JP2011190184A - New dicarboxylic acid type compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new dicarboxylic acid type compound that has hydrolysis stability and biodegradability and exhibits excellent surface activity. <P>SOLUTION: The dicarboxylic acid type compound is one represented by formula (1) (wherein C<SB>n</SB>H<SB>2n+1</SB>is a linear or branched alkyl group; n is an integer of 1-22; R<SB>1</SB>is a 1-22C alkylene group; R<SB>2</SB>is a 1-22C alkyl group; R<SB>3</SB>is a hydrogen atom or a methyl group; X is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion or an ammonium ion; provided that R<SB>1</SB>and R<SB>2</SB>are selected so that the -R<SB>1</SB>-CH-CH-R<SB>2</SB>portion forms a 9-25C hydrocarbon structure). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel dicarboxylic acid type compound.

One-chain one-hydrophilic surfactants such as solid soaps using fatty acids that are natural raw materials are widely used in the world because of their high biodegradability and safety. Surfactants with carboxyl groups have various structures, but water-soluble, good detergency and foaming, mild to skin and hair, and effective in small amounts are desired. Yes. Corresponding to these, acylated amino acid salts, ether carboxylates, amide ether carboxylates, amide ether sulfates and the like are known. Recently, expectation for 2-chain 2-hydrophilic surfactant (Gemini surfactant) as an environmentally friendly next-generation surfactant that has excellent surface activity and can reduce the amount of surfactant used. Various research and development of the novel surfactant has been made (Non-patent Document 1).
For example, Patent Document 1 discloses a bis-amide carboxylic acid or a salt thereof, and Patent Document 2 discloses a multi-chain bipolar group compound. In addition, those with different types of hydrophilic groups, those with asymmetric structures of alkyl chains, and two-chain two-hydrophilic surfactants with asymmetric structures of hydrophilic groups and alkyl chains are also being studied. (Non-Patent Document 2).
In addition, gemini-type cationic surfactants or sugar surfactants having an amide bond in the hydrophobic chain have been reported (Non-patent Documents 3 and 4).
A gemini surfactant having an ester bond in a hydrophobic chain has also been reported (Non-patent Document 5).

JP-A-10-175934 JP 2000-219654 A

R. Zana, Journal of Colloid and Interface Science 248, 203-220 (2002) E. Alami and K.M. Holberg, Advances in Colloid and Interface Science 100-102 (2003) 13-46 T.A. Tatsumi, W. et al. Zhang, T .; Kida, Y .; Nakatsuji, D.H. Ono, T .; Takeda, I, Ikeda Journal of Surfactants and Detergents 3, 167 (2000) K. A. Wilk, L.M. Syper, B.M. W. Domagalska, U .; Komorek, I.D. Maliszewska, R.M. Gancarz, Journal of Surfactants and Detergents 5, 235 (2002) T.A. Tatsumi, W. et al. Zhang, T .; Kida, Y .; Nakatsuji, D.H. Ono, T .; Takeda, I, Ikeda Journal of Surfactants and Detergents 4, 279 (2001)

However, 2-chain 2-hydrophilic surfactants often require the use of relatively expensive raw materials in their production, and usually a linking group (spacer) that connects 1-chain 1-hydrophilic surfactants together. It is necessary to carry out a reaction for binding a portion called “the main chain of the surfactant”, which increases the number of steps and complicates the synthesis route. Furthermore, for the synthesis of 2-chain 2-hydrophilic surfactants having asymmetric lengths of 2-hydrophobic groups, two types of 1-chain 1-hydrophilic surfactants having hydrophobic groups with different chain lengths are prepared. , There is a problem that the number of reaction steps increases because it is necessary to combine them. In addition, since the biodegradability is generally inferior due to the compound structure, it is the fact that there is almost nothing that has been put into practical use despite its excellent performance. For example, the gemini-type surfactants of Non-Patent Document 3 and Non-Patent Document 4 having an amide bond do not exhibit biodegradability at all, or exhibit defects such as a slow degradation rate although they exhibit biodegradability.
As described in Non-Patent Document 5, a structure having an ester bond in the hydrophobic chain portion of the gemini surfactant is considered in order to impart biodegradability, but there is a concern that it lacks hydrolysis stability.
As a result of intensive studies to solve the above problems, the present inventors use an unsaturated fatty acid that is industrially easily available as a raw material and has a double bond site that leads to a linking group, or an amide thereof. Succeeded in obtaining a novel dicarboxylic acid type compound that can be easily synthesized, biodegradable, and usable as a surfactant having hydrolytic stability, leading to the completion of the present invention. It was.

但し、上記一般式（１）中、
Ｃ_nＨ_2n+1は直鎖状の又は分岐状のアルキル基を示し、
ｎは１〜２２の整数を示し、
Ｒ₁は炭素原子数１〜２２のアルキレン基を示し、
Ｒ₂は炭素原子数１〜２２のアルキル基を示し、
Ｒ₃は、水素原子または、メチル基を示し、
Ｘは、水素イオン、アルカリ金属イオン、アルカリ土類金属イオン、又はアンモニウムイオンを示すが、但し、前記Ｒ₁及びＲ₂は−Ｒ₁−ＣＨ−ＣＨ−Ｒ₂部分が炭素原子数９〜２５の炭化水素構造をなすように選択される。
本発明はまた、前記のジカルボン酸型化合物を含む、界面活性剤に関する。
本発明は更に、下記一般式（２´）

（式中、
Ｃ_nＨ_2n+1は直鎖状の又は分岐状のアルキル基を示し、
ｎは１〜２２の整数を示し、
Ｒ₁は炭素原子数１〜２２のアルキレン基を示し、
Ｒ₂は炭素原子数１〜２２のアルキル基を示し、
Ｒ₃は、水素原子または、メチル基を示すが、但し、前記Ｒ₁及びＲ₂は−Ｒ₁−ＣＨ−ＣＨ−Ｒ₂部分が炭素原子数９〜２５の炭化水素構造をなすように選択される。）で表される化合物と無水コハク酸を反応させて下記一般式（１´）

（式中、Ｃ_nＨ_2n+1、ｎ、Ｒ₁、Ｒ₂及びＲ₃は、一般式（２´）における定義と同様の意味を表わす。）で表される化合物を製造する段階と、続いて、場合により、一般式（１´）で表される化合物をアルカリ金属若しくはアルカリ土類金属の水酸化物又はアミンと反応させて下記一般式（１）

（式中、Ｃ_nＨ_2n+1、ｎ、Ｒ₁、Ｒ₂及びＲ₃は、一般式（２´）における定義と同様の意味を表わし、Ｘは、水素イオン、アルカリ金属イオン、アルカリ土類金属イオン、又はアンモニウムイオンを示す。）で表される化合物を製造する段階とを含む、ジカルボン酸型化合物の製造方法にも関する。 That is, the present invention is a novel dicarboxylic acid type compound represented by the following general formula (1).

