CN103974690B - Composition of skin cleanser - Google Patents

Composition of skin cleanser Download PDF

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Publication number
CN103974690B
CN103974690B CN201280060484.8A CN201280060484A CN103974690B CN 103974690 B CN103974690 B CN 103974690B CN 201280060484 A CN201280060484 A CN 201280060484A CN 103974690 B CN103974690 B CN 103974690B
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composition
quality
skin cleanser
alkyl
general formula
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CN103974690A (en
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园田纯子
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Kao Corp
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Kao Corp
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap

Abstract

The present invention relates to a kind of composition of skin cleanser, wherein containing following composition (A) ~ (E), the alkyl ether carboxylic acid represented by (A) general formula (1), its content is 1 ~ 20 quality %, R in this alkyl ether carboxylic acid 1average carbon atom number be 10.8 ~ 12.8, comprise composition 4.3 ~ 30 quality % of n=0, the total content of the composition of n=1 and the composition of n=2 is more than 20 quality % and is less than 40 quality %; (B) fatty acid represented by general formula (2), its content is 1 ~ 20 quality %; (C) cationic polymer, its content is 0.1 ~ 5 quality %; (D) alkali; (E) water, composition (A) and (B) exist in a salt form with composition (D) at least partially, and composition (D) is (composition (D)/(composition (A)+composition (B)))=0.9 ~ 1.1 relative to the mol ratio of composition (A) and (B).R 1-O-(CH 2cH 2o) n-CH 2-COOH? (1) (in formula, R 1represent that carbon number is the alkyl of 4 ~ 22, n represents the number of 0 ~ 20) R 2 -cOOH? (2) (in formula, R 2represent that carbon number is the straight chain of 9 ~ 21 or the alkyl of side chain or thiazolinyl).

Description

Composition of skin cleanser
Technical field
The present invention relates to composition of skin cleanser.
Background technology
In recent years, the mildness to skin is sought for clean body agent.Particularly for foam time clean, have and think if with the cleaning not having the coarse foam duration of elastic quality to have friction, then can produce the consumer of xerosis cutis or the skin problem such as speckle, wrinkle, along with the raising of defying age consciousness, seek the cleaning agent that can obtain more resilient foam.
For thinking one of the cleaning agent that can obtain resilient foam, the cleaning agent of the paste making fatty acid crystallization can be enumerated.Fatty acid and the high molecular combination of cationic is disclosed in patent documentation 1.
In addition, in order to produce elasticity in the foam, there is the method (patent documentation 2) specific non-ionic surface active agent and anion surfactant being combined vacuolar membrane is strengthened; Attempt by specific soap and other surfactant are combined, form creamy alveolar substance (patent documentation 3) with homogenizing.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-20941 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-150303 publication
Patent documentation 3: Japanese Unexamined Patent Publication 11-35972 publication
Summary of the invention
The present invention relates to a kind of composition of skin cleanser, it contains following composition (A), (B), (C), (D) and (E):
(A) alkyl ether carboxylic acid represented by general formula (1), its content is 1 ~ 20 quality %,
R 1-O-(CH 2CH 2O) n-CH 2-COOH(1)
(in formula, R 1represent that carbon number is the alkyl of 4 ~ 22, n represents the number of 0 ~ 20.)
R in described alkyl ether carboxylic acid 1average carbon atom number be 10.8 ~ 12.8, comprise composition 4.3 ~ 30 quality % of n=0, the total content of the composition of n=1 and the composition of n=2 is more than 20 quality % and is less than 40 quality %;
(B) fatty acid represented by general formula (2), its content is 1 ~ 20 quality %;
R 2-COOH(2)
(in formula, R 2represent that carbon number is the straight chain of 9 ~ 21 or the alkyl of side chain or thiazolinyl.)
(C) cationic polymer, its content is 0.1 ~ 5 quality %;
(D) alkali;
(E) water,
Composition (A) and (B) exist in a salt form with composition (D) at least partially, and composition (D) is 0.9 ~ 1.1 relative to the mol ratio (composition (D)/(composition (A)+composition (B))) of composition (A) and (B).
Detailed description of the invention
Make the cleaning agent of the paste of fatty acid crystallization need a large amount of fatty acids as described in Patent Document 1, as the use sense after clean, easily produce tight sense, dry sensation, vary with each individual and can produce uncomfortable situation.On the other hand, although the combination of the combination of anion surfactant as described in Patent Document 2 and specific non-ionic surface active agent or as described in Patent Document 3 soap and other surfactant forms creamy alveolar substance, there is the technical problem that the elasticity of foam is weak.
The present invention relates to the fine and smooth elasticity of a kind of alveolar substance excellent, the skin wet after having cleaned, and the composition of skin cleanser that inhibit tight sense.
Present inventor finds: if specific alkyl ether carboxylic acid and specific fatty acid, cationic polymer compositions used, then can obtain the fine and smooth elasticity of alveolar substance excellent, and the skin wet after cleaning, inhibit the composition of skin cleanser of tight sense.
The fine and smooth elasticity of composition of skin cleanser alveolar substance of the present invention is excellent, and the skin wet after cleaning, tight sense can be suppressed.In the present invention, tight sense is when having cleaned, such as towel off dry after, skin surface tightens the same sensation
Composition (A) alkyl ether carboxylic acid used in the present invention represents with general formula (1).
In formula, R 1for carbon number is the alkyl of 4 ~ 22, being preferably carbon number is the alkyl of 6 ~ 20, and be more preferably the alkyl that carbon number is 8 ~ 18, be more preferably the alkyl that carbon number is 8 ~ 16, more preferably carbon number is the alkyl of 10 ~ 16.In addition, R 1alkyl chain can be any one of straight chain or side chain, from the view point of foaming characteristic, be preferably straight chained alkyl.In addition, R 1average carbon atom number be 10.8 ~ 12.8, be preferably 10.8 ~ 12.5, more preferably 12.1 ~ 12.4.If within the scope of this, then due to foaming characteristic, alveolar substance, further low-temperature stability aspect is excellent, therefore preferably.
In addition, R 1preferably comprise alkyl of more than two kinds, the composition with the maximum alkyl chain length of content is preferably more than 55 quality % and is less than 97 quality %, and more preferably 60 ~ 95 quality %, from bubble amount and alveolar substance excellence, are more preferably 70 ~ 95 quality %.
In addition, in formula, n represents the number of 0 ~ 20, more preferably 0 ~ 12.In addition, n represents the addition molal quantity of ethylene oxide, good from the view point of alveolar substance, average addition molal quantity (meansigma methods of n) in the composition of composition (A) is preferably 1.5 ~ 10, more preferably 2.5 ~ 4.5, be more preferably 2.5 ~ 3.4, be more preferably 2.8 ~ 3.4, be more preferably 2.8 ~ 3.1 further.
The alkyl ether carboxylic acid of composition (A), be included in composition 4.3 ~ 30 quality % of n=0 in general formula (1), be preferably 4.9 ~ 27 quality %, more preferably 9.6 ~ 27 quality %, be more preferably 9.9 ~ 16 quality %, be more preferably 9.9 ~ 15 quality % further.By within the scope of this, improve not soapy feeling during flushing.
Further, the total content of the composition of n=1 and the composition of n=2 is more than 20 quality % and is less than 40 quality %, from the view point of alveolar substance, bubble amount, is preferably 20 ~ 37 quality %, more preferably 27 ~ 36.5 quality %, are more preferably 35 ~ 36.1 quality %.
In the alkyl ether carboxylic acid of composition (A), from the view point of not soapy feeling when taking into account foaming characteristic, cleaning, flushing, n=0 in preferred formula (1), 1,2,3, the mass ratio of the composition of 4 is (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:0.99 ~ 3.50:0.89 ~ 3.00:0.76 ~ 3.00:0.63 ~ 1.6.
Further, from the view point of foaming characteristic and washability, be preferably, in general formula (1), the composition of n=0 contains more than 9.6 quality % and is less than 12 quality %, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.53 ~ 1.87:1.59 ~ 2.25:1.33 ~ 2.16:1.14 ~ 1.52, or, the composition of n=0 contains more than 12 quality % and below 17 quality %, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:0.99 ~ 1.34:0.89 ~ 1.40:0.76 ~ 1.23:0.63 ~ 0.99.
