CN1242037C - detergent composition - Google Patents
detergent composition Download PDFInfo
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- CN1242037C CN1242037C CNB018185452A CN01818545A CN1242037C CN 1242037 C CN1242037 C CN 1242037C CN B018185452 A CNB018185452 A CN B018185452A CN 01818545 A CN01818545 A CN 01818545A CN 1242037 C CN1242037 C CN 1242037C
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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
- A61K8/30—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
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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
- A61K8/30—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
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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
- A61K8/30—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
- A61K8/37—Esters of carboxylic acids
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/42—Amides
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- 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
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- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming compositions
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
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- Public Health (AREA)
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- Organic Chemistry (AREA)
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- Detergent Compositions (AREA)
Abstract
The present invention provides a detergent composition characterized by containing a: at least one member selected from the group consisting of higher fatty acid salts (a1), amidoethersulfate-type anionic surfactants (a2), and acyltaurate-type anionic surfactants (a 3); and undecenylamidoacetic acid betaine-type amphoteric surfactant (b) containing 5-35 wt% of a1, a2 and a3 and 0.5-20 wt% of b, wherein the weight ratio of a/b is 3/4-10/1. This composition exhibits high foamability even in the presence of an oil, is rich in foam, has good foam quality, gives a refreshing feeling and a good feeling upon and after washing, does not cause skin dryness even when frequently used, can keep the skin moist, and has good stability over time, and therefore can be used for a cleansing composition, a shampoo composition, a detergent composition for tableware, a hand cleanser composition, a bath foam composition, and the like. In addition, the composition can be used for preventing acne, face cleaning composition, dandruff removing shampoo, kitchen detergent composition with antibacterial effect, (tableware detergent composition), hand sanitizer composition, etc.
Description
Technical field
Even the present invention relates in the presence of oil content, also to demonstrate high whipability, low to the pungency of skin, last the cleansing composition that has good stability.
Background technology
As people's skin and the main occasion that cleansing composition directly contacts, can enumerate the occasion of the oil content that adheres on the wash dining set, occasions such as used soap or shampoo such as have a bath.Recently, it is also more and more with the example of various makeup such as setting agent to wash lady's makeup, hair with cleansing composition.During the makeup of washing face or hair surface, important being can utilize detergent to remove makeup well, and the detergent whipability well also is important during washing.Reason is that the whipability by the washing fashion can make the user feel that makeup are removed well.But, when being washing object use detergent, also have detergent to be difficult to blistered this phenomenon with makeup.
Even as also fizzy tensio-active agent in the presence of oil content, up to the present can enumerate the alkylbenzene sulfonate type anionic surfactant who uses with the major ingredient of cleansing composition as tableware always, alkyl sulfuric ester type anionic surfactant etc.But, use these tensio-active agents can cause pachylosis etc., strong to the stimulation of skin.The tendency that therefore, the cleansing composition that do not use such tensio-active agent conduct and skin directly to contact (as tableware with cleansing composition etc.) composition is arranged recently.Therefore, such tensio-active agent is unfavorable as the pore forming material that is the cleansing composition of washing object with makeup.
Composition preferred surfactants as cleansing composition low to skin irritation, that directly contact with skin has amide ether sulfate type anionic surfactant, acyl taurate type anionic surfactant etc.
As the cleansing composition that uses amide ether sulfate type anionic surfactant, known amide ether sulfate type anionic surfactant is the composition that is combined into by following table surface-active agent etc.: the composition that amino acid surfactant and amphoterics combine (spy opens flat 10-182367 communique); The composition that amido betaine type amphoterics and cationic surfactant combine (spy opens flat 6-293620 communique); The composition that imidazolinium betaine type amphoterics combines (spy opens flat 6-49484 communique); The composition that acyl methyl N-taurate type anionic surfactant and amino amino acid type amphoteric surface active agent combine (spy opens flat 6-186792 communique); The mercerising composition (spy opens flat 5-43889 communique) that the salt of acylate of polypeptide combines of deriving; The composition that glucoside type nonionic surfactant combines (spy opens flat 4-126799 communique) etc.
As the composition that uses acyl taurate type anionic surfactant, known acyl taurate type anionic surfactant is the composition that is formed by combining by the following table surface-active agent: the composition that amide ether sulfate type anionic surfactant and amide group amino acid type amphoteric surface active agent combine (spy opens flat 4-15298 communique); Betaines tensio-active agent, HLB are 10～16 nonionic surfactant, alkanolamine type nonionic surfactant or amine oxide type nonionic surfactant and gather the composition (spy opens flat 3-93711 communique) that (dimethyl diallyl ammonium halide) type cationic macromolecular compound combines; The composition (spy opens flat 3-48608 communique) that amino sultaine type amphoterics or sultaine type amphoterics and alkanolamine type nonionic surfactant combine; The composition that sulfosuccinate ester salt type anionic surfactant combines (spy opens flat 2-105894 communique); The composition that alkyl glucoside type nonionic surfactant combines (spy opens flat 1-178596 communique) etc.
Above-mentioned amide ether sulfate type anionic surfactant and acyl taurate type anionic surfactant demonstrate higher whipability when water-soluble components such as washing sweat; but when with oil contents such as makeup, tablewares serving as the washing object, the significantly reduced shortcoming of whipability is arranged.And, even in the cleansing composition that forms by these tensio-active agents and above-mentioned other combinations-of surfactants, do not overcome this shortcoming yet.And, by these tensio-active agents and above-mentioned other surface-active combination, take place to solidify at low temperatures and produce down painted etc. of throw out, high temperature and last and can have problems more than the stable aspect.
Therefore, truth be do not obtain as yet under the situation that still has oil content, demonstrating high whipability, low to the pungency of skin, last the cleansing composition that has good stability.
On the other hand, as body cleaning agent such as bathing agentss, the general detergent that uses based on higher fatty acid salt.Higher fatty acid salt do not have stick-slip sense after having high washing force, washing, wash the back clearly feel, bubble many, alveolar substance good, but also have degreasing power by force, to the stimulation of skin such worry by force.Therefore, general in order to relax pungency to skin, more based on the situation of the detergent of higher fatty acid salt and other tensio-active agent and usefulness.For example: the known composition that combinations such as higher fatty acid salt and following table surface-active agent are arranged: the composition that amide ether sulfate type anionic surfactant and alkyl phosphate type anionic surfactant combine (spy opens flat 5-201852 communique); Lauroleate and 2 grades of compositions (spy opens flat 5-156284 communique) that amine type N-acyl amino hydrochlorate combines; The composition that potassium laurate, potassium myristate or potassium oleate and polyethylene oxide Viscotrol C combine (spy opens clear 61-300 communique); Soap and o-replace the composition (spy opens clear 59-15500 communique) that oxysuccinic acid combines; The composition that the triethanolamine salt of lipid acid and acyl glutamic acid ester type anionic surfactant combine (spy opens clear 61-287992 communique); The composition that soap and Natvosol cationization thing combine (spy opens clear 58-167699 communique) etc.
In addition, also once attempted with in the basic aminoacids and higher fatty acid to relax skin irritation.For example, alkaline amino acid salt of known use higher fatty acid etc. has following composition: the composition that lipid acid alkaline amino acid salt and Beta-alanine type amphoterics combine (spy opens flat 9-151391 communique); The composition that lipid acid alkaline amino acid salt and amine oxide combine (waiting out flat 9-118896 communique) etc.
In addition, open flat 5-262639 communique the spy, the spy opens and points out in the flat 9-13096 communique that the purpose of cleansing composition is: with soap and polyoxyethylene glycol or specific nonionic surfactant combination, to reduce stimulation to skin.
By such discussion research,, after the body cleaning agent of use based on higher fatty acid salt, still there is this class problem of xerosis cutis although progressively improve based on the skin irritation problem of the body cleaning agent of higher fatty acid salt.Since higher fatty acid salt pH be from weakly alkaline to alkalescence, degreasing power is more intense, so according to the people of use or the difference of season or usage frequency, variant on the degree, be easy to generate xerodermatic problem after having washing.
As for xerosis cutis, particularly in the nurse (helper) who is engaged in person's nursing at advanced age, become problem recently.These nurses will carry out several times the work that helps person's balneation at advanced age, clean health to tens times sometimes, if use existing detergent, can cause hand skin drying, pachylosis inevitably, majority all needs to carry out maintenance by dew of preserving moisture (moisturizing creams) etc.
The feature of dry skin is: can see that from outward appearance decortication or be full of cracks are usually arranged, old stratum corneum is difficult for peeling off, and cutin is at the skin surface residual buildup, so that an ancient term for country school.If the epidermal keratinocyte of this dry skin is sampled by adhesive tape strip-up etc., examine under a microscope, just often can see that significant distortion of shape or nuclear have remaining parakeratosis.In addition, lead, as can be known, can see that in most cases electricity is led reduction, humidity reduces if measure the electricity of skin.Therefore, can know by inference and reduced the original maintenance moisture of stratum corneum, prevent that foreign matter from invading these functions.Particularly in air dried winter, cause the xerosis cutis after the washing easily.
With tenderizer, amino acid or alpha hydroxy acid or these compositions of preserving moisture of their derivative such as wetting Agent for Printing Inkss such as glycerine, vegetables oil or squalenes, or polyoxygenated ethylidene glycol polyoxyethylene sorbitanic class nonionic surfactant is coupled in the detergent, the xerosis cutis of being followed when attempting suppressing to wash, and keep moistening.But this can not say effect of sufficient.
Therefore, people expect and can accomplish, though have in the presence of oil content, also have high whipability, good alveolar substance and storage stability; Pungency to skin is low; The washing aftersensation is salubrious and in a good humor; Even and frequent use can not cause xerodermatic yet; And can keep the cleansing composition of skin wet.
