JPH0585209B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel emulsifying and dispersing agent composition. Conventionally, surfactants made by converting higher alcohols and compounds obtained by adding ethylene oxide to higher alcohols and alkylphenols into phosphate esters have been widely used as emulsifying and dispersing agents for various substances in oil and water systems. However, as the target objects of emulsifying and dispersing agents have recently expanded, there has been a demand for emulsifying and dispersing agents with even higher performance. As a result of intensive research into improving the emulsifying and dispersing performance of phosphate ester type surfactants from this perspective, the present inventors found that when such conventionally known phosphate ester type surfactants are used in combination with nitrogen-containing surfactants. We found that there was a significant improvement in performance,
This led to the present invention. That is, the present invention relates to general formula (1) or general formula (2)

[Chemical formula] (However, R ₁ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and R ₂ is OH or R ₁ O.)

[Chemical formula] (However, R ₃ is an alkyl group having 8 to 22 carbon atoms, a higher alcohol having an alkenyl group, or an alkylphenol having an alkyl group having 4 to 12 carbon atoms, and 1 to 1 to 1 mol of ethylene oxide or/and propylene oxide. 100 mole added residue,
R ₄ is OH or R ₃ O. ) for 100 parts by weight of at least one compound represented by general formula (3), (4),
(5) or (6)

[Chemical formula] [R ₅ is ethylene or propylene, R ₆ is a hydrogen atom or (R ₅ O)nH, n is an integer from 1 to 50]

[ka]

[Chemical formula] {However, R ₇ is an alkyl group or alkenyl group having 7 to 21 carbon atoms, and R ₈ is a formula

[However, x is 0 or an integer from 1 to 3, R ₉ is R ₇
CON or (R ₅ O)nH]

[Chemical formula] {However, R ₁₀ is (R ₅ O)nH, or the following formula

[C] However, R ₁₁ is R ₆ ,

[Formula] (y is 0 or an integer of 1 to 2, R ₁₂ is

[Formula] Ma Taha

[Formula]). } A new emulsifying and dispersing agent composition is provided by blending 20 to 500 parts by weight of at least one of the compounds shown in the following. The emulsifying and dispersing agent composition of the present invention can be obtained as follows. First, phosphoric acid ester type surfactants represented by general formulas (1) and (2) are decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, cetyl alcohol, oleyl alcohol, and 11 carbon atoms from the oxo method. ~15 mixed alcohols, secondary alcohols with 12 to 13 carbon atoms, and nonionic surfactants with 1 to 100 moles of ethylene oxide or/and propylene oxide added to 1 mole of these higher alcohols by a known method, butyl phenol. , octylphenol, nonylphenol,
Using a nonionic surfactant made by adding 1 to 100 moles of ethylene oxide or/and propylene oxide to 1 mole of dodecylphenol or dinonylphenol using a known method as a raw material, 1 mole of these raw materials is mixed with phosphorus oxychloride and pentoxide. It is obtained by reacting 0.3 to 1.0 mol of phosphorus, preferably phosphorus pentoxide, by a known method, and is usually obtained as a mixture of a monoester and a diester. Preferred in terms of performance are lauryl alcohol, tridecyl alcohol, oleyl alcohol, mixed alcohols having 11 to 15 carbon atoms from the oxo method, octylphenol, and nonionic surfactants prepared by adding 5 to 15 moles of ethylene oxide to 1 mole of nonylphenol. A phosphate ester type surfactant made from a surfactant is preferred. Aminoether type surfactants represented by general formulas (3), (4), (5) and (6) include decylamine, dodecylamine, ministylamine, palmotylamine, cetylamine, stearylamine, tallow amine, and behenylamine. , lauryl aminopropylamine, tallow aminopropylamine, and higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid, and ethylenediamine, propylenediamine, aminoethylethanolamine, diethylenetriamine, triethylenepentamine, and tetraethylene. R ₇ CONHC ₂ H ₄ NH ₂ , R ₇ CONHC ₂ H ₄ NHC ₂ obtained by reacting with amines such as pentamine by a known method.
H ₄ OH, R ₇ CONHC ₂ H ₄ NHC ₃ H ₆ NH ₂ , R ₇
CONHC ₂ H ₄ NHC ₂ H ₄ NHOCR ₇ , R ₇ CONH (C ₂
H ₄ NH) ₂ C ₂ H ₄ NH ₂ , R ₇ CONH (C ₂ H ₄ NH) ₂ C ₂ H ₄
NHOCR ₇ , R ₇ CONH (C ₂ H ₄ NH) ₃ C ₂ H ₄ NH ₂ , R _{7
CONH ( C2H4NH ) 3C2H4NHOCR7 ,}