Further, from bubble amount, the viewpoint of alveolar substance and washability is set out, in preferred formula (1), the composition of n=0 contains 9.9 ~ 11.5 quality %, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.58 ~ 1.84:1.72 ~ 2.17:1.49 ~ 2.00:1.14 ~ 1.52, or, in general formula (1), the composition of n=0 contains 13 ~ 17 quality %, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.00 ~ 1.31:0.93 ~ 1.34:0.79 ~ 1.18:0.63 ~ 0.99.
In composition (A), preferably: R in general formula (1) 1for carbon number is the alkyl of 4 ~ 22, R 1average carbon atom number be 10.8 ~ 12.8, in addition, the composition with the maximum alkyl chain length of content is more than 55 quality % and is less than 97 quality %, further, n represents the number of 0 ~ 20, meansigma methods is that the composition of 1.5 ~ 10, n=0 contains 4.9 ~ 27 quality %, and the total content of the composition of n=1 and the composition of n=2 is 20 ~ 37 quality %.Foaming characteristic can be accelerated like this.
In composition (A), preferably: R in general formula (1) 1for carbon number is the alkyl of 6 ~ 20, R 1average carbon atom number be 10.8 ~ 12.8, in addition, the composition with the maximum alkyl chain length of content is more than 55 quality % and is less than 97 quality %, further, n represents the number of 0 ~ 20, meansigma methods is that the composition of 2.5 ~ 4.5, n=0 contains 9.6 ~ 27 quality %, and the total content of the composition of n=1 and the composition of n=2 is 27 ~ 36.5 quality %.Foaming characteristic can be accelerated like this.
In composition (A), preferably: R in general formula (1) 1for carbon number is the alkyl of 8 ~ 18, R 1average carbon atom number be 10.8 ~ 12.8, in addition, the composition with the maximum alkyl chain length of content is more than 55 quality % and is less than 97 quality %, further, n represents the number of 0 ~ 20, meansigma methods is that the composition of 2.5 ~ 3.4, n=0 contains 9.6 ~ 27 quality %, and the total content of the composition of n=1 and the composition of n=2 is 27 ~ 36.5 quality %.Flushing when can strengthen flushing like this completes sense (stopfeeling).
In composition (A), preferably: R in general formula (1) 1for carbon number is the alkyl of 8 ~ 16, R 1average carbon atom number be 10.8 ~ 12.5, in addition, the composition with the maximum alkyl chain length of content is 60 ~ 95 quality %, further, n represents the number of 0 ~ 20, and meansigma methods is that the composition of 2.8 ~ 3.4, n=0 contains 9.6 ~ 27 quality %, total content preferably containing the composition of 9.9 ~ 16 quality %, n=1 and the composition of n=2 is 27 ~ 36.5 quality %.Bubble amount, alveolar substance can be improved like this.
In composition (A), preferably: R in general formula (1) 1for carbon number is the alkyl of 10 ~ 16, R 1average carbon atom number be 12.1 ~ 12.4, in addition, the composition with the maximum alkyl chain length of content is 60 ~ 95 quality %, further, n represents the number of 0 ~ 20, meansigma methods is that the composition of 2.8 ~ 3.1, n=0 contains 9.9 ~ 15 quality %, and the total content of the composition of n=1 and the composition of n=2 is 35 ~ 36.1 quality %.Can improve bubble amount, alveolar substance and foam is like this difficult to dripping.
In addition, in composition of the present invention (A), R 1the distribution of alkyl chain length, R 1the component amount of long, the n=0 of mean alkyl chain, the average addition molal quantity of n, n=0,1,2,3, the mass ratio of the composition of 4 can be analyzed by the alkyl ether carboxylic acid represented by gas chromatogram mutual-through type (1), try to achieve according to following method.
[R 1the distribution of alkyl chain length]
In the peak area obtained by gas chromatogram, try to achieve the peak area of each alkyl chain length being equivalent to n=0mol, using its summation as 100, try to achieve the percentage rate of each alkyl chain length distribution.Calculate similarly for n=1 ~ 3mol, the percentile value of each alkyl chain length distribution of average n=0 ~ 3mol, tries to achieve R 1the distribution of alkyl chain length (thus, can specific R 1containing maximum alkyl component in composition).
[R 1mean alkyl chain long]
According to the R tried to achieve in the manner described above 1the distribution of alkyl chain length, try to achieve the ratio of each composition, the ratio obtained is multiplied by the carbon number of corresponding alkyl chain length composition respectively, tries to achieve their summation.It can be used as mean alkyl chain long.
[the total content of the composition of the component amount of n=0, the composition of n=1 and n=2]
Specific R 1composition in containing maximum alkyl chain length, add up to the area being equivalent to the gas chromatogram of n=0 ~ 10 of its composition.Using this total amount as 100%, calculate the total content of the composition of the component amount of n=0, the composition of n=1 and n=2.
[the average addition molal quantity of n]
Specific R 1composition in containing maximum alkyl chain length, add up to the area (n is the composition of more than 11 is trace, removing from calculating) being equivalent to the gas chromatogram of n=0 ~ 10 of its composition.Using this total amount as 1, try to achieve each ratio of n=0 ~ 10 respectively.This ratio is multiplied by each addition molal quantity, using the average addition molal quantity of their total as n.
[mass ratio of the composition of n=0, n=1, n=2, n=3, n=4]
For the ratio of the different each composition of EO addition molal quantity, by the peak area obtained by gas chromatogram, try to achieve R by the method shown in above-mentioned 1the distribution of alkyl chain length, specific R 1the alkyl chain length composition of maximum level in composition, comes specific by the area ratio of n=0, n=1, n=2, n=3, n=4 of this maximum composition.
Because the alkyl ether carboxylic acid of composition (A) has composition as above, therefore, sufficient bubble amount, good alveolar substance is obtained from during cleaning, and suppress the viewpoint of tight sense to be set out, containing more than 1 quality % in all forming, preferably containing more than 5 quality %, be more preferably containing more than 6 quality %.In addition, the content of composition (A) is preferably below 20 quality %, more preferably below 15 quality % in all forming, and is more preferably below 12 quality %.In addition, composition (A) preferably containing 1 ~ 20 quality %, preferably contains 2 ~ 15 quality % further, is more preferably containing 4 ~ 12 quality % in all forming.In addition, composition (A) forms salt by composition (D) its part or all, thus can show above effect.
The fatty acid of the composition (B) used in the present invention is the material represented with above-mentioned general formula (2).
In formula, R 2for alkyl or thiazolinyl that carbon number is 9 ~ 21, can be any one of straight chain or side chain, more preferably carbon number be the alkyl of 11 ~ 21, is more preferably the alkyl that carbon number is 13 ~ 17.
As composition (B), be preferably myristic acid, Palmic acid, stearic acid or behenic acid.
In addition, from making, the quality of foam is finer and smoother, suppresses the viewpoint of tight sense to be set out, in the fatty acid of composition (B), and R in general formula (2) 2carbon number be that the alkyl of 15 ~ 21 or the fatty acid of thiazolinyl are preferably 40 ~ 100 quality % in all fatty acids of composition (B), be more preferably containing 50 ~ 80 quality %.
Composition (B) can use a kind or two or more, from the view point of obtaining spatter property and foaming characteristic, containing more than 1 quality % in whole compositions, being preferably more than 5 quality %, being more preferably more than 6 quality %.In addition, the easiness of the foaming of the suppression from the view point of the elasticity and tight sense of taking into account foam and the viscosity by compositions etc., the content of composition (B) in all forming is preferably below 20 quality %, more preferably below 15 quality %, are more preferably below 12 quality %.In addition, composition (B) preferably containing 1 ~ 20 quality %, preferably contains 5 ~ 15 quality % further, is more preferably containing 6 ~ 12 quality % in all forming.
In composition of skin cleanser of the present invention, from the view point of obtaining more resilient foam, the total content of composition (A) and (B) is preferably 2 ~ 40 quality %, more preferably 5 ~ 30 quality % in all forming, and is more preferably 10 ~ 30 quality %.