However, in the general formula (1),
C _n H _{2n + 1} represents a linear or branched alkyl group,
n represents an integer of 1 to 22,
R ₁ represents an alkylene group having 1 to 22 carbon atoms,
R ₂ represents an alkyl group having 1 to 22 carbon atoms,
R ₃ represents a hydrogen atom or a methyl group,
X represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, or an ammonium ion, provided that R ₁ and R ₂ have a —R ₁ —CH—CH—R ₂ moiety of 9 to 25 carbon atoms. The hydrocarbon structure is selected.
The present invention also relates to a surfactant comprising the dicarboxylic acid type compound.
The present invention further includes the following general formula (2 ′):

(Where
C _n H _{2n + 1} represents a linear or branched alkyl group,
n represents an integer of 1 to 22,
R ₁ represents an alkylene group having 1 to 22 carbon atoms,
R ₂ represents an alkyl group having 1 to 22 carbon atoms,
R ₃ represents a hydrogen atom or a methyl group, provided that R ₁ and R ₂ are selected so that the —R ₁ —CH—CH—R ₂ moiety forms a hydrocarbon structure having 9 to 25 carbon atoms. Is done. ) And a succinic anhydride are reacted to give the following general formula (1 ′)

(Wherein, C _n H _{2n + 1} , n, R ₁ , R ₂ and R ₃ have the same meaning as defined in formula ( ₂ ′)), Subsequently, in some cases, the compound represented by the general formula (1 ′) is reacted with an alkali metal or alkaline earth metal hydroxide or amine to give the following general formula (1):

(In the formula, C _n H _{2n + 1} , n, R ₁ , R ₂ and R ₃ represent the same meaning as defined in the general formula ( _{2 ′} ), and X represents a hydrogen ion, an alkali metal ion, an alkaline earth, And a method for producing a compound represented by the following formula:

The dicarboxylic acid type compound of the present invention is a naturally occurring unsaturated fatty acid that is industrially easily available or its amide used as a raw material, so that the double bond site of the unsaturated fatty acid part of the raw material becomes a linking group, and Since the dicarboxylic acid or a salt thereof can be easily bonded to the hydroxyl group obtained by oxidizing the double bond portion, the production has an advantage that it can be easily synthesized with a small number of reaction steps. In the dicarboxylic acid type compound of the present invention,
The hydrophilic-hydrophobic balance is easily adjusted by selecting the length of the alkyl chain (C _n H _{2n + 1} ) in the starting amine to be amide-bonded to the terminal carboxylic acid moiety of the fatty acid chain, or an unsaturated fatty acid. Thus, the compounds of the present invention are useful as surfactants. Further, the surfactant of the present invention is excellent in emulsifying power in a small amount, has excellent surface activity, and has biodegradability which is an indispensable condition for use as a surfactant. From the viewpoint of use, it is excellent in hydrolysis stability that is required to the extent that performance is not impaired when it is assumed to be used according to the application. The dicarboxylic acid type compound of the present invention having these characteristics is also very useful from the viewpoints of industrial applicability, resource saving, and low load on the environment.

FIG. 1 shows the ¹ H-NMR spectrum of the dicarboxylic acid type compound obtained in Example 2. FIG. 2 shows the ¹³ C-NMR spectrum of the dicarboxylic acid type compound obtained in Example 2.

但し、上記一般式（１）中、Ｃ_nＨ_2n+1は直鎖状の又は分岐状のアルキル基を示し、ｎは１〜２２の整数を示す。Ｒ₁は炭素原子数１〜２２のアルキレン基を示し、Ｒ₂は炭素原子数１〜２２のアルキル基を示す。但し、Ｒ₁及びＲ₂は−Ｒ₁−ＣＨ−ＣＨ−Ｒ₂部分が炭素原子数９〜２５の炭化水素構造をなすように選択される。Ｒ₃は、水素原子または、メチル基を示す。Ｘは、水素イオン、アルカリ金属イオン、アルカリ土類金属イオン、又はアンモニウムイオンを示す。 The dicarboxylic acid type compound of the present invention is represented by the following general formula (1).

However, in the general formula _{(1), C n H 2n} + 1 is a straight or branched alkyl group, n is an integer of 1 to 22. R ₁ represents an alkylene group having 1 to 22 carbon atoms, and R ₂ represents an alkyl group having 1 to 22 carbon atoms. However, R ₁ and R ₂ are selected so that the —R ₁ —CH—CH—R ₂ moiety forms a hydrocarbon structure having 9 to 25 carbon atoms. R ₃ represents a hydrogen atom or a methyl group. X represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, or an ammonium ion.

In the general formula (1), examples of the linear or branched alkyl group having 1 to 22 carbon atoms represented by C _n H _{2n + 1} include a methyl group, an ethyl group, an n-propyl group, an n- Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n- Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, isopropyl group, isobutyl group, sec -Butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, 2-ethylhexyl group and the like are mentioned, but n-butyl group, n-hexyl group, n- Ptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-docosyl group, isopropyl group, isobutyl group, 2 -An ethylhexyl group is preferred.

In the general formula (1), examples of the alkylene group having 1 to 22 carbon atoms represented by R ₁ include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, and n-hexylene. Group, n-heptylene group, n-octylene group, n-nonylene group, n-
Decylene group, n-undecylene group, n-dodecylene group, n-tridecylene group, n-tetradecylene group, n-pentadecylene group, n-hexadecylene group, n-heptadecylene group, n-octadecylene group, n-nonadecylene group, n- Examples include icosylene group, n-henicosylene group, n-docosylene group, etc., preferably methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene. Group, n-octylene group, n-nonylene group, n-decylene group, n-undecylene group, n-dodecylene group, n-tridecylene group and n-pentadecylene group. More preferably, a methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-nonylene group, n-decylene group, n-undecylene group, etc. Is mentioned.

In the general formula (1), examples of the alkyl group having 1 to 22 carbon atoms represented by R ₂ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group Group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, etc., in order to ensure hydrophobic interaction, preferably n -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-nonadecyl Group, and the like.

