JP2011132418A - Nonionic surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonionic surfactant which is excellent in surface active performance even in the case of low concentration and which is low in environmental loads and has low acridity and such a molecular structure that a balance between hydrophilicity and hydrophobicity can be controlled according to the application. <P>SOLUTION: Disclosed is the nonionic surfactant represented by general formula (2) (wherein m and n are each a number of 0-100 and satisfy m+n=1-200). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a nonionic surfactant.

  Two-chain, two-hydrophilic group-containing surfactants known as gemini-type surfactants have been studied. Compared with single-chain surfactants, compounds with various structures have been synthesized. (Non-Patent Document 1), researches on different types of hydrophilic groups, those with asymmetric structures of alkyl chains, and gemini surfactants with asymmetric structures of hydrophilic groups and alkyl chains (Non-Patent Document 2). Compared with conventional surfactants containing 1-chain and 1-hydrophilic groups and 1-chain and 2-hydrophilic groups, it has superior surface activity and requires only a low concentration to be added, reducing the burden on the environment (Non-Patent Document 1, Non-Patent Document) 2) Since it has features such as excellent safety and almost no skin irritation, it has been developed as a cosmetic (Patent Document 1).

Japanese Patent No. 3426493

R. Zana, J. et al. Xia (Eds.), Gemini Surfactants, Synthesis, Interface and Solution-Phase Behavior, and Applications, Marcel Dekker, New York, 2003. Xia (Eds.), Gemini Surfactants, Synthesis, Interfacial and Solution-Phase Behavior, and Applications. E. Alami and K.M. Holberg, Advances in Colloid and Interface Science 100-102 (2003) 13-46 E. Alami and K.M. Holberg, Journal of Colloid and Interface Science 239, 230-240 (2001)

  However, when considering the molecular design of a surfactant containing two-chain hydrophobic groups and two terminal hydrophilic groups that are gemini-type on the premise of industrial implementation, the two-molecule linkage, hydrophobic group, hydrophilic group Despite its excellent performance, it is not always easy to introduce, has to be limited in molecular design, and is often forced to use relatively expensive raw materials. However, there are still few things that have been put into practical use, and it is the actual situation that nothing has been put into practical use only in the nonion type. There are few research reports on nonionic gemini surfactants using polyoxyethylene chains as hydrophilic groups (Non-patent Document 1, Non-patent Document 2, Non-patent Document 3). For example, nonion using oleylnitrile as a raw material Gemini type surfactants (Non-patent Document 3) have been studied, but because the hydrophobic chain is short and the alkyl chain length cannot be controlled, it is said that Gemini type has sufficiently high surface activity. It is difficult and furthermore, since an expensive hydrophilic group is used as a raw material, no fundamental solution has been reached. In view of this background, the present invention provides a nonionic surfactant containing a two-chain two-hydrophilic group that can control the alkyl chain length and hydrophilicity and can be easily produced using only inexpensive raw materials. With the goal.

  That is, the present invention is represented by the following general formula (2) in which two hydrophilic groups are introduced at the position of the double bond of the alkylamide of the unsaturated fatty acid having 10 to 26 carbon atoms represented by the following general formula (1). Nonionic surfactant.

In general formula (1), R ₁ —CH═CH—R ₂ is an alkenyl group having 9 to 25 carbon atoms, R ₃ is an alkyl group having 1 to 20 carbon atoms, and in general formula (2), AO is carbon. The oxyalkylene groups derived from the alkylene oxides of formulas 2 to 3, m and n are the same or different numbers of 0 to 100, and m + n = 1 to 200.

  The nonionic surfactant of the present invention has a critical micelle concentration (cmc) of about one-tenth as compared with a one-chain one-hydrophilic group-containing surfactant such as polyoxyalkylene alkyl ether, and a lower concentration. Even when blended, it exhibits excellent surface activity such as foaming, washing, emulsification, dispersion, wetting and solubilization. For this reason, the nonionic surfactant of the present invention is superior in surface active ability such as foaming, washing, emulsification, dispersion, wetting, solubilization, etc., even at low concentrations, and blended at a low concentration The load on the environment is reduced. In addition, it is hypoallergenic and has an excellent molecular structure that can control the hydrophilic-hydrophobic balance according to the application. It is a detergent, emulsifier, dispersant, solubilizer, greasing agent, antistatic agent, dustproof agent, It is useful for various applications such as penetrants.