In addition, in composition of skin cleanser of the present invention, think that the dissolubility of composition (B) improves, thus can improve the orientation of composition (B) in the vacuolar membrane formed at composition (A) by composition (A) and (B) being mixed.Its result, can obtain the alveolar substance of exquisite quality.Particularly, suppress tight sense from the view point of the elasticity improving foam, composition (A) and (B) as sour mass ratio, preferably (A)/(B)=0.3 ~ 5, more preferably 0.5 ~ 2, be more preferably 0.5 ~ 1.5.
Further, in composition (A) and composition (B), suppress tight sense, R in general formula (2) from the view point of the elasticity improving foam 2carbon number be the alkyl of 15 ~ 21 fatty acid (composition (B-1)) as acid mass ratio, be preferably (A)/(B-1)=0.2 ~ 5, more preferably 0.3 ~ 3.5, be more preferably 0.3 ~ 2, be more preferably 0.4 ~ 2 further.
As the cationic polymer of the composition used in the present invention (C), such as, Poise C-80M can be enumerated, cationic starch, JR-125, cationization tara gum, cationization locust bean gum, cationization trigonella bean gum, cationization xanthan gum, the polymer of poly (dially dialkyl) based quaternary ammonium salt, poly (dially dialkyl) based quaternary ammonium salt/acrylamide copolymer, poly (dially dialkyl) based quaternary ammonium salt/acrylamide/acrylic acid copolymer, vinyl tri-chlorination imidazoles/vinylpyrrolidone copolymer, hydroxyethyl-cellulose/dimethyl diallyl ammonium chloride copolymer, vinyl pyrrolidone/quaternized dimethyl amino ethyl methacrylate copolymer, polyvinyl pyrrolidone/alkyl amido acrylate copolymer, polyvinyl pyrrolidone/alkyl amido acrylate/vinyl caprolactam copolymer, vinyl pyrrolidone/Methacrylamide hydroxypropyltrimonium chloride copolymer, alkyl acrylamide/acrylate/alkylaminoalkyl group acrylamide/polyethylene glycol methacrylate-styrene polymer copolymer, adipic acid/dimethylamino hydroxypropyl ethylenetriamine copolymer (Sandoz company of the U.S., CARTARETIN), Japanese Laid-Open Patent Publication 53-139734 publication, the cationic polymer etc. recorded in Japanese Laid-Open Patent Publication 60-36407 publication.
Wherein, from the view point of obtaining resilient foam, be preferably selected from poly (dially dialkyl) based quaternary ammonium salt/acrylamide copolymer, poly (dially dialkyl) based quaternary ammonium salt/acrylamide/acrylic acid copolymer, JR-125, Poise C-80M a kind or two or more.
Composition (C) can use more than a kind, from the view point of obtaining more resilient foam, containing more than 0.1 quality % in all forming, preferably containing more than 0.5 quality %, preferably containing below 5 quality %, further preferably containing below 2 quality %.In addition, the content of composition (C) is preferably 0.1 ~ 5 quality % in all forming, and is more preferably 0.5 ~ 2 quality %.
As the alkali of the composition used in the present invention (D), such as, can enumerate the alkali-metal hydroxide of sodium hydroxide, potassium hydroxide etc.; Ammonia; The organic amine compound of triethanolamine etc.; The basic amino acid etc. of arginine etc.Wherein, from the view point of stability, be preferably alkali-metal hydroxide, from the view point of the adjustment of fluidity, be preferably potassium hydroxide.
In the present invention, composition (A) and (B's) exists with composition (D) form in a salt form at least partially.
Composition (D) is 0.9 ~ 1.1 relative to the mol ratio (composition (D)/(composition (A)+composition (B))) of composition (A) and (B), preferably contains in the mode becoming 0.95 ~ 1.05.By using in this wise, more resilient foam can be obtained.
Composition of skin cleanser of the present invention can contain composition (E) water further as solvent.Water preferably containing more than 10 quality %, is preferably more than 15 quality % in all forming, preferred containing more than 30 quality % further, be preferably below 96 quality %, more preferably below 90 quality %, are more preferably below 87 quality %, are more preferably below 85 quality % further.In addition, water preferably can contain 10 ~ 96 quality %, more preferably 15 ~ 90 quality % in all forming, and is more preferably 30 ~ 87 quality %, becomes and forms the described composition of cleanser compositions and the remainder of other composition.
Composition of skin cleanser of the present invention, by comprising composition (A) ~ (E), can make the exquisite quality of foam, improves the elasticity of foam, therefore, be difficult to time clean injure skin, the high clean true feeling of smooth sense of touch can be improved, tight sense can be suppressed.
Composition of skin cleanser of the present invention can contain (F) polyhydric alcohol further, thus has cleaned rear skin wet, can improve further and not have tight sense of touch.
As described polyhydric alcohol, such as, can enumerate Sorbitol, glycerol, butanediol, propylene glycol, dipropylene glycol, erythritol, mannitol, xylitol etc.Wherein, the elastic viewpoint of the skin feel more moistening, not tight from the skin cleaned and foam, is preferably glycerol, Sorbitol.
The polyhydric alcohol of composition (F) can use more than a kind, from the view point of the skin feel of having cleaned, preferably in all forming, contain more than 1 quality %, further preferably containing more than 5 quality %, preferably containing below 40 quality %, further preferably containing below 30 quality %.In addition, preferred component (F) contains 1 ~ 40 quality % in all forming, further preferably containing 5 ~ 30 quality %.
Composition of skin cleanser of the present invention can further containing the composition used in common cleaning agent, such as, salt, pearling agent, frosting agent (scrubbingagent), spice, creeping chill agent, pigment, UV absorbent, antioxidant, plant extract etc. beyond the surfactant beyond composition (A) and (B), wetting agent, oil components, antibacterial, anti-inflammatory agent, antiseptic, chelating agen, viscosifier, composition (D).
Composition of skin cleanser of the present invention can assign to manufacture by fitting in usual way mixing.The cleanser compositions obtained can be aqueous or any one in solid, shaped, when for aqueous, viscosity when measuring with Brookfield viscometer (manufacture of Tokyo gauge company) at 25 DEG C is preferably 200 ~ 80000mPas, can assign to regulate by suitably selecting to fit in.
In addition, pH is preferably 3 ~ 12, and more preferably 5 ~ 10.5, be more preferably 5 ~ 7.In addition, the mensuration of pH each cleanser compositions is diluted to ion exchange water the value measured after 20 times at 25 DEG C.
Composition of skin cleanser of the present invention, such as, be suitable as cleansing milk, bath gel (bodysoap), handwashing liquid (handsoap) etc., is preferably cleansing milk, bath gel.
Use the method for composition of skin cleanser cleaning skin of the present invention, such as described below.That is, used by composition of skin cleanser of the present invention in right amount in health, namely the body skin position of face, trick, body etc., after foaming cleansing, utilizes the method for the warm water washing of shower etc.In addition, also can use appropriate on the cleaning aid of resinous towel, resinous sponge, brush etc., bubble and use, more effectively clean thus.
About above-mentioned embodiment, the present invention discloses following compositions, method, purposes further.
<1> composition of skin cleanser, wherein, containing following composition (A), (B), (C), (D) and (E):
(A) alkyl ether carboxylic acid represented by general formula (1), its content is 1 ~ 20 quality %,
R 1-O-(CH 2CH 2O) n-CH 2-COOH(1)
(in formula, R 1represent that carbon number is the alkyl of 4 ~ 22, n represents the number of 0 ~ 20.)
R in described alkyl ether carboxylic acid 1average carbon atom number be 10.8 ~ 12.8, comprise composition 4.3 ~ 30 quality % of n=0, the total content of the composition of n=1 and the composition of n=2 is more than 20 quality % and is less than 40 quality %;
(B) fatty acid represented by general formula (2), its content is 1 ~ 20 quality %;
R 2-COOH(2)
(in formula, R 2represent that carbon number is the straight chain of 9 ~ 21 or the alkyl of side chain or thiazolinyl.)
(C) cationic polymer, its content is 0.1 ~ 5 quality %;
(D) alkali;
(E) water,
Composition (A) and (B) exist in a salt form with composition (D) at least partially, and composition (D) is 0.9 ~ 1.1 relative to the mol ratio (composition (D)/(composition (A)+composition (B))) of composition (A) and (B).
