JPH08252448A - Nonionic surfactant - Google Patents

Abstract

PURPOSE: To obtain a nonionic surfactant in which safety for the human body is high and foaming property and foam stability are excellent. CONSTITUTION: This nonionic surfactant consists of a glycoside compound shown in a general formula (1) or (2); [Z(OH)q-1 ]-O[C3 H5 (OH)O]-R<1> (1), [Z(OH)q-1 ]-O[C3 H5 (OH)O]x -R<2> (2), (in the formulas, [Z(OH)q-1 ] denotes sacchare residue in which hydroxyl group bonded to anomeric carbon is removed from q pieces of hydroxyl groups bonded to sacchare compound shown as the formula [Z(OH)q ], and O[C3 H5 (OH)O] denotes glycerol residue in which two hydrogen atoms are removed form glycerol H-O[C3 H5 (OH)O]-H, R<1> denotes a 1-12C aliphatic group, 1<x<=7, and R<2> denotes a 13-22C aliphatic group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is excellent in foaming property and foam stability and has a good foam feeling,
It relates to a nonionic surfactant that is mild to the hair.

[0002]

2. Description of the Related Art Nonionic surfactants are generally known to have excellent skin mildness and safety, and are widely used in cosmetics such as foaming agents for toothpaste, kitchen detergents, skin care and hair care. ing. As the nonionic surfactant, ethylene oxide or propylene oxide adduct of higher alcohol, glycerin esters such as glycerin fatty acid ester and polyglycerin fatty acid ester,
Many are known, such as sugar alcohol esters such as sorbitan fatty acid ester, and oligosaccharide esters such as sucrose fatty acid ester and maltose fatty acid ester. However, these nonionic surfactants have various properties such as excellent solubilization of oils such as ethylene oxide or propylene oxide adducts of higher alcohols, and excellent emulsifying power such as sucrose fatty acid esters and glycerin esters. Although it has the features of
Generally, foaming is poor, and for use in products requiring foaming such as foaming agents for toothpaste, kitchen detergents, skin care cosmetics, hair care cosmetics, compared to anionic surfactants such as sodium lauryl sulfate, Since the foaming is significantly inferior, it is not used alone but is currently used in combination with various additives or other surfactants to improve the foaming. On the other hand, various glycosides are known as nonionic surfactants having high safety to the human body (JP-A-60-204794, JP-A-4-244094,
JP-A-6-145188). However, these glycosides, like the above-mentioned nonionic surfactants, also have the drawback of being inferior in foaming property, and are also inferior in foam stability.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a nonionic surfactant which is highly safe for the human body and has excellent foaming properties and foam stability.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. According to the present invention, a nonionic surfactant comprising a glycoside compound represented by the following general formula (1) or (2) is provided. Formula (1): [Z (OH) q- _1] -O [C ₃ H ₅ (OH) O] -R ¹ (1) (in the formula, [Z (OH) q- _1] of the formula [ Z (OH) q] represents a sugar residue excluding the hydroxyl group bonded to the anomeric carbon among the q hydroxyl groups bonded to the sugar compound, and is represented by —O [C ₃ H ₅ (OH) O]- Is glycerin HO
[C ₃ H ₅ (OH) O] -H represents a glycerin residue obtained by removing two hydrogen atoms, and R ¹ represents an aliphatic group having 1 to 12 carbon atoms. General formula (2): [Z (OH) q- _1] -O [C ₃ H ₅ (OH) O] x-R ^{2 (2)} (in the formula, with [Z (OH) q- _1] of the formula [Z (OH) q] shows a sugar residue obtained by removing the hydroxyl group bonded to the anomeric position carbon of the q hydroxyl groups bonded to a sugar compound represented, -O [C ₃ H ₅ (OH) O] x- polyglycerol H
-O [C ₃ H ₅ (OH) O] x-H 2 from (1 <x ≦ 7)
Shows a polyglycerin residue excluding the number of hydrogen atoms, R ²
Represents an aliphatic group having 13 to 22 carbon atoms)

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The sugar compounds used in the present invention include monosaccharides, oligosaccharides and sugar polymers. Hereinafter, these sugar compounds will be described in detail. (1) Monosaccharides Monosaccharides include those represented by the following general formula (3). CnH ₂ nOn (3) In the above formula, n represents a number of 5 or 6. Specific examples of such monosaccharides include arabinose, ribose, xylose, xylulose, ribulose, glucose, galactose, fructose, mannose, sorbose, talose, fucose, glucoheptose, sedoheptulose,
Examples thereof include mannoheptulose and glucoheptulose. (2) Oligosaccharides Examples of oligosaccharides include those represented by the following formula. _{P (CnH 2 nOn) - (} P-1) H 2 O (4) In the formula, n is a number of 5 or 6. P shows the number of 1-10. Such oligosaccharides include maltose, lactose, cellobiose, isomaltose, gentiobiose, laminaribiose, xylobiose, mannobiose, maltotriose, cellotriose, manninotriose, maltotetraose, polysaccharides (cellulose, hemicellulose, (Starch, inulin, dextrin, dextran, xylan, etc.) are hydrolyzed into low molecular weight compounds. (3) Sugar Polymer As the sugar polymer, for example, a mannose polymer, a glucose polymer and the like can be mentioned.