  The nonionic surfactant of the present invention represented by the general formula (2) is an unsaturated fatty acid alkylamide represented by the general formula (1) which is an amide of an unsaturated fatty acid having one double bond and an aliphatic amine. It can be obtained by addition polymerization of an alkylene oxide such as ethylene oxide or propylene oxide to the hydroxyl group of a dihydroxy fatty acid alkylamide represented by the following general formula (3) obtained by oxidizing the double bond of this compound to introduce a hydroxyl group. A dihydroxy fatty acid alkylamide obtained by introducing a hydroxyl group into the double bond portion of the unsaturated fatty acid alkylamide represented by the general formula (1) is obtained from an unsaturated fatty acid alkylamide, for example, from an organic acid such as hydrogen peroxide and formic acid. It can be obtained by reacting an organic peroxide to oxidize double bonds, and further by introducing a hydroxyl group by allowing a base such as sodium carbonate or potassium carbonate to act in an alcohol such as methyl alcohol. Further, the dihydroxy fatty acid alkylamide represented by the general formula (3) uses an unsaturated fatty acid as a raw material to react an organic peroxide obtained from hydrogen peroxide and an organic acid such as formic acid to oxidize a double bond. Then, a dihydroxy fatty acid and an aliphatic amine represented by the general formula (4) obtained by acting a base such as sodium hydroxide or potassium carbonate and introducing a hydroxyl group can be converted into dicyclohexylcarbondiimide (DCC) or diisopropylcarbodiimide (DIPC). N-ethyl-N′-3-dimethylaminopropylcarbodiimide and its hydrochloride, benzotriazol-1-yl-tris (dimethylamino) phosphonium hexafluorophosphide salt, diphenylphosphoryl azide and the like, or their condensation N-hydroxysuccinimi It can also be obtained by condensation with an additive such as 1-hydroxybenzotriazole (HOBt) or 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine to form an amide bond. I can do it.

  The unsaturated fatty acid alkylamide represented by the general formula (1) can be obtained by an amidation reaction of an unsaturated fatty acid having 10 to 26 carbon atoms and an aliphatic amine having 1 to 20 carbon atoms. Examples of the unsaturated fatty acid having 10 to 26 carbon atoms include decenoic acid (C′10), undecenoic acid (C′11), dodecenoic acid (C′12) such as lindelic acid, succinic acid, lauroleic acid, and tridecenoic acid. (C'13), tetradecenoic acid (C'14) such as tuzuic acid and myristoleic acid, pentadecenoic acid (C'15), hexadecenoic acid (C'16) such as palmitoleic acid, heptadecenoic acid (C'17) Octadecenoic acid (C′18) such as oleic acid, elaidic acid and basenic acid, nonadecenoic acid (C′19), eicosenoic acid such as gondoic acid (C′20), heneicosenoic acid (C′21), erucic acid, Docosenoic acid (C′22) such as brassic acid, tricosenoic acid (C′23), tetracosenoic acid (C′24) such as ceracoleic acid, pentacosenoic acid (C′25), hex Cocenoic acid (C′26) and the like can be mentioned, but in order to enhance the hydrophobic interaction, hexadecenoic acid (C′16) such as palmitoleic acid, octadecenoic acid (C′18) such as oleic acid and elaidic acid, Eicosenoic acid (C′20) such as gondonic acid, docosenoic acid (C′22) such as erucic acid, tetracosenoic acid (C′24) such as ceracoleic acid and the like are preferable. More preferably, oleic acid is preferred from the viewpoint of industrial raw material supply and inexpensive raw materials. Examples of the aliphatic amine having 1 to 20 carbon atoms include methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, heptylamine, hexylamine, octylamine, 2-ethylhexylamine, decylamine, dodecylamine, tetra Examples thereof include aliphatic primary amines such as decylamine, hexadecylamine, octadecylamine, and eicosylamine. From the viewpoint that the raw material is relatively inexpensive, butylamine, octylamine, dodecylamine, and octadecylamine are preferable. The HLB of the surfactant can be controlled by the difference in the length of the alkyl group of these aliphatic amines.