The composition of skin cleanser of <2> as described in above-mentioned <1>, wherein, in composition (A), in general formula (1), R 1for carbon number is the alkyl of 4 ~ 22, being preferably carbon number is the alkyl of 6 ~ 20, and be more preferably the alkyl that carbon number is 8 ~ 18, be more preferably the alkyl that carbon number is 8 ~ 16, more preferably carbon number is the alkyl of 10 ~ 16, in addition, and R 1alkyl chain can be any one of straight chain or side chain, be preferably straight chained alkyl.
The composition of skin cleanser of <3> as described in above-mentioned <1> or <2>, wherein, in composition (A), in general formula (1), R 1average carbon atom number be 10.8 ~ 12.8, be preferably 10.8 ~ 12.5, more preferably 12.1 ~ 12.4.
The composition of skin cleanser of <4> according to any one of above-mentioned <1> ~ <3>, wherein, in composition (A), in general formula (1), R 1comprise alkyl of more than two kinds, the composition with the maximum alkyl chain length of content is preferably more than 55 quality % and is less than 97 quality %, and more preferably 60 ~ 95 quality %, are more preferably 70 ~ 95 quality %.
The composition of skin cleanser of <5> according to any one of above-mentioned <1> ~ <4>, wherein, in composition (A), in general formula (1), the meansigma methods (average addition molal quantity) of n is preferably 1.5 ~ 10, more preferably 2.5 ~ 4.5, be more preferably 2.5 ~ 3.4, be more preferably 2.8 ~ 3.4, be more preferably 2.8 ~ 3.1 further.
The composition of skin cleanser of <6> according to any one of above-mentioned <1> ~ <5>, wherein, in composition (A), in general formula (1), the composition of n=0 comprises 4.3 ~ 30 quality %, be preferably 4.9 ~ 27 quality %, more preferably 9.6 ~ 27 quality %, be more preferably 9.9 ~ 16 quality %, more preferably comprise 9.9 ~ 15 quality % further.
The composition of skin cleanser of <7> according to any one of above-mentioned <1> ~ <6>, wherein, in composition (A), in general formula (1), the total content of the composition of n=1 and the composition of n=2 is preferably 20 ~ 37 quality %, more preferably 27 ~ 36.6 quality %, are more preferably 35 ~ 36.1 quality %.
The composition of skin cleanser of <8> according to any one of above-mentioned <1> ~ <7>, wherein, in composition (A), be preferably, R in general formula (1) 1for carbon number is the alkyl of 6 ~ 20, R 1average carbon atom number be 10.8 ~ 12.8, in addition, the composition with the maximum alkyl chain length of content is more than 55 quality % and is less than 97 quality %, further, n represents the number of 0 ~ 20, the meansigma methods of n is that the composition of 2.5 ~ 4.5, n=0 comprises 9.6 ~ 27 quality %, and the total content of the composition of n=1 and the composition of n=2 is 27 ~ 36.5 quality %.
The composition of skin cleanser of <9> according to any one of above-mentioned <1> ~ <8>, wherein, in composition (A), be preferably, R in general formula (1) 1for carbon number is the alkyl of 8 ~ 18, R 1average carbon atom number be 10.8 ~ 12.8, in addition, the composition with the maximum alkyl chain length of content is more than 55 quality % and is less than 97 quality %, further, n represents the number of 0 ~ 20, the meansigma methods of n is that the composition of 2.5 ~ 3.4, n=0 comprises 9.6 ~ 27 quality %, and the total content of the composition of n=1 and the composition of n=2 is 27 ~ 36.5 quality %.
The composition of skin cleanser of <10> according to any one of above-mentioned <1> ~ <9>, wherein, in composition (A), be preferably, R in general formula (1) 1for carbon number is the alkyl of 8 ~ 16, R 1average carbon atom number be 10.8 ~ 12.5, in addition, the composition with the maximum alkyl chain length of content is 60 ~ 95 quality %, further, n represents the number of 0 ~ 20, the meansigma methods of n is that the composition of 2.8 ~ 3.4, n=0 comprises 9.6 ~ 27 quality %, and the total content of the composition of n=1 and the composition of n=2 is 27 ~ 36.5 quality %.
The composition of skin cleanser of <11> according to any one of above-mentioned <1> ~ <10>, wherein, in composition (A), be preferably, R in general formula (1) 1for carbon number is the alkyl of 10 ~ 16, R 1average carbon atom number be 12.1 ~ 12.4, in addition, the composition with the maximum alkyl chain length of content is 60 ~ 95 quality %, further, n represents the number of 0 ~ 20, the meansigma methods of n is that the composition of 2.8 ~ 3.1, n=0 comprises 9.9 ~ 15 quality %, and the total content of the composition of n=1 and the composition of n=2 is 35 ~ 36.1 quality %.
The composition of skin cleanser of <12> according to any one of above-mentioned <1> ~ <11>, wherein, the alkyl ether carboxylic acid of composition (A) preferably contains more than 1 quality % in all forming, further preferably containing more than 5 quality %, be more preferably containing more than 6 quality %, below 20 quality % are preferably in all forming, more preferably below 15 quality %, be more preferably below 12 quality %, preferably containing 1 ~ 20 quality % in all forming, further preferably containing 2 ~ 15 quality %, be more preferably containing 4 ~ 12 quality %.
The composition of skin cleanser of <13> according to any one of above-mentioned <1> ~ <12>, wherein, preferably in composition (A), in general formula (1), (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:0.99 ~ 3.50:0.89 ~ 3.00:0.76 ~ 3.00:0.63 ~ 1.6.
The composition of skin cleanser of <14> according to any one of above-mentioned <1> ~ <13>, wherein, in composition (A), in general formula (1), comprise more than the composition 9.6 quality % of n=0 and be less than 12 quality %, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.53 ~ 1.87:1.59 ~ 2.25:1.33 ~ 2.16:1.14 ~ 1.52, or, comprise more than the composition 12 quality % of n=0 and below 17 quality %, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:0.99 ~ 1.34:0.89 ~ 1.40:0.76 ~ 1.23:0.63 ~ 0.99.
The composition of skin cleanser of <15> according to any one of above-mentioned <1> ~ <14>, wherein, in composition (A), in general formula (1), comprise composition 9.9 ~ 11.5 quality % of n=0, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.58 ~ 1.84:1.72 ~ 2.17:1.49 ~ 2.00:1.14 ~ 1.52, or, in general formula (1), comprise composition 13 ~ 17 quality % of n=0, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.00 ~ 1.31:0.93 ~ 1.34:0.79 ~ 1.18:0.63 ~ 0.99.
The composition of skin cleanser of <16> according to any one of above-mentioned <1> ~ <15>, wherein, in composition (A), be preferably, R in general formula (1) 1for carbon number is the alkyl of 4 ~ 22, R 1average carbon atom number be 10.8 ~ 12.8, in addition, the composition with the maximum alkyl chain length of content is more than 55 quality % and is less than 97 quality %, further, n represents the number of 0 ~ 20, meansigma methods is that the composition of 1.5 ~ 10, n=0 comprises 4.9 ~ 27 quality %, and the total content of the composition of n=1 and the composition of n=2 is 20 ~ 37 quality %.
The composition of skin cleanser of <17> according to any one of above-mentioned <1> ~ <16>, wherein, in the fatty acid of composition (B), R in general formula (2) 2be preferably alkyl or thiazolinyl that carbon number is 9 ~ 21, can be any one of straight chain or side chain, more preferably carbon number is the alkyl of 11 ~ 21, is more preferably the alkyl that carbon number is 13 ~ 17, is more preferably myristic acid, Palmic acid, stearic acid or behenic acid.
The composition of skin cleanser of <18> according to any one of above-mentioned <1> ~ <17>, wherein, the fatty acid of composition (B) can use a kind or two or more, preferably containing more than 1 quality % in all forming, more preferably more than 5 quality %, be more preferably below 6 quality %, be preferably below 20 quality %, more preferably below 15 quality %, be more preferably below 12 quality %, preferably containing 1 ~ 20 quality % in all forming, further preferably containing 5 ~ 15 quality %, be more preferably containing 6 ~ 12 quality %.