Summary of the invention
The invention provides the cleansing composition of following feature: contain following a and b, containing a is that 5～35 weight %, b are 0.5～20 weight %, and the weight ratio of a/b is 3/4～10/1.In this cleansing composition; a is for being selected from least a in higher fatty acid salt (a1), amide ether sulfate type anionic surfactant (a2) and acyl taurate type anionic surfactant (a3) class, and b is undecylene amide group acetate betaine type amphoteric surfac-tant.
In a preferred embodiment, above-mentioned cleansing composition is a face cleaning milk, and a is higher fatty acid salt (a1), and contained a1 is 15～35 weight %, and b is 0.5～10 weight %, and a1+b is 20～45 weight %, and the weight ratio of a1/b is 3/1～10/1.
In other preferred implementation, above-mentioned cleansing composition is a bathing agents, and a is higher fatty acid salt (a1), and contained a1 is 5～35 weight %, and b is 0.5～15 weight %, and a1+b is 10～40 weight %, and the weight ratio of a1/b is 2/1～10/1.
In addition; in other embodiment of other; above-mentioned cleansing composition is a detergent for kitchen use; a is amide ether sulfate type anionic surfactant (a2) or acyl taurate type anionic surfactant (a3); contained a is 5～30 weight %; b is 0.5～20 weight %, and a+b is 10～45 weight %, and the weight ratio of a/b is 3/4～8/1.
In other preferred implementation; above-mentioned cleansing composition is shampoo; a is amide ether sulfate type anionic surfactant (a2) or acyl taurate type anionic surfactant (a3); contained a is 5～20 weight %; b is 0.5～20 weight %; a+b is 6～30 weight %, and the weight ratio of a/b is 3/4～5/1.
Embodiment
Cleansing composition of the present invention be contain quantitative, a: be selected from least a among higher fatty acid salt (a1), amide ether sulfate type anionic surfactant (a2) and the acyl taurate type anionic surfactant (a3); B: undecylene amide group acetate betaine type amphoteric surfac-tant, in addition, also contain the cleansing composition of water and the necessary additive of cleansing composition.
(higher fatty acid salt (a1))
In the higher fatty acid salt shown in the a1, the preferred higher fatty acid salt that uses by following formula (1) expression.
Chemical formula (1)
R
1COOM
1 (1)
In the formula, R
1CO represents that carbonatoms is 8～22 aliphatic acyl radical, M
1Expression hydrogen atom, basic metal, ammonium, organic ammonium, amino acid, amino acid salts, taurine, taurate, N methyl taurine or N methyl taurine salt.
R
1CO is 8～22 aliphatic acyl radical as carbonatoms, can enumerate capryloyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearyl-, oleoyl, flax acyl group, shellfish than acyl group etc.The higher fatty acid salt that contains these groups can exist on multiple class ground, for example, and R
1CO can be the aliphatic acyl radical residue from coco-nut oil fatty acid, palm kernel oil lipid acid, sunflower oil lipid acid, tallow fatty acids etc.
As basic metal, for example, can enumerate lithium, sodium, potassium.
As organic amine, for example, can enumerate monoethanolamine, di-methylcarbinol amine, trolamine.
As amino acid, for example, can enumerate acidic amino acids such as aspartic acid, L-glutamic acid; Neutral amino acidss such as glycine, sarkosine, L-Ala, Beta-alanine, phenylalanine, Xie Ansuan, L-LEU, L-iLeu, Threonine, methionine(Met), theanine, Serine, proline(Pro), gamma-amino caproic acid; Basic aminoacidss such as arginine, ornithine, Histidine, Methionin, tryptophane; In addition,, can enumerate the salt that these amino acid and basic metal, ammonium or organic amine form as amino acid salts.
As taurate, can enumerate an alkali metal salt, ammonium salt or the organic amine salt of taurine; For example Sodium taurine salt, taurine potassium etc.
As N methyl taurine salt, can enumerate an alkali metal salt, ammonium salt or the organic amine salt of N methyl taurine; For example, N methyl taurine sodium, N methyl taurine potassium etc.
(amide ether sulfate type anionic surfactant (a2))
In the amide ether sulfate type anionic surfactant who represents by a2, the also preferred amide ether sulfate type anionic surfactant who uses by following formula (2) expression.
Chemical formula (2)
R
2CONH(C
2H
4O)
nSO
3M
2 (2)
In the formula, R
2CO represents that carbonatoms is 8～22 aliphatic acyl radical, and n is 1～10, M
2Expression hydrogen atom, basic metal, alkaline-earth metal, ammonium, organic amine, basic aminoacids, taurate, N methyl taurine salt, neutrality or acidic amino acid salt.
As carbonatoms is 8～22 aliphatic acyl radical, can enumerate lauroyl, myristoyl, palmitoyl, stearyl-, oleoyl etc.Contain these basic amide ether sulfate type anionic surfactants and also can exist on multiple class ground, for example, R
2CO can be the aliphatic acyl radical residue from coco-nut oil fatty acid, palm kernel oil lipid acid, tallow fatty acids etc.The carbonatoms of aliphatic acyl radical has the stimulation grow of pair skin, the tendency that whipability reduces 7 when following.Carbonatoms has whipability, lasts the tendency that stability reduces 23 when above.
N represents the average additional mole number of oxyethylene group, is preferably 1～10, more preferably 2～6.The discontented tendency that had the stimulation of pair skin to strengthen at 1 o'clock, lasts poor stability of n surpasses the tendency that the whipability reduction was arranged at 10 o'clock.
As M
1Basic metal, can enumerate sodium, potassium etc.As alkaline-earth metal, can enumerate 1/2 calcium, 1/2 magnesium etc.
As organic amine, can enumerate trolamine etc.
As basic aminoacids, can enumerate Methionin, arginine etc.
As taurate, can enumerate an alkali metal salt, alkaline earth salt, ammonium salt or the organic amine salt of taurine.For example, Sodium taurine salt, taurine potassium etc.
As N methyl taurine salt, can enumerate an alkali metal salt, alkaline earth salt, ammonium salt or the organic amine salt of N methyl taurine.For example, N methyl taurine sodium, N methyl taurine potassium etc.
As neutral or acid amide, can enumerate an alkali metal salt, alkaline earth salt, ammonium salt or the organic amine salt of neutrality or acidic amino acid.For example, neutral amino acids salt such as Sodium glycocollate, glycine potassium, sodium sarcosinate, Beta-alanine sodium; Acidic amino acid salt such as disodium glutamate, L-glutamic acid dipotassium, aspartic acid disodium.
As the amide ether sulfate type anionic surfactant's who represents with formula (2) concrete example, can enumerate following tensio-active agent: polyethylene oxide (2 moles) laurylamide ether sodium sulfate; Polyethylene oxide (3 moles) lauroyl amidogen ether vitriolate of tartar; Polyethylene oxide (4 moles) laurylamide ether ammonium sulfate; Polyethylene oxide (4 moles) myristic amide ether sodium sulfate; Polyethylene oxide (5 moles) palmitic amide ether sodium sulfate; Polyethylene oxide (6 moles) stearylamide ether sodium sulfate; Polyethylene oxide (5 moles) oleylamide ether sodium sulfate; Polyethylene oxide (4 moles) Oleum Cocois fatty amide ether sodium sulfate; Polyethylene oxide (4 moles) coconut fat amide ether vitriolate of tartar; Polyethylene oxide (4 moles) Oleum Cocois fatty acyl amidogen ether sal epsom; Polyethylene oxide (4 moles) Oleum Cocois fatty acyl amidogen ether sulfuric acid trolamine; Polyethylene oxide (4 moles) Oleum Cocois fatty acyl amidogen ether sulfuric acid arginine; The salt of polyethylene oxide (4 moles) coconut fatty oil fat amide ether sulfuric acid and Sodium taurine salt; The salt of polyethylene oxide (4 moles) Oleum Cocois fatty acyl amidogen ether sulfuric acid and N methyl taurine sodium; The salt of polyethylene oxide (4 moles) Oleum Cocois fatty acyl amidogen ether sulfuric acid and disodium glutamate; Polyethylene oxide (3 moles) palm kernel oil fatty amide ether sodium sulfate; Polyethylene oxide (4 moles) palm kernel oil fatty acyl amidogen ether sulfuric acid Methionin; Polyethylene oxide (3 moles) palm kernel oil fatty acyl amidogen ether sal epsom; The salt of polyethylene oxide (3 moles) palm kernel oil fatty acyl amidogen ether sulfuric acid and Sodium taurine salt; The salt of polyethylene oxide (3 moles) palm kernel oil fatty acyl amidogen ether sulfuric acid and N methyl taurine sodium; The salt of polyethylene oxide (3 moles) palm kernel oil fatty acyl amidogen ether sulfuric acid and Sodium glycocollate; Polyethylene oxide (6 moles) tallow fatty amide ether sodium sulfate; Deng.
(acyl taurate type anionic surfactant (a3))
In the acyl taurate type anionic surfactant who represents by a3, the preferred acyl taurate anionic surfactant (a3) who uses by following formula (3) expression.
In the formula, R
2CO and M
2Expression and the same base of above-mentioned formula (2), R
3Expression hydrogen atom or carbonatoms are 1～3 alkyl.
R as formula (3)
2The preferred acyl group of CO can be enumerated and the same base of formula (2).Carbonatoms has the tendency that pungency strengthens, whipability reduces of pair skin 7 when following; Carbonatoms is 23 when above, the tendency that has whipability to reduce.
R
3Be that hydrogen atom or carbonatoms are 1～3 alkyl.Get alkyl as carbonatoms 1～3, can enumerate methyl, ethyl and propyl group.
M
2Kind and preferred example also the same with situation in the above-mentioned formula (2).