By adding an alkylene oxide to each hydroxyl group of the dihydroxy fatty acid alkylamide represented by the general formula (3) at 50 to 200 ° C. in the presence of an acid catalyst such as boron trifluoride or an alkali catalyst such as potassium hydroxide. The nonionic surfactant of the present invention represented by the general formula (2) is obtained. As the alkylene oxide, ethylene oxide and propylene oxide are used, and these can be used together. When ethylene oxide and propylene oxide are used in combination, the polyoxyalkylene chain is a random addition polymerization of ethylene oxide and propylene oxide. Alternatively, it may be one obtained by addition polymerization in a block shape. The number of moles of addition polymerization of alkylene oxide per hydroxyl group of dihydroxy fatty acid alkylamide is 100 moles or less, preferably 50 moles or less, and the total number of moles of addition polymerization of alkylene oxide to two hydroxyl groups is 1 to 1. Although it is 200 mol, 1-100 mol is preferable. The polyoxyalkylene chain formed by addition polymerization of alkylene oxide to each hydroxyl group may have the same or different number of moles of alkylene oxide added, and is composed of different alkylene oxides added and polymerized. May be. In the structure of the raw material dihydroxy fatty acid alkylamide, there is an active hydrogen derived from the secondary amide, and when R _{3 in} the formula (2) has a small number of carbon atoms, if a large amount of alkylene oxide is added, as a side reaction, Alkylene oxide can also be added to secondary amides. In order to prevent this, when the number of carbon atoms of R ₃ shown in (2) is less than 10, the total number of moles of addition polymerization of alkylene oxide is preferably less than 20 moles. When R ₃ has 10 or more carbon atoms, it is unlikely that an alkylene oxide will be added to the secondary amide, so 20 moles or more of the alkylene oxide can be added.

  As an example for producing the surfactant of the present invention, the synthesis flow in the case of addition polymerization of ethylene oxide to dihydroxy fatty acid alkylamide obtained by using cis-9-octadecenoic acid alkylamide as a starting material is shown in Chemical Formula 5 below. In this reaction, first, after adding (i) hydrogen peroxide and formic acid to cis-9-octadecenoic acid alkylamide and reacting at 40 ° C. for 24 hours, the formic acid layer was removed, washed with water, and (ii) carbonic acid carbonate. Potassium and methyl alcohol are added and reacted for 24 hours. Excess potassium carbonate is removed by filtration or washing with water, and then recrystallized with an organic solvent such as methyl ethyl ketone to obtain dihydroxy fatty acid alkylamide. Next, a nonionic surfactant can be obtained by addition polymerization of ethylene oxide to dihydroxy fatty acid alkylamide using potassium hydroxide as a catalyst.

The surfactant of the present invention is selected from the unsaturated fatty acid having 10 to 26 carbon atoms or the aliphatic amine having 1 to 20 carbon atoms to be a hydrophobic group, the polymerization addition mole number of propylene oxide, and the polymerization addition of ethylene oxide to be a hydrophilic group. By adjusting the number of moles, HLB can be adjusted according to the application. For example, for use as an emulsifier, it is preferable to use HLB 8 to 18 for O / W type emulsification, and HLB 3.5 to 6 for W / O type emulsification, and HLB 13 to 15 as a detergent, solubilization. As an agent, 15-18 are preferable. The HLB value can be obtained from the following equation (1) by the Griffin method. For example, in the case of HLB 8-18 for O / W type emulsification, the carbon number of R ₁ —CH═CH—R _{2 in} the general formula (1) is 9-21, and the carbon number of R ₃ is 4-18. It can be obtained by adding ethylene oxide in an amount such that m + n in the general formula (2) is 4 to 100 to the hydroxyl group of the dihydroxy fatty acid alkylamide obtained by oxidizing the unsaturated fatty acid alkylamide. However, at this time, when the carbon number of R ₃ is less than 10, the upper limit of m + n is preferably less than 20. W / O type HLB 3.5 to 6 for HLB 3.5-6 has 9 to 21 carbon atoms in R ₁ —CH═CH—R ₂ and 4 to 18 carbon atoms in R ₃ in general formula (1). It can be obtained by adding ethylene oxide in an amount such that m + n in the general formula (2) is 1.3 to 6 to the hydroxyl group of the dihydroxy fatty acid alkylamide obtained by oxidizing the unsaturated fatty acid alkylamide. The HLB 13-15 for the detergent is an unsaturated fatty acid alkyl having 9 to 21 carbon atoms in R ₁ —CH═CH—R ₂ and 4 to 18 carbon atoms in R _{3 in} the general formula (1). It can be obtained by adding ethylene oxide in an amount such that m + n is 11 to 43 in the general formula (2) to the hydroxyl group of the dihydroxy fatty acid alkylamide obtained by oxidizing the amide. However, at this time, when the carbon number of R ₃ is less than 10, the upper limit of m + n is preferably less than 20. HLB 15-18 for solubilizers are unsaturated fatty acids in which R ₁ —CH═CH—R ₂ has 9 to 21 carbon atoms and R ₃ has 4 to 18 carbon atoms in general formula (1) It can be obtained by adding ethylene oxide in an amount such that m + n is 18 to 100 in the general formula (2) to the hydroxyl group of the dihydroxy fatty acid alkylamide obtained by oxidizing the alkylamide. However, at this time, when the carbon number of R ₃ is less than 10, the upper limit of m + n is preferably less than 20.