In the above general formula (1), the —R ₁ —CH—CH—R ₂ moiety selected to form a hydrocarbon structure having 9 to 25 carbon atoms is, for example, — (CH ₂ ) ₂ —CH—CH. _{- (CH 2) 4 CH 3} , - (CH 2) 7 -CH-CH-CH 3, -CH 2 -CH-CH- (CH 2) 7 -CH 3, - (CH 2) 2 -CH-CH _{- (CH 2) 6 CH 3} , - (CH 2) 3 -CH-CH- (CH 2) 5 CH 3, - (CH 2) 7 -CH-CH- (CH 2) 2 CH 3, - (CH _{2) 2 -CH-CH- (CH} 2) 8 CH 3, - (CH 2) 3 -CH-CH- (CH 2) 7 CH 3, - (CH 2) 7 -CH-CH- (CH 2) ₃ CH ₃ , — (CH ₂ ) ₄ —CH—CH— (CH ₂ ) ₇ CH ₃ , — (CH ₂ ) ₇ —CH—CH— (CH ₂ ) ₄ CH ₃ , —CH ₂ —CH—CH— (CH _{2) 11 H 3, - (CH 2)} 5 -CH-CH- (CH 2) 7 CH 3, - (CH 2) 7 -CH-CH- (CH 2) 5 CH 3, - (CH 2) 5 -CH- _{CH- (CH 2) 8 CH 3} , - (CH 2) 6 -CH-CH- (CH 2) 7 CH 3, - (CH 2) 7 -CH-CH- (CH 2) 6 CH 3, -CH ₂ -CH—CH— (CH ₂ ) ₁₃ CH ₃ , — (CH ₂ ) ₂ —CH—CH— (CH ₂ ) ₁₂ CH ₃ , — (CH ₂ ) ₄ —CH—CH— (CH ₂ ) ₁₀ CH ₃ , — (CH ₂ ) ₅ —CH—CH— (CH ₂ ) ₉ CH ₃ , — (CH ₂ ) ₆ —CH—CH— (CH ₂ ) ₈ CH ₃ , — (CH ₂ ) ₇ —CH—CH _{- (CH 2) 7 CH 3} , - (CH 2) 9 -CH-CH- (CH 2) 5 CH 3, - (CH 2) 7 -CH-CH- (CH 2) 8 CH 3, - (CH _{2) 9 -CH-CH- (CH} 2) 7 _{CH 3, - (CH 2)} 10 -CH-CH- (CH 2) 7 CH 3, - (CH 2) 11 -CH-CH- (CH 2) 7 CH 3, - (CH 2) 8 -CH- _{CH- (CH 2) 11 CH 3} , - (CH 2) 12 -CH-CH- (CH 2) 7 CH 3, - (CH 2) 13 -CH-CH- (CH 2) 7 CH 3, - ( _{CH 2) 3 -CH-CH- (} CH 2) 18 CH 3, - (CH 2) 15 -CH-CH- (CH 2) 6 CH 3, - (CH 2) 15 -CH-CH- (CH 2 ) ₇ CH _{3 and the} like, among which —CH ₂ —CH—CH— (CH ₂ ) ₇ —CH ₃ , — (CH ₂ ) ₂ —CH—CH— (CH ₂ ) ₆ CH ₃ , — _{(CH 2) 3 -CH-CH-} (CH 2) 5 CH 3, - (CH 2) 2 -CH-CH- (CH 2) 8 CH 3, - (CH 2) 3 -CH-CH- (CH _{2) 7} CH _3, - ( _{H 2) 4 -CH-CH- (} CH 2) 7 CH 3, -CH 2 -CH-CH- (CH 2) 11 CH 3, - (CH 2) 5 -CH-CH- (CH 2) 7 CH ₃ , — (CH ₂ ) ₇ —CH—CH— (CH ₂ ) ₅ CH ₃ , — (CH ₂ ) ₅ —CH—CH— (CH ₂ ) ₈ CH ₃ , — (CH ₂ ) ₆ —CH—CH _{- (CH 2) 7 CH 3} , - (CH 2) 7 -CH-CH- (CH 2) 6 CH 3, -CH 2 -CH-CH- (CH 2) 13 CH 3, - (CH 2) 2 _{-CH-CH- (CH 2) 12} CH 3, - (CH 2) 4 -CH-CH- (CH 2) 10 CH 3, - (CH 2) 5 -CH-CH- (CH 2) 9 CH 3 , — (CH ₂ ) ₆ —CH—CH— (CH ₂ ) _{8
CH 3, - (CH 2)} 7 -CH-CH- (CH 2) 7 CH 3, - (CH 2) 9 -CH-CH- (CH 2) 5 CH 3, - (CH 2) 7 -CH- _{CH- (CH 2) 8 CH 3} , - (CH 2) 9 -CH-CH- (CH 2) 7 CH 3, - (CH 2) 10 -CH-CH- (CH 2) 7 CH 3, - ( _{CH 2) 11 -CH-CH- (} CH 2) 7 CH 3 are preferred.

The following general formula (2) which is a raw material of the dicarboxylic acid type compound of the present invention

Is an amidation reaction of an unsaturated fatty acid having 10 to 26 carbon atoms and an aliphatic amine having 1 to 22 carbon atoms, or a lower level of an unsaturated fatty acid having 10 to 26 carbon atoms. It can be obtained by an ester amide exchange reaction between an alkyl ester and an aliphatic amine having 1 to 22 carbon atoms.
Examples of the unsaturated fatty acid having 10 to 26 carbon atoms include 4-decenoic acid having 10 carbon atoms, 9-undecenoic acid having 11 carbon atoms, Linderic acid having 12 carbon atoms, succinic acid, lauroleic acid and the like. 3-dodecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, cis-9-tridecenoic acid having 13 carbon atoms, tzuic acid having 14 carbon atoms, 4-tetradecenoic acid such as myristoleic acid, 5-tetradecene Acid, 9-tetradecenoic acid, 6-pentadecenoic acid having 15 carbon atoms, cis-9-pentadecenoic acid, trans-3-hexadecenoic acid such as palmitoleic acid having 16 carbon atoms, cis-7-hexadecenoic acid, cis-9 Hexadecenoic acid, trans-9-hexadecenoic acid, cis-7-heptadecenoic acid having 17 carbon atoms, cis-8-heptadecenoic acid, c trans-9-octadecenoic acid, cis-3-octadecenoic acid, trans-4-octadecenoic acid such as s-9-heptadecenoic acid, petroselinic acid having 18 carbon atoms, petroseleidic acid, oleic acid, elaidic acid, pasenic acid Cis-6-octadecenoic acid, trans-6-octadecenoic acid, cis-7-octadecenoic acid, trans-7-octadecenoic acid, cis-8-octadecenoic acid, trans-8-octadecenoic acid, cis-9-octadecenoic acid, cis-11-eicosenoic acid such as trans-9-octadecenoic acid, cis-11-octadecenoic acid, trans-11-octadecenoic acid, cis-9-nonadecenoic acid having 19 carbon atoms, and gondonoic acid having 20 carbon atoms, trans -11-eicosenoic acid, 21 carbon atoms 2-Henicosenoic acid, erucic acid having 22 carbon atoms, cis-13-docosenoic acid such as brassic acid, trans-13-docosenoic acid, 10-tricosenoic acid having 23 carbon atoms, 14-tricosenoic acid, 24 carbon atoms Cis-15-tetracosenoic acid such as ceracoleic acid, trans-15-tetracosenoic acid, cis-15-pentacosenoic acid having 25 carbon atoms, cis-17-pentacenoic acid, cis-17-hexacosenic acid having 26 carbon atoms, etc. Unsaturated fatty acids having 12 to 22 carbon atoms are preferred, and oleic acid and erucic acid are preferred from the viewpoint of industrial raw material supply and inexpensive raw materials.

