ ■-Ro+~ -~ -~ C') IN N 020 Nro'? O o oc
oo c.

Dimensions − Ri − Dimensions −
C'5--C1') +1 -
■ -0 RO ri■ Moan-〇0 0 ROW + ■(II)...
- Approximate average molecular acid of the main component of the produced phosphoric acid di- or monoester These are the same as the phosphoric acid diester of Example 1, acid form, organic amine salt and metal 11! It was commonly used as a pigment dispersion aid, flushing aid, etc.

Claims (2)

[Claims] (1) A phosphoric acid ester compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, R1 in the formula is a self-condensed polyester of hydroxycarboxylic acid, the terminal thereof is a carboxyl group or an ester group with alcohol, and R2 is a hydrogen atom or a cation. , and R3 is R1, R2 or a hydrocarbon group. ] (2) Claim No. 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.
The phosphoric acid ester compound described in section.