(Equation 1)
HLB = 20 × sum of formula weight of hydrophilic part / molecular weight

  EXAMPLES Next, an Example is given and this invention is demonstrated still in detail.

Example 1
Cis-9-octadecenoic acid octylamide (88.5 g, 0.225 mol) and 88% formic acid (235.6 g, 4.5 mol) were placed in a reaction vessel and stirred, and at 40 ° C., 35% peroxidation was performed. Hydrogen (43.7 g, 0.45 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 (31.1 g, 0.225 mol) and 203 ml of methyl alcohol were added, and the mixture was stirred at 25 ° C. for 24 hours and filtered to remove excess carbonate. After removing potassium, methyl alcohol was removed and recrystallization was performed with methyl ethyl ketone to obtain 9,10-dihydroxyoctadecanoic acid octylamide (42 g, 0.10 mol). Next, 9,10-dihydroxyoctadecanoic acid octylamide (21 g, 0.049 mol) and 0.06 g of potassium hydroxide as a catalyst were added to a 100 mL autoclave, and the system was purged with nitrogen. The dehydration was performed for 20 minutes under reduced pressure. After completion of the dehydration, 4 mole equivalents of ethylene oxide were introduced into the autoclave at a reaction temperature of 120 to 130 ° C. and an internal pressure of 5 kg / cm ² with respect to 1 mole of 9,10-dihydroxyoctadecanoic acid octylamide to carry out an addition reaction. . After the introduction of the specified amount of ethylene oxide, aging was performed until the pressure became 2 kg / cm ² or less, and further aging was promoted for about 30 minutes while maintaining an internal pressure of 5 kg / cm ² with nitrogen, and a reaction product was obtained after cooling. Alkaline adsorbent (KYOWARD 600S: manufactured by Kyowa Chemical Co., Ltd.) is used in an amount of 1.5% by weight with respect to the reaction product. And filtered under pressure to obtain 25 g (sample 1) of a yellow transparent liquid.

The obtained sample 1 was dissolved in deuterated chloroform at a rate of 10 mg / 0.5 ml using AV400M NMR manufactured by Bruker Biospin Co., Ltd., and ¹ H-NMR (CDCl ₃ , 400 MHz) was measured. As a result of confirmation, ethylene oxide was introduced into both hydroxyl groups from the integral ratio of the proton of methine observed at around 3.2 to 3.3 ppm and the proton of methine observed at around 3.1 ppm. It was confirmed that a symmetric structure and an asymmetric structure in which an ethylene oxide chain was introduced into only one hydroxyl group was unreacted at a ratio of 14:86 (mol%). The average addition mole number calculated | required from the integration ratio of the peak of 3.7 ppm vicinity was 4.1 mol. The HLB was determined by the Griffin method and found to be 5.9.