The composition of skin cleanser of <19> according to any one of above-mentioned <1> ~ <18>, wherein, the total content of composition (A) and (B) is preferably 2 ~ 40 quality % in all forming, more preferably 5 ~ 30 quality %, are more preferably 10 ~ 30 quality %.
The composition of skin cleanser of <20> according to any one of above-mentioned <1> ~ <19>, wherein, composition (B) is preferably containing R in general formula (2) 2carbon number be 15 ~ 21 fatty acid 40 ~ 100 quality %, further preferably containing 50 ~ 80 quality %.
The composition of skin cleanser of <21> according to any one of above-mentioned <1> ~ <20>, wherein, composition (A) and (B) are preferably (A)/(B)=0.3 ~ 5 as sour mass ratio, more preferably 0.5 ~ 2, be more preferably 0.5 ~ 1.5.
The composition of skin cleanser of <22> according to any one of above-mentioned <1> ~ <21>, wherein, in composition (A) and composition (B), R in general formula (2) 2carbon number be the alkyl of 15 ~ 21 fatty acid (composition (B-1)) as acid mass ratio be preferably (A)/(B-1)=0.2 ~ 5, more preferably 0.3 ~ 3.5, be more preferably 0.3 ~ 2, be more preferably 0.4 ~ 2 further.
The composition of skin cleanser of <23> according to any one of above-mentioned <1> ~ <22>, wherein, composition (C) is preferably Poise C-80M, cationic starch, JR-125, cationization tara gum, cationization locust bean gum, cationization trigonella bean gum, cationization xanthan gum, the polymer of poly (dially dialkyl) based quaternary ammonium salt, poly (dially dialkyl) based quaternary ammonium salt/acrylamide copolymer, poly (dially dialkyl) based quaternary ammonium salt/acrylamide/acrylic acid copolymer, vinyl tri-chlorination imidazoles/vinylpyrrolidone copolymer, hydroxyethyl-cellulose/dimethyl diallyl ammonium chloride copolymer, vinyl pyrrolidone/quaternized dimethyl amino ethyl methacrylate copolymer, polyvinyl pyrrolidone/alkyl amido acrylate copolymer, polyvinyl pyrrolidone/alkyl amido acrylate/vinyl caprolactam copolymer, vinyl pyrrolidone/Methacrylamide hydroxypropyltrimonium chloride copolymer, alkyl acrylamide/acrylate/alkylaminoalkyl group acrylamide/polyethylene glycol methacrylate-styrene polymer copolymer, adipic acid/dimethylamino hydroxypropyl ethylenetriamine copolymer (Sandoz company of the U.S., CARTARETIN), Japanese Laid-Open Patent Publication 53-139734 publication, the cationic polymer recorded in Japanese Laid-Open Patent Publication 60-36407 publication, is more preferably selected from poly (dially dialkyl) based quaternary ammonium salt/acrylamide copolymer, poly (dially dialkyl) based quaternary ammonium salt/acrylamide/acrylic acid copolymer, 1 kind in JR-125 and Poise C-80M or two or more.
The composition of skin cleanser of <24> according to any one of above-mentioned <1> ~ <23>, wherein, composition (C) can use more than a kind, preferably containing more than 0.1 quality % in all forming, more preferably more than 0.5 quality %, preferably containing below 5 quality %, more preferably below 2 quality %, in addition, preferably containing 0.1 ~ 5 quality %, more preferably 0.5 ~ 2 quality % in all forming.
The composition of skin cleanser of <25> according to any one of above-mentioned <1> ~ <24>, wherein, the alkali-metal hydroxide of sodium hydroxide, potassium hydroxide is preferably as the alkali of composition (D); Ammonia; The organic amine compound of triethanolamine; Arginic basic amino acid, more preferably potassium hydroxide.
The composition of skin cleanser of <26> according to any one of above-mentioned <1> ~ <25>, wherein, composition (D) is preferably 0.9 ~ 1.1 relative to the mol ratio (composition (D)/(composition (A)+composition (B))) of composition (A) and (B), and more preferably 0.95 ~ 1.05.
The composition of skin cleanser of <27> according to any one of above-mentioned <1> ~ <26>, wherein, contain composition (E) water further as solvent, its content is preferably more than 10 quality % in all forming, more preferably more than 15 quality %, be more preferably more than 30 quality %, be preferably below 96 quality %, more preferably below 90 quality %, be more preferably below 87 quality %, be more preferably below 85 quality % further, in addition, 10 ~ 96 quality % are preferably in all forming, more preferably 15 ~ 90 quality %, be more preferably 30 ~ 87 quality %.
The composition of skin cleanser of <28> according to any one of above-mentioned <1> ~ <27>, wherein, further containing (F) polyhydric alcohol.
The composition of skin cleanser of <29> as described in above-mentioned <28>, wherein, as composition (F) polyhydric alcohol, be preferably Sorbitol, glycerol, butanediol, propylene glycol, dipropylene glycol, erythritol, mannitol, xylitol, more preferably glycerol, Sorbitol.
The composition of skin cleanser of <30> as described in above-mentioned <28> or <29>, wherein, the polyhydric alcohol of composition (F) can use more than a kind, preferably containing more than 1 quality % in all forming, more preferably more than 5 quality %, preferably containing below 40 quality %, more preferably below 30 quality %, in addition, preferably containing 1 ~ 40 quality % in all forming, preferably contain 5 ~ 30 quality % further.
The composition of skin cleanser of <31> according to any one of above-mentioned <1> ~ <30>, wherein, composition of skin cleanser of the present invention can assign to manufacture by fitting in usual way mixing, the cleanser compositions obtained can be aqueous or any one in solid, shaped, when for aqueous, viscosity when measuring with Brookfield viscometer (manufacture of Tokyo gauge company) at 25 DEG C is preferably 200 ~ 80000mPas.
The composition of skin cleanser of <32> according to any one of above-mentioned <1> ~ <31>, wherein, the pH of composition of skin cleanser of the present invention is preferably 3 ~ 12, more preferably 5 ~ 10.5, be more preferably 5 ~ 7.
The composition of skin cleanser of <33> according to any one of above-mentioned <1> ~ <32>, wherein, composition of skin cleanser of the present invention is suitable as cleansing milk, bath gel, handwashing liquid, is preferably cleansing milk, bath gel.
<34> skin cleaning method, wherein, after composition of skin cleanser according to any one of above-mentioned <1> ~ <33> being applied on skin part cleaning, rinse.
Composition of skin cleanser according to any one of the above-mentioned <1> ~ <33> of <35> is applied on skin and carries out the purposes in the cleaning agent of cleaning in manufacture with foam.
(assay method)
In the present invention, the ratio of the alkyl of alkyl ether carboxylic acid composition, EO addition molar distribution and each composition, is measured according to following analytical method by gas chromatographic analysis (GC).
(GC analysis condition)
GC instrument: AgilentTechnologies, Inc. manufacture, 7890A
Post: AgilentTechnologies, Inc. manufacture, DB-5
(30m, internal diameter 0.25mm, thickness 0.25 μm)
Detector: FID
Carrier gas: helium, 1mL/min
Elevated Temperature Conditions: be warming up to 325 DEG C with 5 DEG C/min from 100 DEG C.Afterwards, keep 325 DEG C 35 minutes.
(pre-treating method of sample)
With 50mL dissolve with methanol 150mg alkyl ether carboxylic acid.In addition, for cleanser compositions, take 150mg as alkyl ether carboxylic acid, use 50mL dissolve with methanol.In addition, when cleanser compositions contains the surfactant of the strong anionic property of polyoxyethylene alkyl ether sulfate salt etc., the mode becoming below 250mg with them is taken.Take this solution of 1mL, be applicable to the solid-phase extraction column (Biotage manufactures, IsoluteSAX, 1g, 3mL, 500-0100-B) carrying out regulating with 4mL methanol in advance, collect with 10mL round bottom test tube and pass through liquid.Afterwards, carry out eluting with the solution that 100mL methanol obtains that adds in 4.6g formic acid of 6mL, eluent is also collected with identical test tube.The solution collected is arranged in the heater (blockheater) being heated to 50 DEG C, is blown into nitrogen, after being concentrated into about 1mL, being at room temperature blown into nitrogen further and making it dry.Add 2mL Azimethylene .-ethereal solution wherein, stir at room temperature to place and carry out derivatization in 10 minutes.Afterwards, be at room temperature blown into nitrogen, after being concentrated into 500 below μ L, add chloroform furnishing 500 μ L, be supplied to GC and analyze.