The glycoside compound represented by the general formula (1) in the present invention is a glycoside compound represented by the following general formula (5) Z (OH) q (5) A skeleton, and (OH) q represents q hydroxyl groups bonded to the sugar skeleton), and a sugar compound represented by the following general formula (6) HO [C ₃ H ₅ (OH) O] -R ¹ ( 6) It is produced by reacting with a glycerin derivative represented by the formula (wherein R ¹ represents an aliphatic group having 1 to 12 carbon atoms). The reaction in this case can be expressed by the following equation. Z (OH) q + HO [C ₃ H ₅ (OH) O] -R ¹ (7) → [Z (OH) q- _1] -O [C ₃ H ₅ (OH) O] -R ¹ wherein the general formula ( In the glycoside compound represented by 1), the glycerin residue is derived from unpolymerized glycerin. The carbon number of the aliphatic group R ¹ is 1 to 12, preferably 8 to 12, corresponding to the unpolymerized glycerin residue. The aliphatic group R ¹ includes a linear or branched saturated or unsaturated alkyl group. Examples of such an aliphatic group include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, undecyl, dodecyl, decenyl, undecenyl, dodecenyl and the like.

The glycoside compound represented by the general formula (2) in the present invention is represented by the following general formula (5) Z (OH) q (5) (wherein Z and q have the same meanings as described above). And a sugar compound represented by the following general formula (8) HO [C ₃ H ₅ (OH) O] x-R ² (8) (wherein R ² represents an aliphatic group having 13 to 22 carbon atoms, x
Is produced by reacting with a glycerin derivative represented by a number greater than 1 and 7 or less (1 <x ≦ 7). In the glycoside compound represented by the general formula (2), the glycerin residue has an average degree of polymerization x of more than 1 and 7 or less (1 <x ≦ 7), preferably 2 to
It is derived from 4 (2 ≦ x ≦ 4) polymerized glycerin. The aliphatic group R ² has 13 to 22 carbon atoms,
It is preferably 13-18. The aliphatic group R ² includes a linear or branched saturated or unsaturated alkyl group. Such aliphatic groups include dodecyl, tridecyl, tetradecyl, pentadecyl, pentadecenyl, hexadecyl, octadecyl, nonadecyl, eicosyl,
Heneicosyl, hexadecenyl, nonadecenyl and the like can be mentioned.

The glycerin derivatives represented by the above general formulas (6) and (8) can be obtained by reacting glycerin or polyglycerin with an alkylating agent such as an alkyl halide or an alkyl sulfate metal salt.

Each of the glycoside compounds represented by the general formula (1) or (2) has a proper balance of hydrophilicity due to glycerin residues and hydrophobicity due to aliphatic groups, and has an excellent interface. It shows an active action. The glycoside compound (1) represented by the general formula (1) and the glycoside compound (2) represented by the general formula (2) are preferably used alone, respectively, and the glycoside compounds (1) and (2) are used respectively. When mixed, it tends to cause a decrease in the surfactant effect.

The glycoside compound represented by the general formula (1) or (2) is preferably a mixture of stereoisomers at the anomeric position, and α-form and β-form which are stereoisomers at the anomeric position. The weight ratio of
0/20 to 5/95, preferably 70/30 to 10/9
It is 0, more preferably 60/40 to 50/50. α
When the weight ratio α / β of the body to the β body deviates from the above range, the surfactant tends to have a poor foaming property, a low water solubility, and a poor foam feel.

Generally, in order to generate a foam having excellent foam stability with good foaming property by using a surfactant, it is important to arrange the surfactants regularly at the oil / water interface and the gas / liquid interface. From this point of view, the glycoside represented by the general formula (1) is better in foaming power and foam stability when used in the α form or β form alone than in the mixture of the α form and the β form. Although it was considered to have excellent surfactant activity, surprisingly, when used in the form of a mixture of α-form and β-form, a synergistic effect was obtained, and when the α-form and β-form were used alone It has been found to show a better surfactant effect.