Example 2
cis-13-docosenoic acid butyramide (100 g, 0.254 mol) and 88% formic acid (265.5 g, 5.1 mol) were placed in a reaction vessel and stirred, and at 40 ° C., 35% hydrogen peroxide (49 0.3 g, 0.51 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 (35.1 g, 0.254 mol) and 229 ml of methyl alcohol were added, and the mixture was stirred at 25 ° C. for 24 hours and filtered to remove excess carbonate. After removing potassium, methyl alcohol was removed, and recrystallization was performed with methyl ethyl ketone to obtain 13,14-dihydroxydocosanoic acid butyramide (76 g, 0.18 mol). Next, 13,14-dihydroxydocosanoic acid butyramide (50 g, 0.12 mol) and 0.15 g of potassium hydroxide as a catalyst were charged into a 300 mL autoclave, and the system was purged with nitrogen. The dehydration was performed for 20 minutes under reduced pressure. After completion of dehydration, 8 mole equivalents of ethylene oxide were introduced into the autoclave at a reaction temperature of 120 to 130 ° C. and an internal pressure of 5 kg / cm ² with respect to 1 mole of 13,14-dihydroxydocosanoic acid butyramide to carry out an addition reaction. After introduction of the specified amount of ethylene oxide, ripening at the same temperature until the pressure is 2 kg / cm ³ or less, further aging is promoted for about 30 minutes while maintaining an internal pressure of 5 kg / cm ² with nitrogen, and a reaction product is obtained after cooling It was. Alkaline adsorbent (KYOWARD 600S: manufactured by Kyowa Chemical Co., Ltd.) is used in an amount of 1.5% by weight with respect to the reaction product. And filtered under pressure to obtain 75.8 g (sample 2) of a yellowish white liquid.

The obtained sample 2 was dissolved in deuterated chloroform at a rate of 10 mg / 0.5 ml using AV400M NMR manufactured by Bruker Biospin, and ¹ H-NMR (400 MHz) was measured to confirm the structure. As a result, from the integral ratio of methine protons observed near 3.2 to 3.3 ppm and methine protons observed near 3.1 ppm, a symmetrical type in which ethylene oxide is introduced into both hydroxyl groups. The structure and one hydroxyl group were unreacted, and it was confirmed that an asymmetric structure in which an ethylene oxide chain was introduced was contained only in one hydroxyl group at a ratio of 30:70 (mol%). ^The average addition mole number calculated | required from < ¹ > H-NMR was 8.0 mol. The HLB obtained by the Griffin method was 9.0.

Example 3
Into a 100 mL autoclave, 9,10-dihydroxyoctadecanoic acid octylamide (21 g, 0.049 mol) obtained in the same manner as in Example 1 and 0.06 g of potassium hydroxide as a catalyst were added, and the inside of the system was purged with nitrogen. After that, dehydration was performed at 100 to 120 ° C. under reduced pressure for 20 minutes. After completion of the dehydration, 13 mole equivalents of ethylene oxide per 1 mole of 9,10-dihydroxyoctadecanoic acid octylamide were introduced into the autoclave under the conditions of a reaction temperature of 120 to 130 ° C. and an internal pressure of 5 kg / cm ² to carry out an addition reaction. . After introduction of the specified amount of ethylene oxide, ripening at the same temperature until the pressure is 2 kg / cm ³ or less, further aging is promoted for about 30 minutes while maintaining an internal pressure of 5 kg / cm ² with nitrogen, and a reaction product is obtained after cooling It was. Alkaline adsorbent (KYOWARD 600S: manufactured by Kyowa Chemical Co., Ltd.) is used in an amount of 1.5% by weight with respect to the reaction product. And filtered under pressure to obtain 40 g (sample 3) of a yellow transparent liquid.

The obtained sample 3 was dissolved in deuterated chloroform at a rate of 10 mg / 0.5 ml using NMR of AV400M manufactured by Bruker Biospin Co., Ltd., and ¹ H-NMR (CDCl ₃ , 400 MHz) was measured. As a result of confirmation, ethylene oxide was introduced into both hydroxyl groups from the integral ratio of the proton of methine observed at around 3.2 to 3.3 ppm and the proton of methine observed at around 3.1 ppm. It was confirmed that a symmetric structure and an asymmetric structure in which an ethylene oxide chain was introduced into only one hydroxyl group was unreacted at a ratio of 50:50 (mol%). The average addition mole number calculated | required from the integration ratio of the peak of 3.7 ppm vicinity was 13.3 mol. When HLB was determined by the Griffin method, it was 11.6.