Examples of the aliphatic amine having 1 to 22 carbon atoms include methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine. N-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-icosylamine, n-hecosylamine, n-docosylamine, isopropylamine, isobutylamine, sec-butylamine, tert-butylamine, isopentylamine, neopentylamine, tert-pentylamine, 2- Echi Saturated aliphatic primary amines such as hexylamine, dimethylamine, N-methylethylamine, N-methylpropylamine, N-methylbutylamine, N-methylpentylamine, N-methylhexylamine, N-methylheptylamine, N -Methyloctylamine, N-methylnonylamine, N-methyldecylamine, N-methylundecylamine, N-methyldodecylamine, N-methyltridecylamine, N-methyltetradecylamine, N-methylpentadecylamine N-methylhexadecylamine, N-methylheptadecylamine, N-methyloctadecylamine, N-methylnonadecylamine, N-methylicosylamine, N-methylhenicosylamine, N-methyldocosylamine, N -Methylisopropylamine, N-methyl Sobutylamine, N-methyl-sec-butylamine, N-methyl-tert-butylamine, N-methylisopentylamine, N-methyl-neopentylamine, N-methyl-tert-pentylamine, N-methyl-2-ethylhexyl Saturated aliphatic secondary amines such as amines can be mentioned, but n-butylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, n-tetra Decylamine, n-hexadecylamine, n-octadecylamine, n-docosylamine, isopropylamine, isobutylamine, 2-ethylhexylamine, N-methylbutylamine, N-methylhexylamine, N-methylheptylamine, N-methyloctyl Amine, N-methyl Nonylamine, N-methyldecylamine, N-methyldodecylamine, N-methyltetradecylamine, N-methylhexadecylamine, N-methyloctadecylamine, N-methyldocosylamine, N-methylisopropylamine, N-methyl Isobutylamine and N-methyl-2-ethylhexylamine are preferred.

As described above, X in the general formula (1) represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, or an ammonium ion.
Examples of the alkali metal ions include lithium ions, sodium ions, and potassium ions.
Examples of the alkaline earth metal ions include calcium ions, strontium ions, barium ions, and the like.
Examples of the ammonium ions include aliphatic amines, cycloaliphatic amines, aromatic amines, ammonium ions derived from alkanolamines, and the like.
Examples of the aliphatic amine include ammonia, hydroxyamine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine.
Examples of the cyclic aliphatic amine include pyrrolidine, piperidine, piperazine and the like.
Examples of the aromatic amine include pyridine and pyrrole.
Examples of the alkanolamine include ethanolamine, diethanolamine, and triethanolamine.

Next, a method for synthesizing the dicarboxylic acid type compound of the present invention will be described. In general, an unsaturated fatty acid alkylamide, which is a reaction product of an unsaturated fatty acid and an aliphatic amine, is reacted with an organic peroxide obtained from hydrogen peroxide and an organic acid such as formic acid to oxidize double bonds. Then, a base such as sodium carbonate or potassium carbonate is allowed to act to introduce a hydroxyl group to synthesize a dihydroxy fatty acid alkylamide. Alternatively, another method for synthesizing dihydroxy fatty acid alkylamides is to first react an unsaturated fatty acid with an organic peroxide obtained from hydrogen peroxide and an organic acid such as formic acid to oxidize double bonds, The following general formula (3) obtained by introducing a hydroxyl group by acting a base such as sodium oxide or potassium carbonate

A dihydroxy fatty acid represented by the formula: dicyclohexylcarboxylic diimide (DCC), diisopropylcarbodiimide (DIPC), N-ethyl-N′-3-dimethylaminopropylcarbodiimide and its hydrochloride, benzotriazol-1-yl-tris (Dimethylamino) phosphonium hexafluorophosphide salt, diphenylphosphoryl azide and other condensing agents, or these condensing agents, N-hydroxysuccinimide, 1-hydroxybenzotriazole (HOBt) and 3-hydroxy-4-oxo-3, It can also be obtained by condensation with an additive such as 4-dihydro-1,2,3-benzotriazine to form an amide bond.
Next, by reacting the dihydroxy fatty acid alkylamide with succinic anhydride, the dicarboxylic acid type compound (X is hydrogen ion) of the present invention can be obtained. Furthermore, when X is an alkali metal ion, an alkaline earth metal ion, or an ammonium ion (for example, an ammonium ion derived from an aliphatic amine, a cyclic aliphatic amine, an aromatic amine, an alkanolamine, etc.), for example, A dicarboxylic acid type compound (X is a hydrogen ion) in a solvent such as water or ethyl alcohol, and a corresponding hydroxide or amine such as an alkali metal or alkaline earth metal (for example, aliphatic amine, cycloaliphatic amine, aromatic Group amines, amines such as alkanolamines) and the like.

上記合成フローに示すように、まずｃｉｓ−９−オクタデセン酸アルキルアミド（オレイン酸アルキルアミド）を、過酸化水素及びギ酸を用いて酸化し、その後、メチルアルコール、エチルアルコール等のアルコール中で炭酸カリウムを用いて処理することにより、９，１０−ジヒドロキシオクタデカン酸アルキルアミドを合成する（第１工程）。次に、トルエン、ジクロロメタン、ヘキサン、ヘプタン、テトラヒドロフラン等の有機溶媒中で９，１０−ジヒドロキシオクタデカン酸アルキルアミドと、該アミドの２〜４倍ｍｏｌ当量の無水コハク酸と、該アミドの１．０〜３．０倍ｍｏｌ当量のトリエチルアミン（ＴＥＡ）とを、２０〜１１０℃、好ましくは６０〜１００℃の温度で、８〜２４時間攪拌しながら反応させ、次にこの反応液を塩酸水溶液で洗浄し、その後水洗した後、冷却し、析出した結晶をろ別する、又は、溶媒を減圧留去させる、又は、スプレードライヤー装置を用
いて溶媒を乾燥させることで、目的物を得ることができる。また必要に応じてトルエン、酢酸エチル等の溶媒を用いた再結晶或いは、シリカゲルを固定相とし、クロロホルム・アセトン・メタノール混合溶媒を移動相とするカラムクロマトグラフィー等によって精製することにより、上記合成フローで示されるジカルボン酸化合物を得ることができる（第２工程）。 As an example of a specific synthesis method of a dicarboxylic acid type compound (X is hydrogen ion), a synthesis method in the case of using cis-9-octadecenoic acid alkylamide (oleic acid alkylamide) as a starting material will be described.