The acyl taurate type anionic surfactant's of above-mentioned formula (3) expression concrete example can be enumerated following tensio-active agent: lauroyl N-methyltaurine sodium; Lauroyl ethyl taurine potassium; Lauroyl propyl group taurine ammonium; Myristoyl N-methyltaurine sodium; Palmitoyl N-methyltaurine sodium; Stearyl-N-methyltaurine sodium; Oleoyl N-methyltaurine sodium; Oleum Cocois fatty acyl group Sodium taurine salt; Oleum Cocois fatty acyl group N-methyltaurine sodium; Oleum Cocois fatty acyl group N-methyltaurine potassium; Oleum Cocois fatty acyl group N-methyltaurine magnesium; Oleum Cocois fatty acyl group N-methyltaurine trolamine; The salt of Oleum Cocois fatty acyl group N-methyltaurine and Sodium taurine salt; The salt of Oleum Cocois fatty acyl group N-methyltaurine and N methyl taurine sodium; The salt of Oleum Cocois fatty acyl group N-methyltaurine and disodium glutamate; Palm nuclear fatty acyl group Sodium taurine salt; Palm nuclear fatty acyl group N-methyltaurine sodium; Palm nuclear fatty acyl group N-methyltaurine lysine salt; Palm nuclear fatty acyl group N-methyltaurine magnesium; The salt of palm nuclear fatty acyl group N-methyltaurine and Sodium taurine salt; The salt of palm nuclear fatty acyl group N-methyltaurine and N methyl taurine sodium; The salt of palm nuclear fatty acyl group N-methyltaurine and Sodium glycocollate; Tallow fatty acyl group N-methyltaurine sodium; Deng.
(undecylene amide group acetate betaine type amphoteric surfac-tant (b))
In the undecylene amide group acetate betaine type amphoteric surfac-tant who represents by b, the also preferred undecylene amide group acetate betaine type amphoteric surfac-tant who uses by following formula (4) expression.
In the formula, m is 1～3, be preferably 2～3 integer.R
4And R
5Represent independently that respectively carbonatoms is that 1～3 alkyl or carbonatoms are 1～3 hydroxyalkyl.
Preferred undecylene amide group acetate betaine type amphoteric surfac-tant (b) can enumerate: undecylene amidopropyl dimethylaminoethyl acid trimethyl-glycine, undecylene amido-ethyl diethyl amino guanidine-acetic acid trimethyl-glycine, undecylene amido-ethyl dihydroxy ethyl Padil trimethyl-glycine etc.
In addition, just know that since ancient times the undecylene acid derivative has fungi-proofing efficiently antimold activity.When CTFA type amphoterics is used as fungi-proofing mould inhibitor, it is said to be effective more than the 0.5 weight %.Therefore, the cleansing composition of the present invention that contains the above CTFA type amphoterics of 0.5 weight % also has good fungi-proofing mildew-resistant (sterilization effect) property.
(other additive)
In cleansing composition of the present invention, water can also be contained, and as required, under the situation of not damaging effect of the present invention, tensio-active agent beyond a and the b and other the used additive of general cleansing composition can also be contained.
As the tensio-active agent beyond a and the b, for example, can be the amphoterics that contains amide group acetate trimethyl-glycine.As such amide group acetate betaine type amphoteric surfac-tant, can enumerate decoyl amido propyl-dimethyl Padil trimethyl-glycine, caprinoyl amido propyl-dimethyl Padil trimethyl-glycine, lauroyl amido propyl-dimethyl Padil trimethyl-glycine, mnyristoyl amido propyl-dimethyl Padil trimethyl-glycine, palmityl amido propyl-dimethyl Padil trimethyl-glycine, stearyl amido propyl-dimethyl Padil trimethyl-glycine, oleoyl amido propyl-dimethyl Padil trimethyl-glycine; mountain Yu amidopropyl dimethylaminoethyl acid trimethyl-glycine, Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine, palm kernel oil fatty acyl amido propyl-dimethyl Padil trimethyl-glycine, sunflower oil fatty acyl amido propyl-dimethyl Padil trimethyl-glycine, sclerosis tallow fatty acyl amido propyl-dimethyl Padil trimethyl-glycine, lauroyl amido ethyl diethyl amino guanidine-acetic acid trimethyl-glycine, mnyristoyl amido ethyl diethyl amino guanidine-acetic acid trimethyl-glycine, Oleum Cocois fatty acyl amido ethyl diethyl amino guanidine-acetic acid trimethyl-glycine, palm kernel oil fatty acyl amido ethyl diethyl amino guanidine-acetic acid trimethyl-glycine, lauroyl amido ethyl dihydroxy ethyl Padil trimethyl-glycine, mnyristoyl amido ethyl dihydroxy ethyl Padil trimethyl-glycine, Oleum Cocois fatty acyl amido ethyl dihydroxy ethyl Padil trimethyl-glycine, palm kernel oil fatty acyl amido ethyl dihydroxy ethyl Padil trimethyl-glycine etc.
Be used for the additive of cleansing composition as general other, for example, can enumerate: higher alcoholss such as hexadecanol, stearyl alcohol; Polyvalent alcohols such as glycerine, ethylene glycol, propylene glycol, 1,3 butylene glycol; The oil content of squalane, Jojoba oil, sweet oil, Viscotrol C, lanolin, Yelkin TTS etc.; Cationic macromolecular compounds such as the multipolymer of ether of cellulose type cationic macromolecular compound, cationic Polyvinylpyrolidone (PVP) derivative, cationic polyacrylic acid derivative, cationic polymeric amide derivative, polychlorostyrene dimethyl diallylamine, chlorination dimethyl diallyl amine and acrylic amine, alkyl polyvinyl imines; Silicone derivatives such as high polymerization methyl polysiloxane, dimethyl siloxane methyl (polyethylene oxide) silicone copolymers; Granulating agents such as two glycol stearates, styrene polymer; Hair tonic preparations (tonic agents) such as 5-methyl-2-isopropyl cyclohexanol, pimento tincture; Sequestrants such as edetate, citric acid, nitrilotriacetic acid trisodium; UV light absorber such as benzophenone derivates, benzotriazole derivatives; Pigment; Spices etc.
(cleansing composition)
Cleansing composition of the present invention is characterized in that: contain at least a kind in the class of the above-mentioned a1 of being selected from of 5～35 weight %, a2 and a3, and, contained b is 0.5～20 weight %, the weight ratio of a/b is 3/4～10/1, also contains water and a as required and b tensio-active agent and other additive in addition.
By having the proportioning of above-mentioned a and b, even can provide under the situation that oil content exists, also have high whipability, good alveolar substance and storage stability; Pungency to skin is low, and the sensation after cleaning is salubrious and in a good humor; Even and frequently use also seldom causes xerosis cutis, and can keep the cleansing composition of skin wet.
Cleansing composition of the present invention is preferably used as face cleaning milk, bathing agents, dishwashing detergent, shampoo etc., and is more preferably corresponding with used for various applications, has the cleansing composition of the specific composition of following explanation.
(face cleaning milk)
When cleansing composition of the present invention is used as face cleaning milk, be preferably higher fatty acid salt (a1) and undecylene amide group acetate betaine type amphoteric surfac-tant's (b) combination.A1 preferably contains 15～35 weight %, more preferably contains 18～32 weight %.During less than 15 weight %, can not obtain whipability, alveolar substance, washing force, the usability satisfied face cleaning milk of people in addition; During greater than 35 weight %, can cause overwass, the xerosis cutis after the washing, the salubrious sense after the washing is poor.
B preferably contains 0.5～10 weight %, more preferably contains 2～8 weight %.B is during less than 0.5 weight %, the xerosis cutis after the washing, and in addition, whipability, alveolar substance are insufficient; B is during greater than 10 weight %, has the salubrious sense after stick-slip sense and the washing poor during washing.
And a1+b is preferably 20～45 weight %, more preferably 25～40 weight %.The weight ratio of a1/b is preferably 3/1～10/1, and more preferably 3/1～7/1.In the time of beyond this scope, stick-slip sense is arranged when having washing, therefore also poor the or easy exsiccant tendency of washing back skin of the salubrious sense after the washing will not be selected for use.
(bathing agents)
When cleansing composition of the present invention is used as bathing agents, be preferably higher fatty acid salt (a1) and dodecylene amide group acetate betaine type amphoteric surfac-tant's (b) combination.At this moment, higher fatty acid salt (a1) preferably contains 5～35 weight %, more preferably contains 10～30 weight %.During less than 5 weight %, can not obtain whipability, alveolar substance, washing force, the usability satisfied bathing agents of people in addition; During greater than 35 weight %, can cause overwass, the xerosis cutis after the washing, the salubrious sense after the washing is poor.
B is preferably and contains 0.5～15 weight %, more preferably contains 2～12 weight %.B is during less than 0.5 weight %, the xerosis cutis after the washing, and in addition, whipability, alveolar substance are insufficient; During greater than 15 weight %, have during washing stick-slip sense and the washing after salubrious sense also poor.
A1+b is preferably 10～40 weight %, more preferably 12～35 weight %.The weight ratio of a1/b is preferably 2/1～10/1, and more preferably 2/1～7/1.In the time of beyond this scope, stick-slip sense is arranged when having washing, therefore also poor the or easy exsiccant tendency of washing back skin of the salubrious sense after the washing will not be selected for use.
(detergent for kitchen use)
When cleansing composition of the present invention was used as detergent for kitchen use, a was preferably amide ether sulfate type anionic surfactant (a2) or acyl taurate type anionic surfactant (a3).Any one can be used alone, but also also mix together a2 or a3.In addition, the mixture that is included in the compound among the a2 can also be used, also the mixture that is included in the compound among the a3 can be used.
A2 or a3 preferably contain 5～30 weight %, more preferably contain 10～25 weight %.During less than 5 weight %, because the existence of oil content, whipability reduces; During greater than 30 weight %, the stability of lasting under the low temperature worsens.
B preferably contains 0.5～20 weight %, more preferably contains 1～15 weight %.B is during less than 0.5 weight %, because the existence of oil content, whipability reduces; During greater than 20 weight %, the stability of lasting under the high temperature worsens.
And a2+b or a3+b are preferably 10～45 weight % and a/b (being the weight ratio of a2 or a3 and b) is preferably 3/4～8/1.In the time of beyond this scope, because the existence of oil content has whipability to reduce, pungency strengthens, and lasts the tendency that stability reduces.