In addition, Azimethylene .-ethereal solution uses Azimethylene. generating apparatus (Gong Benli grinds industry manufacture, GM-50), modulates according to following order.Be connected the 1st with Teflon (registered trade mark) pipe with the 3rd receptor silicone rubber switch with the 2nd receptor, the 2nd.Take 0.8gN-methyl-N '-nitro-N nitrosoguanidine with the 2nd receptor, add the ion exchange water of 2.5mL.10mL t-butyl methyl ether is taked with the 3rd receptor.The ice-cold receptor of the 1st, the 2nd, the 3rd.Next, plastic injector installed by the 2nd receptor, what in this syringe, add 3mL is dissolved in 20g sodium hydroxide the solution obtained in 100mL ion exchange water.Slowly drip this sodium hydrate aqueous solution, generate Azimethylene. gas, be blown into nitrogen quietly from the 1st receptor side, make it to be dissolved in the t-butyl methyl ether of the 3rd receptor, obtain Azimethylene .-ethereal solution.
Reagent in the pre-treatment of above-mentioned sample employs following material.
Methanol (Northeast chemistry manufactures, high performance liquid chromatograph use, 25183-1B)
Formic acid (manufacture with the pure pharmaceutical worker's industry of light, reagent is superfine, 066-00461)
Chloroform (Northeast chemistry manufactures, deer 1 grade, 07278-01)
N-methyl-N '-nitro-N nitrosoguanidine (Northeast chemistry manufactures, deer 1 grade, 25596-51)
T-butyl methyl ether (Northeast chemistry manufactures, and deer is superfine, 04418-00)
Sodium hydroxide (manufacture with the pure pharmaceutical worker's industry of light, superfine, 196-13761)
The alkyl ether carboxylic acid of the composition (A) used in composition of skin cleanser of the present invention such as can manufacture according to following method.In addition, unless otherwise specified " % " represents quality %.
Production Example 1
1144g (6.14mol) lauryl alcohol [trade name: KALCOL2098 is added in the stainless steel autoclave possessing stirring and temp regulating function, flower king manufacture], 60.2g (0.281mol) myristyl alcohol [trade name: KALCOL4098, flower king manufacture], 2.68g (0.0478mol) potassium hydroxide, carry out decompression dehydration.Next, at 155 DEG C, importing 996g (22.6mol) ethylene oxide (EO), is 155 DEG C in reaction temperature, and reaction pressure is carry out reaction in 2 hours under 0.4MPa.After reaction terminates, 80 DEG C, stir 30 minutes under the reduced pressure of 6kPa, after removing unreacted ethylene oxide, import nitrogen to normal pressure, 90% lactic acid of 4.82g (0.0482mol) is added in autoclave, stir 30 minutes at 80 DEG C, obtain the alkyl ethoxylates (hereinafter also referred to as " generating AE ") that EO addition molal quantity is 3.55mol.
90g (0.2mol) above-mentioned product, 48% sodium hydrate aqueous solution (be 0.2mol as sodium hydroxide) of 16.7g, 0.9g palladium-platinum-bismuth class catalyst (support 4% palladium, 1% platinum and 5% bismuth on the activated carbon, moisture content is 50%), 494.4g water is added respectively in the glass reaction vessel being provided with agitating function, temp regulating function and airway.Under agitation, liquid temperature is warming up to 70 DEG C, blows into oxygen with the ratio of 27mol% (relatively generating the AE/ time), at reaction temperature is 70 DEG C, has carried out the contact oxidation of 3.5 hours simultaneously.Response rate is 89%.
After reaction terminates, from reactant liquor, leach catalyst, obtain the aqueous solution of alkyl ether carboxylic acid's sodium salt.Next, add 35% hydrochloric acid, implement separatory operation, obtain alkyl ether carboxylic acid.It can be used as EC1.
The result of gas chromatographic analysis is, EC1 is the M=H in general formula (1), R 1for lauryl/myristyl=95/5, average carbon atom number is the meansigma methods of 12.1, n is 2.8, comprises the composition 14.7 quality % of n=0, and the total amount of the composition of n=1 and the composition of n=2 is 36.1 quality %.
In addition, about the ratio of the different each composition of EO addition molal quantity, by R 1composition in maximum composition measured value calculate result be, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.22:1.23:1.06:0.83.
Production Example 2
Imitate Production Example 1, make EO with by decanol [trade name: KALCOL1098, flower king manufacture], lauryl alcohol [trade name: KALCOL2098, flower king manufacture], myristyl alcohol [trade name: KALCOL4098, flower king manufacture], spermol [trade name: KALCOL6098, flower king manufactures] be 10/70/15/5 raw material reaction mixed with mass ratio, obtaining EO addition molal quantity is the alkyl ethoxylates of 3.55mol.It being carried out oxidation reaction similarly to Example 1, by carrying out HCl treatment to the alkyl ether carboxy acid salt obtained, obtaining alkyl ether carboxylic acid.
The result of gas chromatographic analysis is, in general formula (1), and M=H, R 1for decyl/lauryl/myristyl/palmityl=10/70/15/5, average carbon atom number is the meansigma methods of 12.3, n is 3.3, comprises the composition 15.2 quality % of n=0, and the total amount of the composition of n=1 and the composition of n=2 is 31.4 quality %.
In addition, about the ratio of the different each composition of EO addition molal quantity, by R 1composition in the result that calculates of the measured value of maximum composition be, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.07:1.00:0.85:0.67.
Production Example 3
372g (2.00mol) lauryl alcohol is added in the glass reaction vessel being provided with stirring, temp regulating function, under agitation liquid temperature is warming up to 70 DEG C, 256g (2.20mol) sodium monochloracetate and 88g (2.20mol) sodium hydroxide is added in batches and carries out reaction in 5 hours.Reaction terminate after, filter precipitate, then, add 35% hydrochloric acid, make it acidify, obtain alkyl ether carboxylic acid (in general formula (1), M=H, R 1for lauryl, n=0).
Production Example 4
Imitate Production Example 1, as raw material, EO is reacted with it decanol, obtaining EO addition molal quantity is the alkyl ethoxylates of 3.55mol.It being carried out oxidation reaction equally with Production Example 1, by carrying out HCl treatment to the alkyl ether carboxy acid salt obtained, obtaining alkyl ether carboxylic acid.
The analysis result of gas chromatogram is, in general formula (1), and M=H, R 1for decyl, the meansigma methods of n is 3.1, comprises the composition 16 quality % of n=0, and the total amount of the composition of n=1 and the composition of n=2 is 37 quality %.
Production Example 5
Imitate Production Example 1, as raw material, EO is reacted with it lauryl alcohol, obtaining EO addition molal quantity is the alkyl ethoxylates of 3.55mol.It being carried out oxidation reaction in the same manner as Production Example 1, by carrying out HCl treatment to the alkyl ether carboxy acid salt obtained, obtaining alkyl ether carboxylic acid.
The analysis result of gas chromatogram is, in general formula (1), and M=H, R 1for lauryl, the meansigma methods of n is 3.1, comprises the composition 16 quality % of n=0, and the total amount of the composition of n=1 and the composition of n=2 is 37 quality %.
Production Example 6
Imitate Production Example 1, as raw material, EO is reacted with it myristyl alcohol, obtaining EO addition molal quantity is the alkyl ethoxylates of 3.55mol.It being carried out oxidation reaction in the same manner as Production Example 1, by carrying out HCl treatment to the alkyl ether carboxy acid salt obtained, obtaining alkyl ether carboxylic acid.
The analysis result of gas chromatogram is, in general formula (1), and M=H, R 1for myristyl, the meansigma methods of n is 3.1, comprises the composition 16 quality % of n=0, and the total amount of the composition of n=1 and the composition of n=2 is 37 quality %.