As shown in the above synthesis flow, cis-9-octadecenoic acid alkylamide (oleic acid alkylamide) is first oxidized using hydrogen peroxide and formic acid, and then potassium carbonate in alcohol such as methyl alcohol and ethyl alcohol. 9,10-dihydroxyoctadecanoic acid alkylamide is synthesized by treating with (first step). Next, 9,10-dihydroxyoctadecanoic acid alkylamide in an organic solvent such as toluene, dichloromethane, hexane, heptane, tetrahydrofuran and the like, succinic anhydride of 2 to 4 mol equivalents of the amide, and 1.0 of the amide are added. -3.0 times mol equivalent of triethylamine (TEA) is allowed to react with stirring at a temperature of 20 to 110 ° C, preferably 60 to 100 ° C for 8 to 24 hours, and then the reaction solution is washed with an aqueous hydrochloric acid solution. Then, after washing with water, it is cooled and the precipitated crystals are filtered off, or the solvent is distilled off under reduced pressure, or the solvent is dried using a spray dryer device, whereby the desired product can be obtained. If necessary, recrystallization using a solvent such as toluene or ethyl acetate, or purification by column chromatography using silica gel as a stationary phase and chloroform / acetone / methanol mixed solvent as a mobile phase, the above synthesis flow. Can be obtained (second step).

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples.

<Measurement equipment>
[FT-IR]
FTIR-8900 (manufactured by Shimadzu Corporation)
[NMR]
AV400M (Bruker Biospin)
[Elemental analysis]
Series II CHNS / O Analyzer 2400 (Perkin Elmer)

Example 1: Production of a compound represented by the formula (4)

1) Dihydroxylation reaction cis-9-octadecenoic acid hexylamide (50 g, 0.14 mol) and 88% formic acid (143.0 g, 2.73 mol) were placed in a reaction vessel and stirred, and at 40 ° C., 35% excess. Hydrogen oxide (26.6 g, 0.27 mol) was added dropwise. After completion of dropping, the mixture was stirred at 40 ° C. for 24 hours. After removing the formic acid layer and washing twice with water, potassium carbonate (18.9 g, 0.14 mol) and 123 mL of ethyl alcohol were added, stirred at 25 ° C. for 24 hours, and filtered to remove excess potassium carbonate. After removal, ethyl alcohol was removed, and recrystallization was performed using methyl ethyl ketone to obtain 9,10-dihydroxyoctadecanoic acid hexylamide (28.1 g, 0.07 mol).
2) Dicarboxylic oxidation reaction 9,10-dihydroxyoctadecanoic acid hexylamide (20 g, 0.049 mol), triethylamine (12.3 g, 0.12 mol), and succinic anhydride (12.1 g, 0.12 mol) were added with 200 mL of toluene. In addition, the mixture was stirred at 80 ° C. for 12 hours in a nitrogen atmosphere. After confirming the formation of the desired product by TLC, the temperature was lowered to 50 ° C., 73 mL of 2M hydrochloric acid was added, stirred and washed, and then washed 3 times with 146 mL of water. Thereafter, anhydrous sodium sulfate was added to the reaction solution, followed by dehydration and filtration. After the filtrate was distilled off under reduced pressure, the resulting solid was recrystallized using ethyl acetate to obtain 20.5 g of a white solid (yield 70.4%).
The results of measuring the obtained white solid by FT-IR (KBr method), ¹ H-NMR, ¹³ C-NMR and elemental analysis are shown below. From this result, the structure (compound represented by the title formula (4)) and purity of the obtained white solid were confirmed.

FT-IR: 1726.0 cm ⁻¹ (C═O (ester), st), 1714.5 cm ⁻¹ (C═O (carboxylic acid), st), 1647.0 cm ⁻¹ (C═O (amide) st )
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.86-0.89 (m, 6H), 1.24-1.62 (m, 34H), 2.21 (t, 2H), 2.59- 2.72 (m, 8H), 3.21-3.26 (m, 2H), 4.99-5.06 (m, 2H), 5.70 (t, 1H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 14.8, 14.9, 22.6, 22.7, 24.6, 25.1, 25.6, 28.4-29.5, 30.7 30.8, 31.8, 36.5, 39.7, 74.2, 74.4, 171.8, 174.5, 176.5, 176.6
Elemental analysis (C ₃₂ H ₅₇ N ₁ O ₉ ):
Actual value (%) C: 64.14%, H: 9.87%, N: 2.41
Calculated value (%) C: 64.08%, H: 9.58%, N: 2.34

Example 2: Production of compound represented by formula (5)

1) Dihydroxylation reaction cis-9-octadecenoic acid octylamide (50 g, 0.12 mol) and 88% formic acid (128.2 g, 2.5 mol) were placed in a reaction vessel and stirred, and at 40 ° C., 35% excess. Hydrogen oxide (23.8 g, 0.25 mol) was added dropwise. After completion of dropping, the mixture was stirred at 40 ° C. for 24 hours. After removing the formic acid layer and washing twice with water, potassium carbonate (17.0 g, 0.12 mol) and 110 mL of ethyl alcohol were added, stirred at 25 ° C. for 24 hours, and filtered to remove excess potassium carbonate. After removal, ethyl alcohol was removed and recrystallization was performed using methyl ethyl ketone to obtain 9,10-dihydroxyoctadecanoic acid octylamide (24 g, 0.056 mol).
2) Dicarboxylic oxidation reaction 9,10-dihydroxyoctadecanoic acid octylamide (20 g, 0.046 mol), triethylamine (11.6 g, 0.12 mol), and succinic anhydride (11.5 g, 0.0.12 mol) in toluene 200 mL was added and stirred at 80 ° C. for 12 hours under a nitrogen atmosphere. After confirming the formation of the desired product by TLC, the temperature was lowered to 50 ° C., 69 mL of 2M hydrochloric acid was added and stirred, washed, and then washed 3 times with 138 mL of water. Thereafter, anhydrous sodium sulfate was added to the reaction solution, followed by dehydration and filtration. After the filtrate was distilled off under reduced pressure, the obtained solid was recrystallized using ethyl acetate to obtain 23.2 g of a white solid (yield). 80.1%).
The results of measuring the obtained white solid by FT-IR (KBr method), ¹ H-NMR, ¹³ C-NMR and elemental analysis are shown below. From this result, the structure (compound represented by the title formula (5)) and purity of the obtained white solid were confirmed.