In addition, a2+b or a3+b be 15～40 weight % more preferably, and a/b more preferably 1/1～5/1.
(shampoo)
When cleansing composition of the present invention was used as shampoo, a was preferably amide ether sulfate type anionic surfactant (a2) or acyl taurate type anionic surfactant (a3).Any one both can be used alone, but also also mix together a2 or a3.
A2 or a3 preferably contain 5～20 weight %, more preferably contain 6～15 weight %.During less than 5 weight %, because the existence of oil content, whipability reduces; During greater than 20 weight %, the stability of lasting under the low temperature worsens.
B preferably contains 0.5～20 weight %, more preferably contains 1～15 weight %.B is during less than 0.5 weight %, because the existence of oil content, whipability reduces; During greater than 20 weight %, the stability of lasting under the high temperature worsens.
And a2+b or a3+b are preferably 6～30 weight % and a/b (being the weight ratio of a2 or a3 and b) is preferably 3/4～5/1.In the time of beyond this scope, because the existence of oil content has whipability to reduce, pungency strengthens, and lasts the tendency that stability reduces.
In addition, a2+b or a3+b are preferably 8～20 weight %, and a/b is preferably 1/1～4/1.
(embodiment)
Below, specifically describe the present invention by embodiment, certainly, the present invention is not limited to these embodiment.In addition; any one of higher fatty acid salt (a1), amide ether sulfate type anionic surfactant (a2) or acyl taurate type anionic surfactant (a3) can be called a composition separately, and undecylene amide group acetate betaine type amphoteric surfac-tant (b) is called the b composition separately.
(embodiment 1～10, comparative example 1～8)
The cleansing composition that contains higher fatty acid salt is formed by the modulation of forming shown in table 1～3.To the project of (1) shown below～(10), the cleansing composition that the laboratory method evaluation of recording and narrating according to projects obtains.
(1) sensation of the skin after cleaning repeatedly
With each 10 people of the men and women of healthy skin as special member, with clean hand of cleansing composition 5g and forearm.Washed once 10 times repeatedly every 20 minutes.Washed repeatedly continuously 3 days, and after last clean 48 hours, reported the drying regime of hand and skin of forearm,, try to achieve 20 people's mean value according to following standard determination by oneself.
2 points: ratio feels not change or have moist feeling before skin and the experiment.
1 point: more or less tight sense of skin or dry sensation more or less.
0 point: the tight sense of skin is very strong or dry sensation is very strong.
With mean value be judged to be more than 1.5 xerosis cutis few, feel good.
(2) humidity of the skin after cleaning repeatedly
Measure electricity and lead (electric conductivity) index as the humidity of skin.The same with above-mentioned (1), before the clean experiment, to measure the electricity of 20 special members' forearm inboard and lead, 3 day in carry out the same with (1) cleaned repeatedly.After last clean 48 hours, measure the electricity of 20 special members' forearm inboard and lead, the drying regime of research skin.Be that the electricity that uses mhometer (SKICON-200, IBS corporate system) to measure 3 forearm inboards is led, and averages after 20 ℃ indoor the keeping quite 30 minutes in temperature.
The electric conductivity value of cleaning 20 preceding people of experiment is in the scope of 300～800 μ S.The electricity of measure cleaning after the experiment is led, and by following formula: (electricity before the electricity after cleaning is led-cleaned is led) * 100/ is cleaned preceding electricity and led, and tries to achieve the decrement that electricity is led.According to this decrement, judge as follows, try to achieve 20 people's mean value.
2 points: the decrement less than 20% that electricity is led.
1 point: the decrement that electricity is led is more than 20%～less than 40%.
0 point: the decrement that electricity is led is more than 40%.
Mean value is being judged to be more than 1.5 and can keeping humidity of skin effectively, respond well.
(3) state of the epidermal keratinocyte after cleaning
The same with above-mentioned (1) carry out 3 days clean repeatedly after, from last clean 48 hours after, take the epidermal keratinocyte of 20 special member's forearm inboards with adhesive tape demoulding method.It is attached on the slide glass, remove adhesive tape with acetone after, give cell dyeing with bright green, Viola crystallina, as the observation test portion.Under 80 times multiplying power, observe 10 visuals field with observation by light microscope.100 cells are examined successively from the upper right corner in the visual field in each visual field, divide forming shape remaining Parakeratotic cell to be arranged, represent to be counted as Normocellular ratio in observed 1000 cells with percentage near the cell or the nuclear of circle or orthogonal normal cell and shape distortion.According to this percentage, followingly judge, try to achieve 20 people's equalization point.
2 points: can regard normal cell as more than 90%.
1 point: can regard normal cell 70～90% as.
0 point: can regard normal cell less than 70% as.
Equalization point is 1.5 when above, for maintaining the state that parakeratosis reduces, old stratum corneum is peeled off the normal epidermis keratinocyte that gets along with effectively, is judged to be good.
(4) skin irritation
Test is estimated according to the sealing skin contact.Promptly, use the aqueous solution of cleansing composition 0.5 weight %, carry out 24 hours sealing skin contact test in the forearm inboard, judge according to naked eyes and estimate each 10 people of men and women of skin health.Do not see that fully skin is 0 point when changing, find out that skin is 1 point when some erythema is arranged, see when skin has obvious erythema, edema being 2 points, obtain 20 people's mean value, with 3 sections following method evaluations.
Skin irritation weak (mean value less than 0.5 point).
Skin irritation moderate (mean value more than 0.5, less than 1.0 points).
Skin irritation strong (mean value is more than 1.0).
(5) foaming power
In the cup of rock paddy industry (strain) system Milser (model IFM-100), take with artificial hard water (with calcium chloride and ion exchanged water modulation, and being converted into lime carbonate is 100ppm) dilution cleansing composition concentration be the experimental solutions 50g of 1 weight %, then to wherein adding 0.3g artificial dirt (forming: sweet oil 50 weight %, oleic acid 20 weight %, lanolin 10 weight %, whiteruss 10 weight %, squalene 10 weight %), give this Cup lid upper cover, under 40 ℃, left standstill 1 hour.After 1 hour, cup is installed on the Milser, stirred for 5 seconds, measure and stir the foaming height that stops after 1 minute with 3000rpm.Highly be evaluated as the high composition of foaming power from the foaming of the extreme lower position of cup for the composition more than the 7cm.
(6) Pao persistence
Measure and stir the foaming height that stops after 5 minutes in above-mentioned (5), try to achieve by following formula.With numerical value is that cleansing composition more than 90% is judged to be bubble persistence height.Lasting rate (%)={ (the foaming height after 5 minutes)/(the foaming height after 1 minute) } * 100
(7) alveolar substance
Each 10 people of men and women are as special member, and the alveolar substance when cleaning hand and forearm with cleansing composition 5g is as described belowly judged, tries to achieve 20 people's mean value.
2 points: the alveolar substance exquisiteness is flexible.
1 point: alveolar substance is coarse.
0 point: alveolar substance is coarse nonelastic
Mean value is being judged to be the good cleansing composition of alveolar substance when cleaning more than 1.5 o'clock.
Stick-slip sense when (8) cleaning
Each 10 people of men and women, judge as described below with the stick-slip sense behind clean hand of cleansing composition 5g and the forearm as special member, try to achieve 20 people's mean value.
2 points: the situation of not feeling stick-slip sense.
1 point: the situation of feeling stick-slip sense a little.
0 point: the situation of feeling stick-slip sense strongly.
Mean value is being evaluated as the cleansing composition that does not have stick-slip sense when cleaning more than 1.5.
(9) the salubrious sense after cleaning
Each 10 people of men and women, judge as described below with the salubrious sense behind clean hand of cleansing composition 5g and the forearm as special member, try to achieve 20 people's mean value.
2 points: the situation of feeling to have salubrious sense.
1 point: the situation of feeling a bit salubrious sense.
0 point: the situation of not feeling salubrious sense.
Mean value is being evaluated as the cleansing composition that salubrious sense is arranged after cleaning more than 1.5.
(10) last stability
Down preserved cleansing compositions 1 month at-5 ℃, the outward appearance of observing it is with 3 sections method evaluations shown in following.
Having good stability, (be dissolved into transparent or little muddy shape, outward appearance does not change.)
It is bad (muddy a little that stability has slightly.)
Stability is bad (can see separation, precipitation or curing.)
The result is shown in table 1～3.In addition, the numeral weight % in the table shown below.