Production Example 7
Imitate Production Example 1, to being that 20/80 raw material mixed carries out EO addition by lauryl alcohol, spermol with mass ratio, obtaining EO addition molal quantity is the alkyl ethoxylates of 3.55mol.It being carried out oxidation reaction in the same manner as Production Example 1, by carrying out HCl treatment to the alkyl ether carboxy acid salt obtained, obtaining alkyl ether carboxylic acid.
The analysis result of gas chromatogram is, in general formula (1), and M=H, R 1for lauryl/palmityl=20/80, the meansigma methods of n is 3.1, comprises the composition 16 quality % of n=0, and the total amount of the composition of n=1 and the composition of n=2 is 37 quality %.
Production Example 8
Imitate Production Example 1, lauryl alcohol is carried out EO reaction as raw material, and obtaining EO addition molal quantity is the alkyl ethoxylates of 4.05mol.It being carried out oxidation reaction in the same manner as Production Example 1, by carrying out HCl treatment to the alkyl ether carboxy acid salt obtained, obtaining alkyl ether carboxylic acid.
The analysis result of gas chromatogram is, in general formula (1), and M=H, R 1for lauryl, the meansigma methods of n is 3.5, comprises the composition 11.4 quality % of n=0, and the total amount of the composition of n=1 and the composition of n=2 is 30.6 quality %.
In addition, about the ratio of the different each composition of EO addition molal quantity, by R 1composition in the result that calculates of the measured value of maximum composition be, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.31:1.38:1.25:1.06.
Production Example 9
To possess stirring and temp regulating function stainless steel autoclave in add 1144g (6.14mol) lauryl alcohol [trade name: KALCOL2098, flower king manufacture], 60.2g (0.281mol) myristyl alcohol [trade name: KALCOL4098, flower king manufacture], 2.6g (0.0478mol) potassium hydroxide, carry out decompression dehydration.Next, at 155 DEG C, importing 718g (16.3mol) ethylene oxide (EO), is 155 DEG C in reaction temperature, and reaction pressure is carry out reaction in 2 hours under 0.4MPa.After reaction terminates, cooling, 80 DEG C, stir 30 minutes under the reduced pressure of 6kPa, after removing unreacted ethylene oxide, import nitrogen to normal pressure, in autoclave, add 90% lactic acid of 4.82g (0.0482mol), stir 30 minutes at 80 DEG C, obtaining EO addition molal quantity is the alkyl ethoxylates of 2.55mol.
600g (2.00mol) above-mentioned product is added in the glass reaction vessel being provided with stirring, temp regulating function, under agitation liquid temperature is warming up to 70 DEG C, adds 256g (2.20mol) sodium monochloracetate and 88g (2.20mol) sodium hydroxide in batches and carry out reaction in 5 hours.After reaction terminates, adding 35% hydrochloric acid to pH is 2.8, acidify, divides and gets oil reservoir, obtain alkyl ether carboxylic acid.It can be used as EC6.
The result of gas chromatographic analysis is, M=H, R in general formula (1) 1for lauryl/myristyl=94/6, average carbon atom number is the meansigma methods of 12.1, n is 3.1, comprises the composition 9.9 quality % of n=0, and the total amount of the composition of n=1 and the composition of n=2 is 35.4 quality %.
In addition, about the ratio of the different each composition of EO addition molal quantity, by R 1composition in maximum composition measured value calculate result be, (quality of n=0 composition): (quality of n=1 composition): (quality of n=2 composition): (quality of n=3 composition): (quality of n=4 composition)=1:1.65:1.92:1.74:1.32.
In embodiment described later, for EC2, be the ratio mixing of 78.75/15/6.25 by each mass ratio by the alkyl ether carboxylic acid obtained in Production Example 5, Production Example 6, Production Example 7, as EC2.
In embodiment described later, for EC3, be the ratio mixing of 90/10 with each mass ratio by the alkyl ether carboxylic acid obtained in Production Example 2, Production Example 3, as EC3.
In embodiment described later, for EC4, be the ratio mixing of 40/60 by each mass ratio by the alkyl ether carboxylic acid obtained in the EC1 obtained in Production Example 1 and Production Example 4, as EC4.
In embodiment described later, for EC5, be the ratio mixing of 40/60 by each mass ratio by the alkyl ether carboxylic acid obtained in Production Example 2, Production Example 8, as EC5.
Embodiment
Embodiment 1 ~ 15, comparative example 1 ~ 4
Manufacture the composition of skin cleanser of composition shown in table 2 ~ 6, the elasticity of assess foam and with or without tight sense.To the results are shown in table 2 ~ 6.
In addition, the formation of the composition (A) used in embodiment is as shown in table 1.
(manufacture method)
Composition (D) is made an addition in composition (E) Purified Water (removing is equivalent to the composition (E) of 5 times amount of composition (C)), after dissolving, be warming up to 75 DEG C.Be added on 70 DEG C in this aqueous solution at, composition (A) and (B) are dissolved, mixed liquid, stir until evenly.Thereafter, as required, add composition (F), be stirred to evenly, be cooled to 25 DEG C.Next, add composition (E) and composition (C) the mixed solution that will be equivalent to 5 times amount of composition (C), be stirred to evenly, obtain composition of skin cleanser.
(evaluation methodology)
(1) elasticity of foam:
To get blisters after net (manufacture of Bai Yuan company) drenches with water (about 8g), 1g cleaning agent is placed in get blisters online.Encase with two palms net of getting blisters, rub two palms to bubble in the mode of drawing 40 circles.
To be collected in shallow chassis (diameter 6.6cm, high 1.8cm) at online the foam risen of getting blisters, removing excessive foam with chi becomes plane to liquid level is consistent with the height on shallow chassis.Use FUDOH flow graph RTC (motionless industrial group manufactures) in the elastic mensuration of foam, use special jointer 3 (elasticity of compression measures jointer, D φ=5).Foam surface on shallow chassis arranges jointer, and the sampling period is 0.1 second, and displacement (stroke) is 20mm, speed is 30cm/ minute, represent in units of g, direction of displacement is set as up and down, being determined at the stress that jointer is subject at the liquid temperature about 25 DEG C of foam.In the measured value obtained, numerical value represented on flow graph, as elastic force, is shown in table by the numerical value of the busy hour that jointer is subject to.
(2) with or without tight sense:
Evaluating group member specially by 5 uses each composition of skin cleanser of 1g to wash one's face, and after rinsing, according to the tight sense after the firm towel of following standardized sensory evaluation, tries to achieve its summation score with water.
3: not tight.
2: almost not tight.
1: tight a little.
0: tight.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
Embodiment 16
The composition of skin cleanser of composition shown below is manufactured in the same manner as embodiment 1 ~ 15.
*1：MERQUATPLUS3331(LubrizolAdvancedMaterials,Inc.)
* the effective ingredient of 2:AMPHITOL20HD (flower king)
The composition of skin cleanser alveolar substance exquisite quality obtained and elasticity is excellent, the skin wet after cleaning, does not feel tight sense.
Embodiment 17
The composition of skin cleanser of composition shown below is manufactured in the same manner as embodiment 1 ~ 15.
*3：JAGUARC-17K(RhodiaOperations(Novecare))
* the effective ingredient of 4:PENETOLGE-EH (flower king)
The composition of skin cleanser alveolar substance exquisite quality obtained and elasticity is excellent, the skin wet after cleaning, does not feel tight sense.

Claims (30)

1. a composition of skin cleanser, wherein,
Containing following composition (A), (B), (C), (D) and (E),
(A) alkyl ether carboxylic acid represented by general formula (1), its content is 1 ~ 20 quality %,
R 1-O-(CH 2CH 2O) n-CH 2-COOH(1)
In formula, R 1represent that carbon number is the alkyl of 4 ~ 22, n represents the number of 0 ~ 20,
R in described alkyl ether carboxylic acid 1average carbon atom number be 10.8 ~ 12.8, comprise composition 4.3 ~ 30 quality % of n=0, the total content of the composition of n=1 and the composition of n=2 is more than 20 quality % and is less than 40 quality %;
(B) fatty acid represented by general formula (2), its content is 1 ~ 20 quality %,
R 2-COOH(2)
In formula, R 2represent that carbon number is the straight chain of 9 ~ 21 or the alkyl of side chain or thiazolinyl;
(C) cationic polymer, its content is 0.1 ~ 5 quality %;
(D) alkali;
(E) water,
Composition (A) and (B) exist in a salt form with composition (D) at least partially, and composition (D) is composition (D)/(composition (A)+composition (B))=0.9 ~ 1.1 relative to the mol ratio of composition (A) and (B).