The glycoside compound represented by the general formula (1) or (2) can be synthesized by a chemical method or an enzymatic method. As a chemical method, the Fischer method [BIO INDUSTRY, 10 , 408 (199
3)] is known.

As a method for adjusting the ratio of the α-form and the β-form of the glycoside compound, a method of mixing a high-purity α-form and a high-purity β-form at a predetermined ratio, and an α-form having a high α-form content ratio A method of adding the β-form at a predetermined ratio to the mixture of β-form and
An enzyme that selectively hydrolyzes the α-form with a mixture of the α-form and the β-form having a high α-form content, for example, α-amylase, α
-Glucosidase, α-galactosidase, α-glycosidase such as α-mannosidase, α-transglycosidase, and a method of hydrolyzing a certain amount of α-form in the presence of α-transglycosidase such as α-galactosyltransferase. .

[0014]

INDUSTRIAL APPLICABILITY The nonionic surfactant of the present invention has excellent foamability and foam stability, and produces a foam having a refreshing and good foam feeling. The nonionic active agent of the present invention is used in various applications in which the nonionic active agent has been conventionally used, for example, as a foaming agent for toothpaste (particularly with enzyme) and other oral compositions, and as a kitchen detergent. Further, it can be effectively used as a main agent of the cleaning agent for skin care such as shampoo, body shampoo, face wash, and hair care products. Further, since it has a high mild property and is less likely to cause protein denaturation, it can be suitably used for liquid detergents, particularly for enzyme-containing liquid detergents, wool detergents and the like.

[0015]

【Example】

 EXAMPLES Next, the present invention will be described in more detail by way of examples.

Reference Example 1 Using a sugar compound and a glycerin derivative as reaction raw materials, Fi
The glucoside compound having the structure shown in Table 1 was synthesized by the scher method. In Table 1, glucoside compounds are shown corresponding to the following structural formulas. In [mA- (OH) q- _1] -O [C ₃ H ₅ (OH) O] x-R (A) This equation, [mA- (OH) q- _1] of the formula [mA
-(OH) q] (sugar compound (average degree of polymerization is m
Among the hydroxyl groups bonded to the glucose (A) polymer, the sugar residue excluding the hydroxyl group bonded to the anomeric carbon is shown. Further, the formula -O [C ₃ H ₅ (OH) O] x-R are glycerin derivative residue obtained by removing a hydrogen atom from a glycerol derivative of the formula HO [C ₃ H ₅ (OH) O] x-R Indicates. Table 1 also shows the weight ratio α / β of the α-form and β-form of the glucoside compound.

[0017]

[Table 1]

Examples 1 to 4 Product Nos. Obtained in Reference Example 1 For the glucosides A to D, their foaming performance and foam feel were measured as follows, and the measurement results are shown in Table 2.

Comparative Example 1 Product No. obtained in Reference Example 1 A glucoside and product no.
With respect to the mixture obtained by mixing C glucoside at a weight ratio of 12/8, the foaming performance and the foam feeling were measured as follows, and the measurement results are shown in Table 2.

Comparative Example 2 Product No. obtained in Reference Example 1 B glucoside and product no.
The foaming performance and the foam feeling of the mixture prepared by mixing D glucoside with the weight ratio of 13/7 were measured as follows, and the measurement results are shown in Table 2.

(Measurement of Foaming Performance) 10 ml of a 0.5% by weight aqueous solution of a sample was put into an Epton tube (100 ml), and 25
After keeping the temperature constant in a water bath at 0 ° C., the mixture was shaken 20 times for 10 seconds, and the foam volume V (1) 30 seconds after the end of the shaking and the foam volume V (2) after 5 minutes were measured. The results are shown in Table 2.

(Evaluation of Bubble Feel) A sample is used at a concentration of 0.5% by weight.
Was dissolved in water at 50 ° C., 50 ml of this aqueous solution was placed in a 100 ml sample bottle with a lid, and this was shaken 10 times at 40 ° C., and then the face was washed with this foamed sample solution and evaluated. ○: There is a refreshing feeling △: There is a refreshing feeling ×: The refreshing feeling is weak

[0023]

Reference Example 2 Glucose (C ₆ H ₁₂ O ₆ ) and decylglycerin [C ₁₀ H
₂₁ OCH (CH ₂ OH) CH ₂ OH] as a raw material,
Decylglyceryl glucoside represented by the general formula (A) by the Fischer method (in the general formula (A), R
= Decyl group, m = 1.5, x = 1) 150 parts by weight was dissolved in methanol as a solvent at a concentration of 80% by weight, and this solution was dissolved in an anion exchange resin (trade name: Dowex 1, O).
After adsorbing to a column filled with H type, particle size 200 to 400 mesh, manufactured by Dow Chemical Co., Ltd., methanol was passed through the adsorption column as an eluent to separate α and β forms by adsorption. As a result of this adsorption separation, 91 parts by weight of α form and 38 parts of β form
Parts by weight were each obtained with a purity of 100%.