Table 1
| Embodiment (weight %) | |||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | |
| (a1) potassium laurate | 10 | 7 | - | 4 | - | 3 | - |
| (a1) potassium myristate | 12 | 7 | - | 2 | 11 | 2 | - |
| (a1) coco-nut oil fatty acid trolamine | - | - | 11 | - | - | - | 15 |
| (a1) potassium oleate | - | 4 | - | - | - | - | - |
| (a1) salt of lauric acid and Sodium glycocollate salt formation | - | - | - | - | 10 | 2 | - |
| (a1) salt of tetradecanoic acid and L-Ala trolamine salt formation | - | - | - | - | - | - | 5 |
| (a1) salt of lauric acid and Sodium Glutamate salt formation | - | - | - | - | - | - | - |
| (a1) salt of coco-nut oil fatty acid and Methionin formation | - | - | - | - | - | - | - |
| (a1) salt of lauric acid and Sodium taurine salt salt formation | - | - | - | - | - | - | - |
| (b) undecylene amidopropyl dimethylaminoethyl acid trimethyl-glycine | 5 | 3 | 3 | 3 | 8 | 3 | 4 |
| (b) undecylene amido-ethyl diethyl amino guanidine-acetic acid trimethyl-glycine | - | - | - | 3 | - | 3 | - |
| A1 adds up to | 22 | 18 | 11 | 6 | 21 | 7 | 20 |
| B adds up to | 5 | 3 | 3 | 6 | 8 | 6 | 4 |
| a1/b | 4.4 | 6 | 3.7 | 1 | 2.6 | 1.2 | 5 |
| Lauroyl amido propyl-dimethyl Padil trimethyl-glycine | - | - | - | 2 | - | 2 | - |
| Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine | 5 | - | - | 1 | 5 | - | - |
| Mnyristoyl amido propyl-dimethyl Padil trimethyl-glycine | - | 4 | - | - | - | - | 3 |
| Lauroyl amido ethyl diethyl amino guanidine-acetic acid trimethyl-glycine | - | - | - | - | - | - | 1 |
| Palmityl amido propyl group dihydroxy ethyl Padil trimethyl-glycine | - | 2 | - | - | - | - | - |
| Methyl p-hydroxybenzoate | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Propylparaben | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Spices | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Pure water | Remainder | ||||||
| PH (5 weight %/25 ℃) | 9.6 | 9.5 | 8.2 | 9.3 | 8.5 | 9.2 | 8 |
| Estimate | |||||||
| (1) cleans the sensation of skin afterwards repeatedly | Well | Well | Well | Well | Well | Well | Well |
| 1.9 | 1.9 | 1.7 | 1.8 | 2 | 1.9 | 1.9 | |
| (2) clean the humidity of skin afterwards repeatedly | Well | Well | Well | Well | Well | Well | Well |
| 2 | 1.9 | 1.8 | 2 | 2 | 2 | 1.8 | |
| (3) clean the state of epidermal keratinocyte afterwards repeatedly | Well | Well | Well | Well | Well | Well | Well |
| 1.8 | 1.7 | 1.7 | 1.8 | 1.9 | 1.9 | 1.9 | |
| (4) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than | A little less than | A little less than |
| 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
| (5) the foaming height (cm) of foaming power after 1 minute | High | High | High | High | High | High | High |
| 9.5 | 9.1 | 8.3 | 8.1 | 9.4 | 8.9 | 9.7 | |
| (6) the foaming height (cm) of Pao lasting rate (%) after 5 minutes | High | High | High | High | High | High | High |
| 98.9 | 97.8 | 98.8 | 98.8 | 98.9 | 98.9 | 99 | |
| 9.4 | 8.9 | 8.2 | 8 | 9.3 | 8.8 | 9.6 | |
| (7) alveolar substance | Well | Well | Well | Well | Well | Well | Well |
| 1.8 | 1.7 | 1.7 | 1.6 | 1.9 | 1.6 | 1.7 | |
| Stick-slip sense when (8) cleaning | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
| 1.8 | 1.7 | 1.8 | 1.6 | 1.7 | 1.7 | 1.8 | |
| (9) the salubrious sense after cleaning | Have | Have | Have | Have | Have | Have | Have |
| 1.9 | 1.9 | 2 | 1.8 | 2 | 1.7 | 2 | |
| (10) last stability | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 2
| Embodiment (weight %) | Comparative example (weight %) | |||||
| 8 | 9 | 10 | 1 | 2 | 3 | |
| (a1) potassium laurate | - | 6 | 8 | 2 | 4 | - |
| (a1) potassium myristate | - | 6 | 12 | 1 | 3 | - |
| (a1) coco-nut oil fatty acid trolamine | - | - | - | - | - | 20 |
| (a1) potassium oleate | - | 3 | 3 | - | - | - |
| (a1) salt of lauric acid and Sodium glycocollate salt formation | 10 | - | - | - | - | - |
| (a1) salt of tetradecanoic acid and L-Ala trolamine salt formation | 10 | - | - | - | - | 18 |
| (a1) salt of lauric acid and Sodium Glutamate salt formation | 10 | - | - | - | - | - |
| (a1) salt of coco-nut oil fatty acid and Methionin formation | - | 7 | - | - | - | - |
| (a1) salt of lauric acid and Sodium taurine salt salt formation | - | - | 9 | - | - | - |
| (b) undecylene amidopropyl dimethylaminoethyl acid trimethyl-glycine | 5 | 8 | 4 | 3 | 0.5 | 5 |
| (b) undecylene amido-ethyl diethyl amino guanidine-acetic acid trimethyl-glycine | - | - | 2 | - | - | - |
| A1 adds up to | 30 | 22 | 32 | 3 | 7 | 38 |
| B adds up to | 5 | 8 | 6 | 3 | 0.5 | 5 |
| a1/b | 6 | 2.75 | 5.3 | 1 | 14 | 7.6 |
| Lauroyl amido propyl-dimethyl Padil trimethyl-glycine | 5 | - | - | 2 | - | 5 |
| Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine | 5 | 10 | - | - | 0.5 | 5 |
| Mnyristoyl amido propyl-dimethyl Padil trimethyl-glycine | - | - | 6 | - | - | - |
| Lauroyl amido ethyl diethyl amino guanidine-acetic acid trimethyl-glycine | - | - | - | - | - | - |
| Palmityl amido propyl group dihydroxy ethyl Padil trimethyl-glycine | - | - | 2 | - | - | - |
| Methyl p-hydroxybenzoate | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Propylparaben | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Spices | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Pure water | Remainder | |||||
| PH (5 weight %/25 ℃) | 8.6 | 9.3 | 9.4 | 9.1 | 9.5 | 8.3 |
| Estimate | ||||||
| (1) cleans the sensation of skin afterwards repeatedly | Well | Well | Well | Well | Bad | Bad |
| 1.8 | 1.9 | 1.8 | 1.8 | 0.8 | 0.5 | |
| (2) clean the humidity of skin afterwards repeatedly | Well | Well | Well | Well | Bad | Bad |
| 1.9 | 2 | 1.7 | 1.7 | 0.9 | 0.6 | |
| (3) clean the state of epidermal keratinocyte afterwards repeatedly | Well | Well | Well | Well | Bad | Bad |
| 1.8 | 1.9 | 1.8 | 1.8 | 1.1 | 0.8 | |
| (4) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than | A little less than |
| 0 | 0 | 0 | 0 | 0 | 0 | |
| (5) the foaming height (cm) of foaming power after 1 minute | High | High | High | High | High | High |
| 9.8 | 10.5 | 9.5 | 7.2 | 7.4 | 9.4 | |
| (6) the foaming height (cm) of Pao lasting rate (%) after 5 minutes | High | High | High | Low | Low | High |
| 98 | 99 | 98.9 | 6.3 | 6.6 | 9.3 | |
| 9.6 | 10.4 | 9.4 | 87.5 | 89.2 | 98.9 | |
| (7) alveolar substance | Well | Well | Well | Bad | Bad | Well |
| 2 | 2 | 1.8 | 0.9 | 1.3 | 1.8 | |
| Stick-slip sense when (8) cleaning | Do not have | Do not have | Do not have | Have | Do not have | Do not have |
| 1.9 | 1.7 | 1.8 | 1.3 | 1.7 | 1.8 | |
| (9) the salubrious sense after cleaning | Have | Have | Have | Do not have | Have | Do not have |
| 2 | 1.7 | 1.8 | 1.2 | 1.7 | 1.2 | |
| (10) last stability | ○ | ○ | ○ | ○ | ○ | ○ |
Table 3
| Comparative example (weight %) | |||||
| 4 | 5 | 6 | 7 | 8 | |
| (a1) potassium laurate | 7 | 8 | - | 10 | - |
| (a1) potassium myristate | - | 12 | - | 12 | 8 |
| (a1) coco-nut oil fatty acid trolamine | - | - | 20 | - | - |
| (a1) potassium oleate | - | 3 | - | - | - |
| (a1) salt of lauric acid and Sodium glycocollate salt formation | 4 | - | - | - | 5 |
| (a1) salt of tetradecanoic acid and L-Ala trolamine salt formation | - | - | 18 | - | - |
| (a1) salt of lauric acid and Sodium Glutamate salt formation | - | - | - | - | - |
| (a1) salt of coco-nut oil fatty acid and Methionin formation | - | - | - | - | - |
| (a1) salt of lauric acid and Sodium taurine salt salt formation | - | 9 | - | - | - |
| (b) undecylene amidopropyl dimethylaminoethyl acid trimethyl-glycine | 10 | 2 | 3 | 2 | - |
| (b) undecylene amido-ethyl diethyl amino guanidine-acetic acid trimethyl-glycine | 6 | - | - | - | - |
| A1 adds up to | 11 | 32 | 38 | 22 | 13 |
| B adds up to | 16 | 2 | 3 | 2 | 0 |
| a1/b | 0.7 | 16 | 12.7 | 11 | - |
| Lauroyl amido propyl-dimethyl Padil trimethyl-glycine | 8 | 2 | 3 | - | - |
| Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine | - | - | 2 | 4 | 13 |
| Mnyristoyl amido propyl-dimethyl Padil trimethyl-glycine | - | - | - | - | - |
| Lauroyl amido ethyl diethyl amino guanidine-acetic acid trimethyl-glycine | - | - | - | 4 | - |
| Palmityl amido propyl group dihydroxy ethyl Padil trimethyl-glycine | - | 2 | - | - | - |
| Methyl p-hydroxybenzoate | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Propylparaben | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Spices | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Pure water | Remainder | ||||
| PH (5 weight %/25 ℃) | 9.3 | 9.6 | 8.4 | 9.7 | 9.3 |
| Estimate | |||||
| (1) cleans the sensation of skin afterwards repeatedly | Well | Bad | Bad | Bad | Bad |
| 1.8 | 0.9 | 0.8 | 0.8 | 0.9 | |
| (2) clean the humidity of skin afterwards repeatedly | Well | Bad | Bad | Bad | Bad |
| 1.7 | 1 | 0.5 | 0.6 | 0.4 | |
| (3) clean the state of epidermal keratinocyte afterwards repeatedly | Well | Bad | Bad | Bad | Bad |
| 1.7 | 1.2 | 1 | 0.9 | 0.8 | |
| (4) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than |
| 0 | 0 | 0.1 | 0 | 0 | |
| (5) the foaming height (cm) of foaming power after 1 minute | High | High | High | High | High |
| 9.8 | 9.4 | 9.6 | 9.6 | 9 | |
| (6) the foaming height (cm) of Pao lasting rate (%) after 5 minutes | High | High | High | High | High |
| 9.5 | 9.3 | 9.5 | 9.4 | 8.8 | |
| 96.9 | 98.9 | 99 | 97.9 | 97.8 | |
| (7) alveolar substance | Well | Well | Well | Bad | Bad |
| 1.7 | 1.6 | 1.7 | 1.4 | 1.2 | |
| Stick-slip sense when (8) cleaning | Have | Do not have | Do not have | Do not have | Do not have |
| 1.3 | 1.7 | 1.6 | 1.8 | 1.6 | |
| (9) the salubrious sense after cleaning | Do not have | Have | Do not have | Have | Have |
| 1.1 | 1.7 | 1.1 | 1.7 | 1.8 | |
| (10) last stability | ○ | ○ | ○ | ○ | ○ |
According to the embodiment 1～10 of table 1 and table 2, use the cleansing composition of composition of the present invention, always can reduce the drying of cleaning the skin after testing repeatedly, and keep the humidity of skin, the state of epidermal keratinocyte also can be regarded as normally in addition.Pungency to skin also weakens in addition.And, in persistence, the alveolar substance of foaming power, bubble, have good stability in, the stick-slip sense when cleaning reduces, the salubrious sense after cleaning is good.