Example 4
cis-4-decenoic acid dodecylamide (70 g, 0.207 mol) and 88% formic acid (216.4 g, 4.1 mol) were placed in a reaction vessel and stirred, and at 40 ° C., 35% hydrogen peroxide ( 40.2 g, 0.41 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 (28.6 g, 0.207 mol) and 186 ml of methyl alcohol were added, and the mixture was stirred at 25 ° C. for 24 hours and filtered to remove excess carbonic acid. After removing potassium, methyl alcohol was removed and recrystallization was performed with methyl ethyl ketone to obtain 4,5-dihydroxydecanoic acid dodecylamide (50 g, 0.13 mol). Next, 4,5-dihydroxydecanoic acid dodecylamide (50 g, 0.13 mol) and 0.15 g of potassium hydroxide as a catalyst were added to a 300 mL autoclave, and the system was purged with nitrogen. The dehydration was performed for 20 minutes under reduced pressure. After completion of the dehydration, 20 mole equivalents of ethylene oxide were introduced into the autoclave under the conditions of a reaction temperature of 120 to 130 ° C. and an internal pressure of 5 kg / cm ² with respect to 1 mole of 3,4-dihydroxydecanoic acid dodecylamide to carry out an addition reaction. After introduction of the specified amount of ethylene oxide, ripening at the same temperature until the pressure is 2 kg / cm ³ or less, further aging is promoted for about 30 minutes while maintaining an internal pressure of 5 kg / cm ² with nitrogen, and a reaction product is obtained after cooling It was. Alkaline adsorbent (KYOWARD 600S: manufactured by Kyowa Chemical Co., Ltd.) is used in an amount of 1.5% by weight with respect to the reaction product. And pressure-filtered to obtain 119 g (sample 4) of yellowish white viscous body.

The obtained sample 4 was dissolved in deuterated chloroform at a rate of 10 mg / 0.5 ml using NMR of AV400M manufactured by Bruker Biospin Co., Ltd., and ¹ H-NMR (CDCl ₃ , 400 MHz) was measured. As a result of confirmation, ethylene oxide was introduced into both hydroxyl groups from the integral ratio of the proton of methine observed at around 3.2 to 3.3 ppm and the proton of methine observed at around 3.1 ppm. It was confirmed that a symmetric structure and an asymmetric structure in which an ethylene oxide chain was introduced only into one hydroxyl group was included in a ratio of 52:48 (mol%). The average addition mole number calculated | required from the integration ratio of the peak of 3.7 ppm vicinity was 20.2 mol. The HLB obtained by the Griffin method was 14.1.

Example 5
Cis-9-octadecenoic acid (100 g, 0.354 mol) and 88% formic acid (370.3 g, 7.1 mol) were placed in a reaction vessel and stirred, and at 40 ° C., 35% hydrogen peroxide (72. 2 g, 0.74 mol) was added dropwise. After completion of dropping, the mixture was stirred for 24 hours. After washing with water, 500 ml of 3N aqueous sodium hydroxide solution was added and stirred at 80 ° C. for 4 hours. After cooling to room temperature, 900 ml of 2N HCl aqueous solution was added and stirred at room temperature for 2 hours. After filtration, recrystallization was performed with methyl ethyl ketone to obtain 9,10-dihydroxyoctadecanoic acid (89.6 g, 0.28 mol). Next, 9,10-dihydroxyoctadecanoic acid (80 g, 0.253 mol), DIPC (33.5 g, 0.266 mol), HOBt (40.2 g, 0.266 mol), 800 ml of tetrahydrofuran were added. After the reaction at 1 ° C. for 1 hour, a solution in which n-octadecylamine (71.7 g, 0.266 mol) was dissolved in 200 ml of tetrahydrofuran was added dropwise, 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 (128 g, 0.225 mol). Finally, 9,10-dihydroxyoctadecanoic acid octadecylamide (40 g, 0.07 mol) and 0.12 g of potassium hydroxide as a catalyst were charged into a 300 mL autoclave, and the system was purged with nitrogen. The dehydration was performed for 20 minutes under reduced pressure. After completion of the dehydration, 30 mole equivalents of ethylene oxide were introduced into the autoclave at a reaction temperature of 120 to 130 ° C. and an internal pressure of 5 kg / cm ² with respect to 1 mole of 9,10-dihydroxyoctadecanoic acid octadecylamide to carry out an addition reaction. After introduction of the specified amount of ethylene oxide, ripening at the same temperature until the pressure is 2 kg / cm ³ or less, further aging is promoted for about 30 minutes while maintaining an internal pressure of 5 kg / cm ² with nitrogen, and a reaction product is obtained after cooling It was. Alkaline adsorbent (KYOWARD 600S: manufactured by Kyowa Chemical Co., Ltd.) is used in an amount of 1.5% by weight with respect to the reaction product. The solution was filtered under pressure to obtain 106 g of yellowish white solid (Sample 5).