【formula】

【formula】

[ka]

It is obtained by adding 1 to 300 moles of ethylene oxide to 1 mole of these raw materials by a known method using an amide compound or imidazoline compound such as , myristylamine, palmitylamine, stearylamine, tallow aminopropylamine, C ₁₇ H ₃₅ CONHC ₂ H ₄ NHC ₂ H ₄ NH ₂ ,
C ₁₇ H ₃₅ CONHC ₂ H ₄ NHC ₂ H ₄ NHC ₂ H ₄ NHOCC _17
H35 ,

【formula】

[Chemical formula] An aminoether type surfactant in which 5 to 20 moles of ethylene oxide is added to 1 mole is preferred.
The ratio of the phosphate ester type surfactant and aminoether type surfactant thus obtained is 1:0.2 to 1:5.
It is preferable that the acid value equivalent of the phosphate ester type surfactant and the amine value equivalent of the aminoether type surfactant are neutralized, and the weight ratio In other words, 1:
The ratio is in the range of 0.5 to 1:2. The characteristics of the novel emulsifying dispersant of the present invention are that it is a proprietary emulsifying dispersing agent with a wide range of applications, exhibits excellent effects, and can also impart rust prevention effects as a secondary effect. Can be used as an emulsifier during polymerization, an emulsifying and dispersing agent for vegetable oils, mineral oils, fragrances, dyes, pigments, etc., a dispersing agent for magnetic iron oxide, metal particles, ceramics, etc. in water and oil, an emulsifying and dispersing stabilizer for water-based paints, etc. . Next, examples of the present invention will be shown. Example 1

[Synthesis of phosphate ester type surfactant (1)] 572 g of 1 mole of poly(8)oxyethylene nonyl phenyl ether, which is obtained by adding 8 moles of ethylene oxide to 1 mole of nonylphenol using a known method, was placed in a four-necked Kolben. , 0.4 mol of phosphorus pentoxide, 57 g was gradually added with stirring at room temperature, and then reacted at 90°C for 5 hours to produce poly(8) in the form of a pale yellow viscous oil with an acid value of 120 measured using a phenolfrethane indicator. Oxyethylene nonyl phenyl ether phosphate was obtained.

[Synthesis of aminoether type surfactant (1)] 1 mol 241 g of hexadecylamine was placed in an autoclave, 0.3 g of sodium acetate was added, and 6 mol 264 g of ethylene oxide was gradually added at 160°C to 3 atm N ₂
The reaction was completed in 4 hours, and poly(6)oxyethylenehexadecylamine was titrated with hydrochloric acid as a yellowish brown viscous oil with an amine value of 111.

[Production of emulsifying dispersant of Example 1] Poly(8) oxyethylene nonyl phenyl ether phosphate (phosphate ester type surfactant (1)
100g and poly(6)oxyethylenehexadecylamine (aminoether type surfactant (1), same below)
95g were mixed at 60°C to obtain Example 1 in the form of a yellowish brown paste. Example 1 is subjected to test values described later.

[Production of Comparative Examples 1, 2, and 3] Poly(8) oxyethylene nonyl phenyl ether phosphate (phosphate ester type surfactant (1)
Comparative Example 1 was obtained by neutralizing 100 g with 32 g of triethanolamine. Comparative Example 2 was prepared by neutralizing 100 g of poly(8)oxyethylene nonyl phenyl ether phosphate with 21.5 g of 40% caustic soda and then dehydrating it. Comparative Example 3 was prepared using poly(6)oxyethylenehexadecylamine alone.