In addition, use the cleansing composition of embodiment 1,2,7,8 and 10, the tight sense that after allowing 5 special members wash one's face respectively, nearly all people feels that all these composition whipabilitys are good, alveolar substance is good, the stick-slip sense when cleaning reduces, salubrious sense is arranged after cleaning, clean back skin reduces.
In addition, with the cleansing composition of embodiment 3,5,7 and 9 as bathing agents, allow 5 special members use respectively, nearly all people all feel all these detergent whipabilitys might as well, alveolar substance is good, the stick-slip sense when cleaning reduces, salubrious sense is arranged after cleaning, the tight sense of cleaning back skin reduces.
On the other hand, the comparative example 4～8 of the comparative example 1～3 of table 2 and table 3 does not obtain enough performances.Because a composition cooperates than the lacking of the scope of the invention in the comparative example 1,, stick-slip sense is arranged when clean so persistence, the alveolar substance of bubble are bad.In comparative example 2 because the weight ratio of a/b be 14/1, bigger than 10/1, so the xerosis cutis after cleaning experiment repeatedly, the humidity of skin, the state aspect of epidermal keratinocyte have problem, the persistence of bubble, alveolar substance are also bad.In comparative example 3, a composition cooperates more than 35 weight %, and the xerosis cutis after cleaning experiment repeatedly, the humidity of skin, the state aspect of epidermal keratinocyte have problem equally.In comparative example 4 because the weight ratio of a/b be 11/16, less than 3/4, so the salubrious sense after the stick-slip sense when cleaning strengthens, cleans is also insufficient.In comparative example 5 and 7, because the weight ratio of a/b is also greater than 10/1, and because do not contain the b composition in the comparative example 8, so the xerosis cutis after cleaning experiment repeatedly, the humidity of skin, the state aspect of epidermal keratinocyte have problem respectively.And in comparative example 7, alveolar substance is also insufficient.In addition, in comparative example 6, because a composition surpasses 35%, the weight ratio of a/b is greater than 10/1, so the xerosis cutis after cleaning experiment, the humidity of skin, the state aspect of epidermal keratinocyte also have problem.
Embodiment 11～13 and comparative example 9～12
Cleansing composition shown in the modulometer 4 is estimated according to above-mentioned assessment item (1)～(4) and (8)～(10).In addition, whipability (11) is carried out following evaluation.The general prescription (comparative example 9～12) of they and other is compared.
(11) whipability
Each 10 people of men and women use cleansing composition 5g as special member, and are as described below, judge the whipability when cleaning health.Try to achieve 20 people's mean value, mean value is being evaluated as whipability, the good cleansing composition of alveolar substance more than 1.5.
2 points: feel that whipability is good and alveolar substance is fine and smooth, resilient situation.
1 point: feel the insufficient or coarse situation of alveolar substance of whipability.
0 point: feel the insufficient and coarse situation of alveolar substance of whipability.
The result is as shown in table 4.
Table 4
| Embodiment (weight %) | Comparative example (weight %) | ||||||
| 11 | 12 | 13 | 9 | 10 | 11 | 12 | |
| (a1) potassium laurate | 7 | - | - | 7 | - | - | - |
| (a1) potassium myristate | 4 | - | - | 4 | - | - | - |
| (a1) coco-nut oil fatty acid trolamine | - | 18 | - | - | 10 | - | - |
| (a1) potassium oleate | 2 | - | - | 2 | - | - | - |
| (a1) salt of lauric acid and Sodium glycocollate salt formation | - | - | 16 | - | - | - | - |
| (a1) salt of tetradecanoic acid and L-Ala trolamine salt formation | - | 2 | - | - | 5 | - | - |
| (b) undecylene amidopropyl dimethylaminoethyl acid trimethyl-glycine | 4 | 4 | 5 | - | - | - | 3 |
| A1 adds up to | 13 | 20 | 16 | 13 | 15 | 0 | 0 |
| B adds up to | 4 | 4 | 5 | 0 | 0 | 0 | 3 |
| a1/b | 3.3 | 5 | 3.2 | - | - | - | - |
| Lauroyl amido propyl-dimethyl Padil trimethyl-glycine | - | 4 | - | - | - | 6 | 1 |
| Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine | 3 | - | 3 | 5 | 4 | - | - |
| Coco-nut oil fatty acid N-methyltaurine sodium | - | 2 | - | - | 2 | 4 | - |
| Oleum Cocois fatty acyl group-L-Sodium Glutamate | - | - | - | - | - | 6 | - |
| Polyethylene oxide (3EO) Sodium Lauryl Sulphate BP/USP | - | - | - | - | - | - | 10 |
| Single oleic acid polyethylene oxide sorbitanic (20EO) | - | - | - | - | 0.5 | - | - |
| The lauric acid diethanolamine | 4 | - | - | 4 | - | - | 3 |
| Macrogol 1540 | - | - | - | 1 | - | - | - |
| Two stearic acid ethylene glycol | 1.8 | 1.8 | - | 1.8 | 1.8 | - | - |
| Methyl p-hydroxybenzoate | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Propylparaben | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Spices | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Pure water | Remainder | ||||||
| PH (1 weight %/25 ℃) | 9.5 | 8.1 | 8.6 | 9.4 | 8.1 | 6.8 | 7.2 |
| Estimate | |||||||
| (1) cleans the sensation of skin afterwards repeatedly | Well | Well | Well | Bad | Bad | Bad | Bad |
| 1.8 | 1.9 | 2 | 0.8 | 0.8 | 1.3 | 1 | |
| (2) clean the humidity of skin afterwards repeatedly | Well | Well | Well | Bad | Bad | Bad | Bad |
| 1.9 | 2 | 1.9 | 0.7 | 0.9 | 1 | 0.9 | |
| (3) clean the state of epidermal keratinocyte afterwards repeatedly | Well | Well | Well | Bad | Bad | Bad | Bad |
| 1.9 | 1.9 | 1.8 | 0.5 | 0.6 | 0.9 | 0.5 | |
| (4) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than | A little less than | A little less than |
| 0 | 0 | 0 | 0 | 0 | 0 | 0.1 | |
| Stick-slip sense when (8) cleaning | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Have |
| 1.9 | 1.7 | 1.8 | 1.7 | 1.6 | 0.3 | 0.1 | |
| (9) the salubrious sense after cleaning | Have | Have | Have | Have | Have | Do not have | Do not have |
| 2 | 1.9 | 1.8 | 1.8 | 1.5 | 0.4 | 0.3 | |
| (10) last stability | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| (11) whipability | Well | Well | Well | Well | Well | Well | Well |
| 2 | 1.8 | 1.8 | 1.8 | 1.7 | 1.6 | 1.8 | |
According to embodiment 11～13 as can be known, use the cleansing composition of composition of the present invention, the state that the humidity of always can reduce repeatedly the drying of cleaning experiment back skin, keeping skin maybe can be regarded epidermal keratinocyte as is normal.Also reduced skin irritation in addition.And whipability, when cleaning and the sense of touch after cleaning good.Known they compare excellent performance significantly with the comparative example 9 and 10 that does not contain the b composition, the comparative example 12 that do not contain the comparative example 11 of a composition and b composition and do not contain a composition.
(embodiment 14～19 and comparative example 13～25)
Use amide ether sulfate type anionic surfactant (a2) as a, the test portion that the cooperation shown in the modulometer 5～6 is formed.To foaming power, the skin irritation of the cleansing composition that obtains and last stability, under the condition that changes embodiment 1～10 slightly, estimate.
(12) foaming power under oil content exists
In the cup of rock paddy industry (strain) system Milser (model IFM-100), take with artificial hard water (with calcium chloride and ion exchanged water modulation, and being converted into lime carbonate is 100ppm) dilution cleansing composition concentration be the experimental solutions 50g of 1 weight %, then to wherein adding 0.5g artificial dirt (forming: sweet oil 50 weight %, oleic acid 20 weight %, lanolin 10 weight %, whiteruss 10 weight %, squalene 10 weight %), give this Cup lid upper cover, under 40 ℃, left standstill 1 hour.After 1 hour, cup is installed on the Milser, stirred for 5 seconds, measure and stir the foaming height that stops after 1 minute with 3000rpm.Highly be evaluated as the high composition of foaming power from the foaming of the extreme lower position of cup for the composition more than the 7cm.
(13) skin irritation
Each 10 people of the men and women of healthy skin use the solution that tensio-active agent is diluted to 0.5 weight %, carry out 24 hours sealing skin contact test in the forearm inboard, judge according to naked eyes and estimate.Do not see that fully skin is 0 point when changing, find out that skin is 1 point when some erythema is arranged, see when skin has obvious erythema, edema being 2 points, obtain 20 people's mean value, with following 3 sections method evaluations.