The obtained sample 5 was dissolved in deuterated chloroform at a rate of 10 mg / 0.5 ml using AV400M NMR manufactured by Bruker Biospin, and ¹ H-NMR (400 MHz) was measured to confirm the structure. As a result, from the integral ratio of methine protons observed near 3.2 to 3.3 ppm and methine protons observed near 3.1 ppm, a symmetrical type in which ethylene oxide is introduced into both hydroxyl groups. The structure and one hydroxyl group were unreacted, and it was confirmed that an asymmetric structure in which an ethylene oxide chain was introduced was contained only in one hydroxyl group at a ratio of 56:44 (mol%). The average addition mole number calculated | required from the integral ratio of the peak of 3.7 ppm was 28.6 mol. When HLB was determined by the Griffin method, it was 14.0.

Example 6
Into a 500 mL autoclave, 9,10-dihydroxyoctadecanoic acid octadecylamide (40 g, 0.07 mol) obtained in the same manner as in Example 5 and 0.18 g of potassium hydroxide as a catalyst were added, and the inside of the system was purged with nitrogen. After that, dehydration was performed at 100 to 120 ° C. under reduced pressure for 20 minutes. After completion of the dehydration, 60 mole equivalent of ethylene oxide was introduced into the autoclave under the conditions of a reaction temperature of 120 to 130 ° C. and an internal pressure of 5 kg / cm ² with respect to 1 mole of 9,10-dihydroxyoctadecanoic acid octadecylamide to carry out an addition reaction. After introduction of the specified amount of ethylene oxide, ripening at the same temperature until the pressure is 2 kg / cm ³ or less, further aging is promoted for about 30 minutes while maintaining an internal pressure of 5 kg / cm ² with nitrogen, and a reaction product is obtained after cooling It was. Alkaline adsorbent (KYOWARD 600S: manufactured by Kyowa Chemical Co., Ltd.) is used in an amount of 1.5% by weight with respect to the reaction product. And filtered under pressure to obtain 158 g (sample 6) of a yellowish white solid.

The obtained sample 6 was dissolved in deuterated chloroform at a rate of 10 mg / 0.5 ml using AV400M NMR manufactured by Bruker Biospin, and ¹ H-NMR (400 MHz) was measured to confirm the structure. As a result, from the integral ratio of methine protons observed near 3.2 to 3.3 ppm and methine protons observed near 3.1 ppm, a symmetrical type in which ethylene oxide is introduced into both hydroxyl groups. The structure and one hydroxyl group were unreacted, and it was confirmed that an asymmetric structure in which an ethylene oxide chain was introduced was contained only in one hydroxyl group at a ratio of 63:37 (mol%). The average addition mole number calculated | required from the integral ratio of the peak of 3.7 ppm was 58.0 mol. When HLB was determined by the Griffin method, it was 16.4.