Example 5 A sample was prepared by mixing α-decylglyceryl glucoside and β-decylglyceryl glucoside obtained in Reference Example 2 at the weight ratio (α / β) shown in Table 3. The performance of this sample was measured in the same manner as in Examples 1 to 4, and the results are shown in Table 3. In addition, for comparison, the results using the existing nonionic surfactant are also shown in Table 3. The specific contents of the nonionic surfactants A, B, and C shown in Table 3 are as follows. A: Sucrose ester (Ryo-to sugar ester, P
-1670, manufactured by Mitsubishi Kasei Foods) B: 9 mol ethylene oxide 9 adduct of alcohol having 12 to 13 carbon atoms C: alkyl polyglucoside (APG-600, manufactured by Henkel)

[0026]

[Table 1]

Next, a composition containing the nonionic surfactant of the present invention is shown. [Composition 1] Shampoo Glucoside (Product No. A) 10.5 (% by weight) Lauryl ethoxy sulfate sodium salt 3.5 Cocoyl diethanolamide 2.0 Sodium sulfate 1.5 Fragrance / dye Appropriate amount of water residue ━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Total 100.0 [Composition 2] Toothpaste composition Dicalcium phosphate dihydrate 45.5 (weight) %) Glycerin 5.0 Sorbitol 15.0 Sodium carboxymethylcellulose 1.0 Glucoside (Product No. B) 1.5 Flavors and sweeteners Appropriate amount of water Residue ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━ Total 100.0 [Composition 3] Liquid stone Ken oleyl tetraglyceryl polyglucoside 20.0 (wt%) Lauryl sulfate sodium salt 10.0 Fragrance Emulsifier Appropriate amount of water Residue ━━━━━━━━━━━━━━━━━━━━━━━━━━ Total 100.0 In addition, the oleyl tetraglyceryl polyglucoside [the above general formula In (A), m: 1.4, x: 4,
R: oleyl group] is a mixture of α-form / β-form weight ratio = 60/40. [Composition 4] Vegetable dishwashing agent Alcohol ethoxylate sulfate sodium salt 20.0 (% by weight) Glucoside (Product No. D) 10.0 Lauryl alkanolamide 5.0 Fragrance / emulsifier Appropriate amount of water residue ━━ ━━━━━━━━━━━━━━━━━━━━━━━━ Total 100.0

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location A61K 7/16 A61K 7/16 7/50 7/50 B01F 17/38 B01F 17/38 C11D 1 / 68 C11D 1/68 (72) Inventor Haruhiko Toda 1-3-7 Honjo, Sumida-ku, Tokyo Lion Corporation

Claims (2)

[Claims] 1. A nonionic surfactant comprising a glycoside compound represented by the following general formula (1) or (2). Formula (1): [Z (OH) q- _1] -O [C ₃ H ₅ (OH) O] -R ¹ (in the formula, [Z (OH) q- _1] of the formula [Z (OH ) shows a saccharide residue obtained by removing the hydroxyl group bonded to the anomeric position carbon of the q hydroxyl groups bonded to a sugar compound represented by q], -O [C ₃ H ₅ (OH) O] - glycerin H -O
[C ₃ H ₅ (OH) O] -H represents a glycerin residue obtained by removing two hydrogen atoms, and R ¹ represents an aliphatic group having 1 to 12 carbon atoms. General formula (2): [Z (OH) q- _1] -O [C during ₃ H ₅ (OH) O] x-R ² (wherein, [Z (OH) q- _1] sugar of the formula [Z (OH) q] shows a sugar residue obtained by removing the hydroxyl group bonded to the anomeric position carbon of the q hydroxyl groups bonded to the compound, -O [C ₃ H ₅ (OH) O] x- polyglycerol H
-O [C ₃ H ₅ (OH) O] x-H 2 from (1 <x ≦ 7)
Shows a polyglycerin residue excluding the number of hydrogen atoms, R ²
Represents an aliphatic group having 13 to 22 carbon atoms) 2. The glycoside compound represented by the general formula (1) or (2) comprises a mixture of isomers of α-form and β-form, and the weight ratio of the α-form to the β-form is 80/20 to 5.
/ 95, The surfactant of claim 1.