The pungency of skin weak (mean value less than 0.5 point).
Skin irritation moderate (mean value more than 0.5, less than 1.0 points).
Skin irritation strong (mean value is more than 1.0).
(14) last stability
The 45g cleansing composition is packed in the 50ml glass spiral tube with cover ,-5 ℃ preserve 12 hours down after, preserved 12 hours down at 45 ℃, carry out repeatedly 1 every day in the middle of the month like this.Observe the outward appearance of cleansing composition, with following two-stage method evaluation.
Zero: have good stability.(outward appearance does not change between 1 month)
*: stability is bad.(confirming to occur separation and precipitation, curing, painted obvious in 1 month)
The result is shown in table 5 and 6.
Table 5
| Embodiment | |||||||
| 14 | 15 | 16 | 17 | 18 | 19 | ||
| a2 | Amide ether sulfate type anionic surfactant 1) | 5 | - | - | 20 | - | 20 |
| Amide ether sulfate type anionic surfactant 2) | - | 10 | - | - | 20 | - | |
| Amide ether sulfate type anionic surfactant 3) | - | - | 15 | - | - | - | |
| b | CTFA type amphoterics | 1 | 1 | 2 | 3 | 10 | 15 |
| Pure water | Remainder | ||||||
| A2 adds up to | 5 | 10 | 15 | 20 | 20 | 20 | |
| B adds up to | 1 | 1 | 2 | 3 | 10 | 15 | |
| a2/b | 5 | 10 | 7.5 | 6.7 | 2 | 1.3 | |
| Estimate | (12) foaming power (cm) under oil content exists | High | High | High | High | High | High |
| 8.5 | 8.1 | 8.2 | 8.3 | 8.7 | 8.9 | ||
| (13) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than | A little less than | |
| 0.2 | 0.2 | 0.2 | 0.2 | 0.3 | 0.3 | ||
| (14) last stability | ○ | ○ | ○ | ○ | ○ | ○ | |
Annotate 1): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be sodium.
2): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be 1/2 magnesium.
3): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be arginine.
Table 6
| Cooperate | Comparative example | |||||||||||||
| 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 | 25 | ||
| a2 | Amide ether sulfate type anionic surfactant 1) | 0.5 | - | - | 5 | 1 | - | - | 30 | - | - | 10 | - | - |
| Amide ether sulfate type anionic surfactant 2) | - | 35 | - | - | - | 30 | - | - | - | - | - | 10 | - | |
| Amide ether sulfate type anionic surfactant 3) | - | - | 3 | - | - | - | 1 | - | - | - | - | - | - | |
| b | CTFA type amphoterics | 1.5 | 1 | 0.1 | 35 | 0.5 | 25 | 25 | 0.2 | - | 1 | - | - | 2 |
| Sodium Lauryl Sulphate BP/USP | - | - | - | - | - | - | - | - | 10 | - | - | - | - | |
| Polyethylene oxide (2 moles) Zetesol NL salt | - | - | - | - | - | - | - | - | - | 10 | - | - | 7.5 | |
| Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine | - | - | - | - | - | - | - | - | 1 | - | 1 | - | 3 | |
| Oleum Cocois fatty amide ethyl-hydroxyethyl Sodium glycocollate | - | - | - | - | - | - | - | - | - | - | - | 1 | - | |
| Pure water | Remainder | |||||||||||||
| A2 adds up to | 0.5 | 35 | 3 | 5 | 1 | 30 | 1 | 30 | 0 | 0 | 10 | 10 | 0 | |
| B adds up to | 1.5 | 1 | 0.1 | 35 | 0.5 | 25 | 25 | 0.2 | 0 | 1 | 0 | 0 | 2 | |
| a2/b | 0.33 | 35 | 30 | 0.14 | 2 | 1.2 | 0.04 | 150 | - | 0 | - | - | 0 | |
| Estimate | (12) foaming power (cm) under oil content exists | Low | High | Low | High | Low | High | High | Low | High | Low | Low | Low | Low |
| 5.7 | 7.6 | 4.8 | 8.5 | 5.9 | 8.7 | 7.4 | 5.2 | 7.3 | 5.4 | 3.7 | 4.1 | 5.2 | ||
| (13) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than | In | A little less than | A little less than | By force | A little less than | A little less than | A little less than | A little less than | |
| 0.2 | 0.3 | 0.2 | 0.3 | 0.1 | 0.6 | 0.2 | 0.3 | 1.2 | 0.4 | 0.2 | 0.3 | 0.3 | ||
| (14) last stability | ○ | × | ○ | × | ○ | × | × | × | × | ○ | ○ | × | ○ | |
Annotate 1): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be sodium.
2): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be 1/2 magnesium.
3): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be arginine.
Even according to table 5 and 6 as can be known the cleansing composition of the embodiment of the invention 14～19 be have in the presence of oil content, also demonstrate high whipability, low to the pungency of skin, last the cleansing composition that has good stability.
Less than 5 weight %, a/b is less than 3/4, so whipability is low in the presence of oil content because of a composition for the cleansing composition of comparative example 13.
The cleansing composition of comparative example 14 is because the amount of a composition and b composition is enough, and a/b surpasses 10, so last poor stability.
Less than 5 weight %, the b composition is less than 0.5 weight % because of a composition for the cleansing composition of comparative example 15, and a/b surpasses 10, so whipability is low in the presence of oil content.
The cleansing composition of comparative example 16 is because the b composition surpasses 20 weight %, and a/b is less than 3/4, so last poor stability.
The cleansing composition of comparative example 17 because a composition less than 5 weight %, so whipability is low in the presence of oil content.
The cleansing composition of comparative example 18 is because the b composition surpasses 20 weight %, so strong to skin irritation, last poor stability.
The cleansing composition of comparative example 19 is because the b composition surpasses 20 weight %, and a/b is less than 3/4, so last poor stability.
The cleansing composition of comparative example 20 because the b composition less than 0.5 weight %, a/b surpasses 10, so in the presence of oil content, whipability is low, last poor stability.
The cleansing composition of comparative example 21 is because use Sodium Lauryl Sulphate BP/USP to replace a composition, use the anti-amidopropyl dimethylaminoethyl acid of coconut grease trimethyl-glycine to replace the b composition in addition, although so whipability height in the presence of oil content the time is strong to skin irritation, last poor stability.
The cleansing composition of comparative example 22 is because use polyethylene oxide (2 moles) Zetesol NL to replace a composition, so in the presence of oil content, whipability is low.
The cleansing composition of comparative example 23 is because use Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine to replace the b composition, so the whipability in the presence of oil content is low.
The cleansing composition of comparative example 24 is because use Oleum Cocois fatty acyl amido ethyl-hydroxyethyl Sodium glycocollate to replace the b composition, so in the presence of oil content, whipability is low, last poor stability.
The cleansing composition of comparative example 25 is because use polyethylene oxide (2 moles) Zetesol NL to replace a composition, and use Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine, so in the presence of oil content, whipability is low.
(embodiment 20)
Modulate face cleaning milk according to the prescription shown in following.
Cooperate (weight %)
(a2) amide ether sulfate type anionic surfactant
1)20
(a2) amide ether sulfate type anionic surfactant
2)3
(b) CTFA type amphoterics 5
Vinylcarbinol 2
Distearyl acid ethylene glycol 2
Sweet oil 0.5
Spices 0.3
The pure water remainder part
1): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be potassium.
2): the R of formula (2)
2CO palm kernel oil fatty acid residue, n are 3, M
2Be sodium.
With carrying out this clean evaluation with composition with embodiment 14 same methods.But, in the evaluation of the foaming power in the presence of (12) oil content, use lipstick (forming: Viscotrol C 75 weight %, glycerine three ricinoleate acid cetyl 20 weight %, pigment 4.7 weight %, spices 0.3 weight %) to replace artificial dirt as oil content.The result is as shown in table 7.This clean cleansing composition that has following characteristic with composition: though in the presence of lipstick, also demonstrate high whipability, low to the pungency of skin, last and have good stability.
(embodiment 21)
Modulate shampoo according to the prescription shown in following.
Cooperate (weight %)
(a2) amide ether sulfate anionic surfactant
1)10
(b) undecylene amido propyl betaine amphoterics 5
Distearyl acid ethylene glycol 2
Polychlorostyrene dimethyl vinyl piperidines 0.3
Citric acid 0.3
Spices 0.3
The pure water remainder part
1): the R of formula (2)
2CO is the palm kernel oil fatty acid residue, and n is 3, M
2Be N methyl taurine sodium.
2): " MERQUAT 100 " of using CALGON CORPORATION system.
With carrying out the evaluation of this hair-washing composition with embodiment 14 same methods.But, in the evaluation of the foaming power in the presence of (12) oil content, use high polymerization methyl polysiloxane (" SH200-1,000, the 000cs " of TORAYDOW CORNING SILICONE (strain) system) to replace artificial dirt as oil content.The result is as shown in table 7.Even this shampoo compositions also demonstrates high whipability in the presence of the methyl polysiloxane of high-polymerization degree, be that the pungency to skin is low, last the cleansing composition that has good stability.
(embodiment 22)
Modulate the tableware cleansing composition according to the prescription shown in following.
Cooperate (weight %)
(a2) amide ether sulfate anionic surfactant
1)20
(b) undecylene amido propyl betaine amphoterics 10
Polyoxyethylene glycol (molecular-weight average 1000) 3
Alcohol 5
The pure water remainder part
1): the R of formula (2)
2CO is a lauroyl, and n is 2, M
2Be sodium.
With carrying out of the evaluation of this tableware with cleansing composition with embodiment 14 same methods.The result is as shown in table 7.Even this tableware also demonstrates high whipability with cleansing composition in the presence of oil content, be that the pungency to skin is low, last the cleansing composition that has good stability.