Example 7
Into a 500 mL autoclave, 9,10-dihydroxyoctadecanoic acid octadecylamide (40 g, 0.07 mol) obtained in the same manner as in Example 5 and 0.24 g of potassium hydroxide as a catalyst were added, and the system was purged with nitrogen. After that, dehydration was performed at 100 to 120 ° C. under reduced pressure for 20 minutes. After completion of the dehydration, 90 mole equivalents of ethylene oxide were introduced into the autoclave under the conditions of a reaction temperature of 120 to 130 ° C. and an internal pressure of 5 kg / cm ² with respect to 1 mole of 9,10-dihydroxyoctadecanoic acid octadecylamide to carry out an addition reaction. After introduction of the specified amount of ethylene oxide, ripening at the same temperature until the pressure is 2 kg / cm ³ or less, further aging is promoted for about 30 minutes while maintaining an internal pressure of 5 kg / cm ² with nitrogen, and a reaction product is obtained after cooling It was. Alkaline adsorbent (KYOWARD 600S: manufactured by Kyowa Chemical Co., Ltd.) is used in an amount of 1.5% by weight with respect to the reaction product. And filtered under pressure to obtain 191 g (sample 7) of a yellowish white solid.

The obtained sample 7 was dissolved in deuterated chloroform at a rate of 10 mg / 0.5 ml using AV400M NMR manufactured by Bruker Biospin, and ¹ H-NMR (400 MHz) was measured to confirm the structure. As a result, from the integral ratio of methine protons observed near 3.2 to 3.3 ppm and methine protons observed near 3.1 ppm, a symmetrical type in which ethylene oxide is introduced into both hydroxyl groups. The structure and one hydroxyl group were unreacted, and it was confirmed that an asymmetric structure in which an ethylene oxide chain was introduced was contained only in one hydroxyl group at a ratio of 70:30 (mol%). The average addition mole number calculated | required from the integration ratio of the peak of 3.7 ppm vicinity was 88.0 mol. The HLB obtained by the Griffin method was 17.4.

Comparative Example 1
A 300 mL autoclave was charged with dodecyl alcohol (50 g, 0.27 mol) and 0.05 g of potassium hydroxide as a catalyst, and the system was purged with nitrogen, followed by dehydration at 120 ° C. under reduced pressure for 5 minutes. After completion of the dehydration, 5 mole equivalents of ethylene oxide with respect to 1 mole of dodecyl alcohol were introduced into the autoclave under the conditions of a reaction temperature of 180 ° C. and an internal pressure of 5 kg / cm ² . The sample was aged at the same temperature for 30 minutes until the pressure decreased and became constant, and after cooling, neutralized with acetic acid equivalent to potassium hydroxide to obtain Sample 8.

Comparative Example 2
Octadecyl alcohol (50 g, 0.18 mol) and 0.05 g of potassium hydroxide as a catalyst were added to a 300 mL autoclave, and the system was purged with nitrogen, followed by dehydration at 120 ° C. under reduced pressure for 5 minutes. After completion of the dehydration, 15 mole equivalents of ethylene oxide with respect to 1 mole of octadecyl alcohol were introduced into the autoclave under the conditions of a reaction temperature of 180 ° C. and an internal pressure of 5 kg / cm ² . The sample was aged at the same temperature for 30 minutes until the pressure decreased and became constant, cooled, and neutralized with acetic acid equivalent to potassium hydroxide to obtain Sample 9.

  The surfactant activity of the two-chain two-hydrophilic group-containing nonionic surfactant of the present invention obtained in Examples 1 to 7 and the one-chain one-hydrophilic group-containing nonionic surfactant of Comparative Examples 1-2 was tested. It was. The results are shown in Table 1.

* 1 Surface tension Various aqueous surfactant solutions (using purified water) were prepared, and the surface tension at 25 ° C was determined by the platinum plate method using Wilhelmy surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. A tension / concentration / relational diagram was prepared, and the critical micelle concentration (cmc) and the surface tension (γcmc) at the critical micelle formation concentration were determined from the bending point.

Claims (1)

Nonionic surface activity represented by the following general formula (2) in which two hydrophilic groups are introduced at the position of the double bond of the alkylamide of the unsaturated fatty acid having 10 to 26 carbon atoms represented by the following general formula (1) Agent.

In general formula (1), R ₁ —CH═CH—R ₂ is an alkenyl group having 9 to 25 carbon atoms, R ₃ is an alkyl group having 1 to 20 carbon atoms, and in general formula (2), AO is carbon. The oxyalkylene groups derived from the alkylene oxides of formulas 2 to 3, m and n are the same or different numbers of 0 to 100, and m + n = 1 to 200.