FT-IR: 1726.2 cm ⁻¹ (C═O (ester), st), 1714.6 cm ⁻¹ (C═O (carboxylic acid), st), 1647.1 cm ⁻¹ (C═O (amide) st )
¹ H-NMR (400 MHz, CDCl ₃ ): δ0.86-0.89 (m, 6H), 1.24-1.62 (m, 38H), 2.21 (t, 2H), 2.59- 2.72 (m, 8H), 3.
21-3.26 (m, 2H), 4.99-5.06 (m, 2H), 5.70 (t, 1H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 14.8, 14.9, 22.6, 22.7, 24.6, 25.1, 25.6, 28.4-29.5, 30.7 30.8, 31.8, 36.5, 39.7, 74.2, 74.4, 171.8, 174.5, 176.5, 176.6
Elemental analysis (C ₃₄ H ₆₁ N ₁ O ₉ ):
Actual value (%) C: 65.21%, H: 10.10%, N: 2.23
Calculated value (%) C: 65.04%, H: 9.79%, N: 2.23

Example 3: Production of compound represented by formula (6)

1) Dihydroxylation reaction cis-9-octadecenoic acid dodecylamide (40 g, 0.082 mol) and 88% formic acid (86.1 g, 1.65 mol) were placed in a reaction vessel and stirred, and at 40 ° C., 35% excess. Hydrogen oxide (16 g, 0.16 mol) was added dropwise. After completion of dropping, the mixture was stirred at 40 ° C. for 24 hours. After removing the formic acid layer and washing twice with water, potassium carbonate (11.4 g, 0.082 mol) and 74 mL of ethyl alcohol were added, and the mixture was stirred at 25 ° C. for 24 hours and filtered to remove excess potassium carbonate. After removal, ethyl alcohol was removed and recrystallization was performed using methyl ethyl ketone to obtain 9,10-dihydroxyoctadecanoic acid dodecylamide (26.4 g, 0.055 mol).
2) Dicarboxylic oxidation reaction 9,10-dihydroxyoctadecanoic acid dodecylamide (20 g, 0.039 mol), triethylamine (9.9 g, 0.098 mol), and succinic anhydride (9.8 g, 0.098 mol) were added with 200 mL of toluene. In addition, the mixture was stirred at 80 ° C. for 12 hours in a nitrogen atmosphere. After confirming the formation of the desired product by TLC, the temperature was lowered to 50 ° C., 59 mL of 2M hydrochloric acid was added and stirred, washed, and then washed 3 times with 118 mL of water. Thereafter, anhydrous sodium sulfate was added to the reaction solution, followed by dehydration and filtration. After the filtrate was distilled off under reduced pressure, the obtained solid was recrystallized using ethyl acetate to obtain 22.3 g of a white solid (yield). 83%).
The results of measuring the obtained white solid by FT-IR (KBr method), ¹ H-NMR, ¹³ C-NMR and elemental analysis are shown below. From this result, the structure (compound represented by the title formula (6)) and purity of the obtained white solid were confirmed.

FT-IR: 1726.2 cm ⁻¹ (C═O (ester), st), 1712.2 cm ⁻¹ (C═O (carboxylic acid), st), 1646.6 cm ⁻¹ (C═O (amide) st )
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.86-0.89 (m, 6H), 1.24-1.62 (m, 46H), 2.21 (t, 2H), 2.59- 2.72 (m, 8H), 3.21-3.26 (m, 2H), 4.99-5.06 (m, 2H), 5.70 (t, 1H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 14.8, 14.9, 22.6, 22.7, 24.6, 25.1, 25.6, 28.4-29.5, 30.7 30.8, 31.8, 36.5, 39.7, 74.2, 74.4, 171.8, 174.6, 176.4, 176.5
Elemental analysis (C ₃₈ H ₆₉ N ₁ O ₉ ):
Actual value (%) C: 66.64%, H: 10.41%, N: 2.03
Calculated value (%) C: 66.73%, H: 10.17%, N: 2.05

Example 4: Production of compound represented by formula (7)

1) Unsaturated fatty acid dihydroxylation reaction cis-9-octadecenoic acid (50 g, 0.1 mol) and 88% formic acid (170.3 g, 3.25 mol) were placed in a reaction vessel and stirred, and at 40 ° C., 35% Hydrogen peroxide (33.2 g, 0.34 mol) was added dropwise. After completion of dropping, the mixture was stirred at 40 ° C. for 24 hours. Then, after washing with water, 250 mL of 3M aqueous sodium hydroxide solution was added and stirred at 80 ° C. for 4 hours. After cooling to room temperature, 450 mL of 2M HCl aqueous solution was added and stirred at room temperature for 2 hours. After filtration, recrystallization was performed using methyl ethyl ketone to obtain 9,10-dihydroxyoctadecanoic acid (43 g, 0.14 mol).
2) Amidation reaction 9,10-dihydroxyoctadecanoic acid (40 g, 0.126 mol), DIPC (16.7 g, 0.13 mol), HOBt (20.1 g, 0.13 mol) and tetrahydrofuran 400 mL were added, After reacting at 60 ° C. for 1 hour, a solution in which N-methyldodecylamine (26.5 g, 0.13 mol) was dissolved in 100 ml of tetrahydrofuran was dropped, and the reaction was performed under reflux for 3 hours. The reaction solution was cooled to room temperature, and the filtered crystals were recrystallized with ethanol to obtain white crystals (45.1 g, 0.091 mol).
3) Dicarboxylic acid oxidation reaction 9,10-dihydroxyoctadecanoic acid N-methyldodecylamide (40 g, 0.079 mol), triethylamine (20 g, 0.20 mol), and succinic anhydride (19.8 g, 0.20 mol) in 400 mL of toluene And stirred at 80 ° C. for 12 hours under a nitrogen atmosphere. After confirming the formation of the desired product by TLC, the temperature was lowered to 50 ° C., 119 mL of 2M hydrochloric acid was added, stirred, washed, and washed 3 times with 238 mL of water. Thereafter, anhydrous sodium sulfate was added to the reaction solution, dehydrated, filtered, the filtrate was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography using chloroform-acetone-methanol as an eluent. And 39.4 g (yield 71.3%) of a white solid was obtained.
The results of measuring the obtained white solid by FT-IR (KBr method), ¹ H-NMR, ¹³ C-NMR and elemental analysis are shown below. From this result, the structure (compound represented by the title formula (7)) and purity of the obtained white solid were confirmed.