2. composition of skin cleanser as claimed in claim 1, wherein,
Further containing (F) polyhydric alcohol.
3. composition of skin cleanser as claimed in claim 1 or 2, wherein,
Composition (B) comprises R in general formula (2) 2carbon number be 15 ~ 21 fatty acid 40 ~ 100 quality %.
4. composition of skin cleanser as claimed in claim 1 or 2, wherein,
The mass ratio as acid of composition (A) and (B) is (A)/(B)=0.3 ~ 5.
5. composition of skin cleanser as claimed in claim 1 or 2, wherein,
In composition (A), the meansigma methods of n is that the meansigma methods of 1.5 ~ 10, n refers to average addition molal quantity in general formula (1).
6. composition of skin cleanser as claimed in claim 1 or 2, wherein,
In composition (A), R in general formula (1) 1to be carbon number be 6 ~ 20 alkyl, the meansigma methods of n is 2.5 ~ 4.5, comprises composition 9.6 ~ 27 quality % of n=0.
7. composition of skin cleanser as claimed in claim 1 or 2, wherein,
In composition (A), R in general formula (1) 1to be carbon number be 8 ~ 18 alkyl, the meansigma methods of n is 2.5 ~ 3.4, comprises composition 9.6 ~ 27 quality % of n=0.
8. composition of skin cleanser as claimed in claim 1 or 2, wherein,
In composition (A), R in general formula (1) 1to be carbon number be 8 ~ 16 alkyl, the meansigma methods of n is 2.8 ~ 3.4, comprises composition 9.6 ~ 27 quality % of n=0, adds up to and comprises the composition of n=1 and composition 27 ~ 36.5 quality % of n=2.
9. composition of skin cleanser as claimed in claim 1 or 2, wherein,
In composition (A), in general formula (1), the quality of n=0 composition: the quality of n=1 composition: the quality of n=2 composition: the quality of n=3 composition: quality=1:0.99 ~ 3.50:0.89 ~ 3.00:0.76 ~ 3.00:0.63 ~ 1.6 of n=4 composition.
10. composition of skin cleanser as claimed in claim 1 or 2, wherein,
In composition (A), R in general formula (1) 1comprise alkyl of more than two kinds, the composition with the maximum alkyl chain length of content is more than 55 quality % and is less than 97 quality %.
11. composition of skin cleanser as claimed in claim 1 or 2, wherein,
In composition (A), in general formula (1), comprise more than the composition 8 quality % of n=0 and be less than 12 quality %, the quality of n=0 composition: the quality of n=1 composition: the quality of n=2 composition: the quality of n=3 composition: quality=1:1.53 ~ 1.87:1.59 ~ 2.25:1.33 ~ 2.16:1.14 ~ 1.52 of n=4 composition, or, comprise more than the composition 12 quality % of n=0 and below 17 quality %, the quality of n=0 composition: the quality of n=1 composition: the quality of n=2 composition: the quality of n=3 composition: quality=1:0.99 ~ 1.34:0.89 ~ 1.40:0.76 ~ 1.23:0.63 ~ 0.99 of n=4 composition.
12. composition of skin cleanser as claimed in claim 1 or 2, wherein,
The alkyl ether carboxylic acid of composition (A) contains 4 ~ 12 quality % in all forming.
13. composition of skin cleanser as claimed in claim 1 or 2, wherein,
The fatty acid of composition (B) is myristic acid, Palmic acid, stearic acid or behenic acid.
14. composition of skin cleanser as claimed in claim 1 or 2, wherein,
The fatty acid of composition (B) contains 6 ~ 12 quality % in all forming.
15. composition of skin cleanser as claimed in claim 1 or 2, wherein,
Composition (B) is containing the R in general formula (2) 2carbon number be 15 ~ 21 fatty acid 50 ~ 80 quality %.
16. composition of skin cleanser as claimed in claim 1 or 2, wherein,
The mass ratio as acid of composition (A) and (B) is (A)/(B)=0.5 ~ 1.5.
17. composition of skin cleanser as claimed in claim 1 or 2, wherein,
The total content of composition (A) and (B) is 2 ~ 40 quality % in all forming.
18. composition of skin cleanser as claimed in claim 1 or 2, wherein,
The total content of composition (A) and (B) is 10 ~ 30 quality % in all forming.
19. composition of skin cleanser as claimed in claim 1 or 2, wherein,
In composition (A) and composition (B), R in described general formula (2) 2carbon number be the fatty acid of the alkyl of 15 ~ 21 be composition (B-1), composition (A) is (A)/(B-1)=0.2 ~ 5 relative to the mass ratio as acid of composition (B-1).
20. composition of skin cleanser as claimed in claim 1 or 2, wherein,
In composition (A) and composition (B), R in described general formula (2) 2carbon number be the fatty acid of the alkyl of 15 ~ 21 be composition (B-1), composition (A) is (A)/(B-1)=0.4 ~ 2 relative to the mass ratio as acid of composition (B-1).
21. composition of skin cleanser as claimed in claim 1 or 2, wherein,
Composition (C) is for being selected from Poise C-80M, cationic starch, JR-125, cationization tara gum, cationization locust bean gum, cationization trigonella bean gum, cationization xanthan gum, the polymer of poly (dially dialkyl) based quaternary ammonium salt, poly (dially dialkyl) based quaternary ammonium salt/acrylamide copolymer, poly (dially dialkyl) based quaternary ammonium salt/acrylamide/acrylic acid copolymer, vinyl tri-chlorination imidazoles/vinylpyrrolidone copolymer, hydroxyethyl-cellulose/dimethyl diallyl ammonium chloride copolymer, vinyl pyrrolidone/quaternized dimethyl amino ethyl methacrylate copolymer, polyvinyl pyrrolidone/alkyl amido acrylate copolymer, polyvinyl pyrrolidone/alkyl amido acrylate/vinyl caprolactam copolymer, vinyl pyrrolidone/Methacrylamide hydroxypropyltrimonium chloride copolymer, alkyl acrylamide/acrylate/alkylaminoalkyl group acrylamide/polyethylene glycol methacrylate-styrene polymer copolymer, more than a kind in adipic acid/dimethylamino hydroxypropyl ethylenetriamine copolymer.
22. composition of skin cleanser as claimed in claim 1 or 2, wherein,
Composition (C) contains 0.5 ~ 2 quality % in all forming.
23. composition of skin cleanser as claimed in claim 1 or 2, wherein,
The alkali of composition (D) is sodium hydroxide, potassium hydroxide, ammonia, triethanolamine or arginine.
24. composition of skin cleanser as claimed in claim 1 or 2, wherein,
Composition (D) relative to the mol ratio of composition (A) and (B) is, composition (D)/(composition (A)+composition (B))=0.95 ~ 1.05.
25. composition of skin cleanser as claimed in claim 2, wherein,
The polyhydric alcohol of composition (F) is more than a kind of being selected from Sorbitol, glycerol, butanediol, propylene glycol, dipropylene glycol, erythritol, mannitol, xylitol.
26. composition of skin cleanser as claimed in claim 2, wherein,
The polyhydric alcohol of composition (F) contains 1 ~ 40 quality % in all forming.
27. composition of skin cleanser as claimed in claim 1 or 2, wherein,
Viscosity at 25 DEG C is 200 ~ 80000mPas.
28. composition of skin cleanser as claimed in claim 1 or 2, wherein,
PH is 3 ~ 12.
The skin cleaning method of 29. 1 kinds of non-treatment objects, wherein,
Composition of skin cleanser according to any one of claim 1 ~ 28 is applied to body skin portion clean after, rinse.
Composition of skin cleanser according to any one of 30. claim 1 ~ 28 is applied on skin and carries out the purposes in the cleaning agent cleaned in manufacture with foam.
CN201280060484.8A 2011-12-08 2012-12-07 Composition of skin cleanser Active CN103974690B (en)

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