[Dispersion test (1) of Example 1 and Comparative Examples 1, 2, and 3] Weighed 5 g of chromium oxide with an average particle size of 0.5μ in a flask, added 0.2 g of the emulsifying dispersant of Example 1 to 10 c.c. of xylene. A solution of a 1:1 (weight ratio) mixed solvent of and methyl ethyl ketone was added thereto, and the mixture was shaken up and down 20 times. The amount of chromium oxide precipitated after being allowed to stand for 2 hours after shaking was 0.1 ml or less, indicating stable dispersion. On the other hand, when Comparative Examples 1, 2, and 3 were used, the amount was 0.3 ml in Comparative Example 1, and 0.6 ml in Comparative Example 2. Examples 2 to 9

[Synthesis of phosphate ester type surfactants (2) to (9)] Synthesize phosphate ester type surfactants (2) to (8) in the same way as the synthesis of phosphate ester type surfactant (1). 1st
The results shown in the table were obtained.

[Synthesis of aminoether type surfactants (2) to (8)] Aminoether type surfactants (2) to (8) were synthesized in the same manner as the synthesis of aminoether type surfactant (1), and the second The results shown in the table were obtained.

[Production of Examples 2 to 20] Examples 2 to 20 were produced in the same manner as Example 1, and the results are shown in Table 3.

[Dispersion test (2)] 5g of 1.5μ aluminum nitride, 30g of methyl ethyl ketone,
Pour 10g of n-butanol and 0.1g of dispersant into a 100cc beaker, and stir using a magnetic stirrer.
After stirring for an hour, the mixture was transferred to a centrifuge tube and left at room temperature for 8 hours, and the amount of sediment was observed to obtain the results shown in Table 4.

【table】

【table】

【table】

【table】

【table】

[Dispersion test (3)] 100g of No. 4 gasoline, 0.5μ magnesium carbonate
5 g of the dispersant and 0.2 g of the dispersant were mixed and treated with an attritor for 5 hours. The resulting dispersion was left at 40° C. for 1 month and the state of separation was observed. Examples (5), (6), (9),
When (10), (11), (12), (14), (16), and (20) were used, the dispersion was stable and no sedimentation was observed, but comparative example (3), ( When using 5) and (7),
In both cases, a large amount of sediment was observed.

[Emulsification test]

120 seconds Spindle 80g of oil and 20g of emulsifier were placed in a beaker and mixed at room temperature. Add water to the mixture using Examples 4, 6, 13, and 15 as an emulsifier to make 20%
When made into an emulsion, a stable emulsion is formed in either case, and there is a possibility that it can be applied as a spinning oil or a cutting oil.

Claims (1)

[Claims] 1 General formula (1) or general formula (2) [Chemical formula] (However, R ₁ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and R ₂ is OH or R ₁ O.) [Chemical formula] (However, R ₃ is an alkyl group having 8 to 22 carbon atoms, a higher alcohol having an alkenyl group, or an alkylphenol having an alkyl group having 4 to 12 carbon atoms, and 1 to 1 to 1 mol of ethylene oxide or/and propylene oxide. 100 mole added residue,
R ₄ is OH or R ₃ O. ) for 100 parts by weight of at least one compound represented by general formula (3), (4),
(5) or (6) [Formula] [R ₅ is ethylene or propylene, R ₆ is a hydrogen atom or (R ₅ O)nH, n is an integer from 1 to 50] [Formula] [Formula] {However, R ₇ is an alkyl group or alkenyl group having 7 to 21 carbon atoms, R ₈ is the formula [However, x is 0 or an integer of 1 to 3, R ₉ is R ₇
CON or (R ₅ O) nH} [Formula] {However, R ₁₀ is (R ₅ O) nH, or the following formula [Formula] However, R ₁₁ is R ₆ , [Formula] (y is 0 or An integer of 1 to 2, R ₁₂ is [Formula] or [Formula]). } An emulsifying and dispersing agent composition comprising 20 to 500 parts by weight of at least one of the compounds shown in the following.