FT-IR: 1726.2 cm ⁻¹ (C═O (ester), st), 1712.2 cm ⁻¹ (C═O (carboxylic acid), st), 1641.2 cm ⁻¹ (C═O (amide) st )
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.86-0.89 (m, 6H), 1.24-1.62 (m, 46H), 2.21 (t, 2H), 2.59- 2.72 (m, 8H), 2.92 (s, 3H), 3.21-3.26 (m, 2H), 4.99-5.06 (m, 2H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 14.8, 14.9, 22.6, 22.7, 24.6, 25.1, 25.6, 28.4-29.5, 30.7 , 30.8, 31
. 8, 32.9, 36.5, 39.7, 74.2, 74.4, 171.8, 174.6, 176.4, 176.5
Elemental analysis _{(C 39 H 71 N 1 O} 9):
Actual value (%) C: 67.15%, H: 10.28%, N: 2.01
Calculated value (%) C: 67.11%, H: 10.25%, N: 2.01

Example 5: Production of compound represented by formula (8)

1) Dihydroxylation reaction Cis-13-docosenoic acid hexylamide (50 g, 0.119 mol) and 88% formic acid (123.9 g, 2.4 mol) were placed in a reaction vessel and stirred. Hydrogen oxide (23.0 g, 0.24 mol) was added dropwise. After completion of dropping, the mixture was stirred at 40 ° C. for 24 hours. After removing the formic acid layer and washing twice with water, potassium carbonate (16.4 g, 0.119 mol) and 107 mL of ethyl alcohol were added, and the mixture was stirred at 25 ° C. for 24 hours and filtered to remove excess potassium carbonate. After removal, ethyl alcohol was removed, and recrystallization was performed using methyl ethyl ketone to obtain 13,14-dihydroxydocosanoic acid hexylamide (40.2 g, 0.088 mol).
2) Dicarboxylic oxidation reaction 13,14-dihydroxydocosanoic acid hexylamide (40 g, 0.088 mol), triethylamine (22.2 g, 0.22 mol), and succinic anhydride (22.0 g, 0.22 mol) in 400 mL of toluene And stirred at 80 ° C. for 12 hours under a nitrogen atmosphere. After confirming the formation of the desired product by TLC, the temperature was lowered to 50 ° C., 132 mL of 2M hydrochloric acid was added, stirred and washed, and then washed 3 times with 263 mL of water. Thereafter, anhydrous sodium sulfate was added to the reaction solution, dehydrated and filtered, and the filtrate was cooled and filtered with suction. The resulting solid was recrystallized using ethyl acetate to obtain 47.6 g of a white solid. (Yield 82.7%) was obtained.
The results of measuring the obtained white solid by FT-IR (KBr method), ¹ H-NMR, ¹³ C-NMR and elemental analysis are shown below. From this result, the structure (compound represented by the title formula (8)) and purity of the obtained white solid were confirmed.

FT-IR: 1727.1 cm ⁻¹ (C═O (ester), st), 1713.4 cm ⁻¹ (C═O (carboxylic acid), st), 1645.6 cm ⁻¹ (C═O (amide) st )
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.86-0.91 (m, 6H), 1.24-1.62 (m, 42H), 2.21 (t, 2H), 2.59- 2.72 (m, 8H), 3.21-3.26 (m, 2H), 4.99-5.06 (m, 2H), 5.70 (t, 1H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 14.8, 14.9, 22.6, 22.7, 24.6, 25.1, 25.6, 28.4-29.5, 30.7 30.8, 31.8, 36.5, 39.7, 74.2, 74.4, 171.8, 174.6, 176.5, 176.6
Elemental analysis (C ₃₆ H ₆₅ N ₁ O ₉ ):
Actual value (%) C: 65.88%, H: 10.11%, N: 2.13
Calculated value (%) C: 65.92%, H: 9.99%, N: 2.14

Example 6: Production of compound represented by formula (9)

1) Dihydroxylation reaction cis-4-dodecenoic acid octadecylamide (20 g, 0.045 mol) and 88% formic acid (46.5 g, 0.89 mol) were placed in a reaction vessel and stirred. Hydrogen oxide (8.6 g, 0.089 mol) was added dropwise. After completion of dropping, the mixture was stirred at 40 ° C. for 24 hours. After removing the formic acid layer and washing twice with water, potassium carbonate (6.2 g, 0.045 mol) and 40 mL of ethyl alcohol were added, and the mixture was stirred at 25 ° C. for 24 hours and filtered to remove excess potassium carbonate. After removal, ethyl alcohol was removed, and recrystallization was performed using methyl ethyl ketone to obtain 4,5-dihydroxydodecanoic acid octadecylamide (15.3 g, 0.032 mol).
2) Dicarboxylic oxidation reaction 150 mL of toluene was added to 4,5-dihydroxydodecanoic acid octadecylamide (15 g, 0.031 mol), triethylamine (7.8 g, 0.078 mol), and succinic anhydride (7.8 g, 0.078 mol). In addition, the mixture was stirred at 80 ° C. for 18 hours under a nitrogen atmosphere. After confirming the formation of the desired product by TLC, the temperature was lowered to 50 ° C., 47 mL of 2M hydrochloric acid was added, stirred, washed, and then washed with 93 mL of water three times. Thereafter, anhydrous sodium sulfate was added to the reaction solution, followed by dehydration and filtration. After the filtrate was distilled off under reduced pressure, the obtained solid was recrystallized using ethyl acetate to obtain 14.9 g of a white solid (yield). Rate 70.3%).
The results of measuring the obtained white solid by FT-IR (KBr method), ¹ H-NMR, ¹³ C-NMR and elemental analysis are shown below. From this result, the structure (compound represented by the title formula (9)) and purity of the obtained white solid were confirmed.

FT-IR: 1724.5 cm ⁻¹ (C═O (ester), st), 1710.4 cm ⁻¹ (C═O (carboxylic acid), st), 1649.2 cm ⁻¹ (C═O (amide) st )
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.86 to 0.89 (m, 6H), 1.24 to 1.64 (m, 44H), 1.81 to 1.84 (m, 2H), 2.22 (t, 2H), 2.60-2.73 (m, 8H), 3.20-3.25 (m, 2H), 5.00-5.08 (m, 2H), 5. 68 (t, 1H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 14.8, 14.9, 22.6, 22.7, 24.6, 25.1, 25.6, 28.4-29.5, 30.7 30.8, 31.8, 36.5, 39.7, 73.2, 73.6, 171.8, 174.6, 176.4, 176.5
Elemental analysis (C ₃₈ H ₆₉ N ₁ O ₉ ):
Actual value (%) C: 66.85%, H: 10.35%, N: 2.07
Calculated value (%) C: 66.73%, H: 10.17%, N: 2.05

Example 7
For the sodium salt compound (X is sodium) obtained by reacting the dicarboxylic acid type compounds obtained in Examples 1 to 6 with sodium hydroxide in an aqueous solvent, a surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) was used. By the Wilhelmy method using a platinum plate,
10 (adjusted with aqueous sodium hydroxide), measure surface tension at each surfactant concentration, create surface tension-concentration plot, critical micelle concentration (cmc) and surface tension at critical micelle concentration (γ _cmc ) Asked. The results are shown in Table 1. As Comparative Example 1, sodium dodecanoate (sodium laurate), which is a 1-chain 1-hydrophilic surfactant, was used.

It is generally known that a two-chain two-hydrophilic surfactant has a lower critical micelle concentration (cmc) and a surface tension (γ _cmc ) at the critical micelle concentration than a one-chain one hydrophilic group-type surfactant. ing.
Therefore, it was examined whether the dicarboxylic acid type compound of the present invention has an excellent surface activity as well as the conventional two-chain two-hydrophilic type surfactant.
From the results in Table 1, the dicarboxylic acid compounds obtained in Examples 1 to 6 showed a lower critical micelle concentration (cmc) of about 1/3 to 1/2000 than that of Comparative Example 1. Also, the surface tension (γ _cmc ) at the critical micelle concentration was lower than that of Comparative Example 1 and showed a high surface tension reducing ability.
From the above results, it can be understood that when the dicarboxylic acid type compound of the present invention is used as a cleaning agent or an emulsifier, a small amount of addition is required as compared with the conventional one-chain one-hydrophilic surfactant.

Example 8 Emulsifying power test A triethanolamine salt compound obtained by reacting the dicarboxylic acid type compound obtained in Examples 1 to 6 with triethanolamine in an ethanol solvent, and 1 chain 1 hydrophilic group type as Comparative Examples 1 and 2 50 ml of each triethanolamine salt compound aqueous solution prepared in 0.1 wt% aqueous solution using dodecanoic acid triethanolamine salt (lauric acid triethanolamine salt), which is a surfactant, was dissolved in toluene. Stir at 10000 rpm with a homogenizer at 40 ° C. for 3 minutes together with 25 mL, then transfer to a 50 mL graduated cylinder and let stand at room temperature. Evaluated. If the separated water content was less than 10%, it was evaluated as ◯ if it was 10% or more and less than 20%, and x if it was 20% or more.

From the results of Table 2, the triethanolamine salt of the dicarboxylic acid compound obtained in Examples 1 to 6 showed higher emulsifying power than Comparative Example 1, and compared to Comparative Example 2 having a high surfactant concentration. Was also equivalent.
From the above results, it can be seen that when the dicarboxylic acid type compound of the present invention is used as an emulsifier, the emulsifying power is high with a small amount of addition compared to the conventional one-chain one-hydrophilic surfactant.

Example 9
The biodegradability test of the dicarboxylic acid compounds obtained in Examples 1 to 6 was performed based on the OECD test guideline 301C modified MITI test using a pressure sensor type BOD measuring device (manufactured by Actac Co.): 100 mg test substance concentration / L, activated sludge concentration: 40 mg / L, test temperature: 25 ° C., test period: 28 days. The results are shown in Table 3. The dicarboxylic acid types obtained in Examples 1 to 6 all showed biodegradability of 60% or more, and showed good biodegradability.

Example 10 Hydrolysis stability test Using a sodium salt compound (X is sodium) obtained by reacting the dicarboxylic acid type compound obtained in Examples 1 to 6 with an aqueous sodium bicarbonate solution in a heavy water solvent, pH 10 (deuterated hydroxide) was used. ¹ H-NMR of a 0.1 wt% aqueous solution prepared in a sodium aqueous solution was measured immediately, 1 month later, 3 months later, and 6 months later (stored at room temperature). When the structure is maintained from the integral ratio of methylene protons next to NH near the amide bond near 3.2 ppm and the integral ratio of methine protons near the ester bond near 5.0 ppm, the structure maintenance ratio is 100%. The structure maintenance rate of each compound was estimated. The results are shown in Table 4. All of the dicarboxylic acid types obtained in Examples 1 to 6 showed a structure retention rate of 90% or more, and showed good hydrolysis stability in the alkaline region.

The dicarboxylic acid type compound of the present invention uses a naturally derived fatty acid which is easily available industrially as a starting material, and can be easily synthesized. Therefore, the industrial applicability is very large.
The surfactant of the present invention can be used for various purposes such as a hair cleaner, a skin cleaner, a kitchen detergent, a machine metal cleaner, etc. Since it has active ability and is excellent in hydrolysis stability and biodegradability, it is suitable as a base for cosmetics such as shampoos, rinses and body shampoos. Further, the surfactant of the present invention is a paper strength enhancer, paper quality improver, sizing agent, various fillers, pigments, dyes, etc., yield improvers in the paper industry, adhesion promoter in the adhesive industry, textile industry. Used for dyeing property improvers, antishrink agents, flameproofing treatment agents, antistatic treatment agents, etc., and cosmetic compositions, cleaning compositions, lubricant additives, rust inhibitors, antifogging agents, etc. be able to. In addition, when the surfactant of the present invention is used in cosmetics, other additives conventionally used in cosmetics may be added as needed as long as the properties of the surfactant of the present invention are not impaired. it can. Additives that can be used in combination include, for example, antibacterial agents, thickeners, fragrances, conditioning agents, sequestering agents, pearlizing agents, foaming agents, slipperiness improvers, smoothing agents, hair styling agents, moisturizing agents, and dispersion stability. Agents, anti-dandruff agents, bactericides, refreshing stimulants, preservatives, appearance modifiers, and the like.

Claims (3)

A dicarboxylic acid type compound represented by the following general formula (1).

However, in the general formula (1),
C _n H _{2n + 1} represents a linear or branched alkyl group,
n represents an integer of 1 to 22,
R ₁ represents an alkylene group having 1 to 22 carbon atoms,
R ₂ represents an alkyl group having 1 to 22 carbon atoms,
R ₃ represents a hydrogen atom or a methyl group,
X represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, or an ammonium ion, provided that R ₁ and R ₂ have a —R ₁ —CH—CH—R ₂ moiety of 9 to 25 carbon atoms. The hydrocarbon structure is selected.   A surfactant comprising the dicarboxylic acid type compound according to claim 1. The following general formula (2 ')

(Where
C _n H _{2n + 1} represents a linear or branched alkyl group,
n represents an integer of 1 to 22,
R ₁ represents an alkylene group having 1 to 22 carbon atoms,
R ₂ represents an alkyl group having 1 to 22 carbon atoms,
R ₃ represents a hydrogen atom or a methyl group, provided that R ₁ and R ₂ are selected so that the —R ₁ —CH—CH—R ₂ moiety forms a hydrocarbon structure having 9 to 25 carbon atoms. Is done. ) And a succinic anhydride are reacted to give the following general formula (1 ′)

(Wherein, C _n H _{2n + 1} , n, R ₁ , R ₂ and R ₃ have the same meaning as defined in formula ( ₂ ′)), Subsequently, in some cases, the compound represented by the general formula (1 ′) is reacted with an alkali metal or alkaline earth metal hydroxide or amine to give the following general formula (1):

(In the formula, C _n H _{2n + 1} , n, R ₁ , R ₂ and R ₃ represent the same meaning as defined in the general formula ( _{2 ′} ), and X represents a hydrogen ion, an alkali metal ion, an alkaline earth, A method for producing a dicarboxylic acid type compound, comprising the step of:

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