(embodiment 23)
Modulate Liquid soap according to the prescription shown in following.
Cooperate (weight %)
(a2) amide ether sulfate anionic surfactant
1)12
(a2) amide ether sulfate anionic surfactant
2)3
(b) undecylene amido propyl betaine amphoterics 6
Glycerine 3
Two stearic acid ethylene glycol 2
Sweet oil 0.3
Spices 0.5
The pure water remainder part
1): the R of formula (2)
2CO palm kernel oil fatty acid residue, n are 3, M
2Be sodium.
2): the R of formula (2)
2CO palm kernel oil fatty acid residue, n are 3, M
2Be 1/2 magnesium.
With carrying out the evaluation of this Liquid soap composition with embodiment 14 same methods.The result is as shown in table 7.Even this Liquid soap composition also demonstrates high whipability in the presence of oil content, be that the pungency to skin is low, last the cleansing composition that has good stability.
(embodiment 24)
Modulate bathing agents according to the prescription shown in following.
Cooperate (weight %)
(a2) amide ether sulfate anionic surfactant
1)18
(b) undecylene amido propyl betaine amphoterics 6
Lauric acid diethanolamine 3
Propylene glycol 2
Two stearic acid ethylene glycol 2
Squalane 0.3
Spices 0.5
The pure water remainder part
1): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be sodium.
With carrying out the evaluation of this bathing liquid composition with embodiment 14 same methods.The result is as shown in table 7.Even this bathing liquid composition also demonstrates high whipability in the presence of oil content, be that the pungency to skin is low, last the cleansing composition that has good stability.
(embodiment 25)
Modulate transparent shampoo composite according to the prescription shown in following with refrigerant sense.
Cooperate (weight %)
(a2) amide ether sulfate anionic surfactant
1)4
(a2) amide ether sulfate anionic surfactant
2)3
(b) undecylene amido propyl betaine amphoterics 5
Ether of cellulose anionic polymer compound 0.5
5-methyl-2-isopropyl cyclohexanol 0.4
Citric acid 0.3
Spices 0.3
The pure water remainder part
1): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be arginine.
2): the R of formula (2)
2CO coco-nut oil fatty acid residue, n are 4, M
2Be Sodium taurine salt.
3): " the Gelner QH300 " that uses Daicel chemical industry (strain) system.
With carrying out the evaluation of this shampoo composite with embodiment 14 same methods.But,, use high polymerization methyl polysiloxane (" SH200-1,000, the 000cs " of TORAYDOW CORNING SILICONE (strain) system) to replace artificial dirt as oil content about the evaluation of the foaming power under the existence of (12) oil content.The result is as shown in table 7.Even this shampoo composite also demonstrates high whipability in the presence of high polymerization methyl polysiloxane, be that the pungency to skin is low, last the cleansing composition that has good stability.
Table 7
| Embodiment | |||||||
| 20 | 21 | 22 | 23 | 24 | 25 | ||
| A2 adds up to | 23 | 10 | 20 | 15 | 18 | 7 | |
| B adds up to | 5 | 5 | 10 | 6 | 6 | 5 | |
| a2/b | 4.6 | 2 | 2 | 2.5 | 3 | 1.4 | |
| Estimate | (12) foaming power (cm) under oil content exists | High | High | High | High | High | High |
| 8.6 | 8.7 | 8.8 | 8.6 | 8.7 | 8.7 | ||
| (13) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than | A little less than | |
| 0.3 | 0.2 | 0.3 | 0.2 | 0.2 | 0.2 | ||
| (14) last stability | ○ | ○ | ○ | ○ | ○ | ○ | |
(embodiment 26～31 and comparative example 26～38)
Use acyl taurate anionic surfactant (a3) as a, cooperate the cleansing composition of forming shown in modulometer 8 and the table 9, estimate its performance.The result is shown in table 8 and table 9.
Table 8
| Embodiment | |||||||
| 26 | 27 | 28 | 29 | 30 | 31 | ||
| a3 | Acyl taurate type anionic surfactant 1) | 5 | - | - | 20 | - | 20 |
| Acyl taurate type anionic surfactant 2) | - | 10 | - | - | 20 | - | |
| Acyl taurate type anionic surfactant 3) | - | - | 15 | - | - | - | |
| b | CTFA type amphoterics | 1 | 1 | 2 | 3 | 10 | 15 |
| Pure water | Remainder | ||||||
| A3 adds up to | 5 | 10 | 15 | 20 | 20 | 20 | |
| B adds up to | 1 | 1 | 2 | 3 | 10 | 15 | |
| a3/b | 5 | 10 | 7.5 | 6.7 | 2 | 1.3 | |
| Estimate | (12) foaming power (cm) under oil content exists | High | High | High | High | High | High |
| 9.3 | 8.9 | 9 | 9.1 | 9.5 | 9.7 | ||
| (13) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than | A little less than | |
| 0.2 | 0.2 | 0.2 | 0.2 | 0.3 | 0.3 | ||
| (14) last stability | ○ | ○ | ○ | ○ | ○ | ○ | |
Annotate 1): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be sodium.
2): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be 1/2 magnesium.
3): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be Sodium taurine salt.
Table 9
| Cooperate | Comparative example | |||||||||||||
| 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 | ||
| a3 | Acyl taurate type anionic surfactant 1) | 0.5 | - | - | 5 | 1 | - | - | 30 | - | - | 10 | - | - |
| Acyl taurate type anionic surfactant 2) | - | 35 | - | - | - | 30 | - | - | - | - | - | 10 | - | |
| Acyl taurate type anionic surfactant 3) | - | - | 3 | - | - | - | 1 | - | - | - | - | - | - | |
| b | Undecylene amido propyl betaine type amphoterics | 1.5 | 1 | 0.1 | 35 | 0.5 | 25 | 25 | 0.2 | - | 1 | - | - | 2 |
| Other additive | Sodium Lauryl Sulphate BP/USP | - | - | - | - | - | - | - | - | 10 | - | - | - | - |
| Polyethylene oxide (2 moles) Zetesol NL | - | - | - | - | - | - | - | - | - | 10 | - | - | 7.5 | |
| Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine | - | - | - | - | - | - | - | - | 1 | - | 1 | - | 3 | |
| Oleum Cocois fatty acyl amido ethyl-hydroxyethyl Sodium glycocollate | - | - | - | - | - | - | - | - | - | - | - | 1 | - | |
| Pure water | Remainder | |||||||||||||
| A3 adds up to | 0.5 | 35 | 3 | 5 | 1 | 30 | 1 | 30 | 0 | 0 | 10 | 10 | 0 | |
| B adds up to | 1.5 | 1 | 0.1 | 35 | 0.5 | 25 | 25 | 0.2 | 0 | 1 | 0 | 0 | 2 | |
| a3/b | 0.33 | 35 | 30 | 0.14 | 2 | 1.2 | 0.04 | 150 | - | 0 | - | - | 0 | |
| Estimate | (12) foaming power (cm) under oil content exists | Low | High | Low | High | Low | High | High | Low | High | Low | Low | Low | Low |
| 6.5 | 8.4 | 5.6 | 9.3 | 6.7 | 9.5 | 8.2 | 6 | 7.3 | 5.4 | 4.5 | 4.9 | 5.2 | ||
| (13) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than | In | A little less than | A little less than | By force | A little less than | A little less than | A little less than | A little less than | |
| 0.2 | 0.3 | 0.2 | 0.3 | 0.1 | 0.6 | 0.2 | 0.3 | 1.2 | 0.4 | 0.2 | 0.3 | 0.3 | ||
| (14) last stability | ○ | × | ○ | × | ○ | × | × | × | × | ○ | ○ | × | ○ | |
Annotate 1): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be sodium.
2): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be 1/2 magnesium.
3): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be Sodium taurine salt.
Know that according to table 8 and table 9 cleansing composition of the embodiment of the invention 26～31 is the cleansing compositions with following characteristic: though in the presence of oil content, also demonstrate high whipability, low to the pungency of skin, last and have good stability.
Less than 5 weight %, a/b is less than 3/4, so in the presence of oil content, whipability is low because of a composition for the cleansing composition of comparative example 26.
The cleansing composition of comparative example 27 is because the amount of a composition and b composition is enough, and a/b surpasses 10, so last poor stability.
Less than 5 weight %, the b composition is less than 0.5 weight % because of a composition for the cleansing composition of comparative example 28, and a/b surpasses 10, so in the presence of oil content, whipability is low.
The cleansing composition of comparative example 29 is because the b composition surpasses 20 weight %, and a/b is less than 3/4, so last poor stability.
The cleansing composition of comparative example 30 because a composition less than 5 weight %, so in the presence of oil content, whipability is low.
The cleansing composition of comparative example 31 is because the b composition surpasses 20 weight %, so strong to skin irritation, last poor stability.
The cleansing composition of comparative example 32 is because the b composition surpasses 20 weight %, and a/b is littler than 3/4, so last poor stability.
The cleansing composition of comparative example 33 because the b composition less than 0.5 weight %, a/b surpasses 10, so in the presence of oil content, whipability is low, last poor stability.
The cleansing composition of comparative example 34 is because use Sodium Lauryl Sulphate BP/USP to replace a composition, use Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine to replace the b composition in addition, so in the presence of oil content, the whipability height, strong to skin irritation, last poor stability.
The cleansing composition of comparative example 35 is because use polyethylene oxide (2 moles) Zetesol NL to replace a composition, so in the presence of oil content, whipability is low.
The cleansing composition of comparative example 36 is because use Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine to replace the b composition, so in the presence of oil content, whipability is low.
The cleansing composition of comparative example 37 is because use Oleum Cocois fatty acyl amido ethyl-hydroxyethyl Sodium glycocollate to replace the b composition, so in the presence of oil content, whipability is low, last poor stability.
The cleansing composition of comparative example 38 is because use polyethylene oxide (2 moles) Zetesol NL to replace a composition, and use Oleum Cocois fatty acyl amido propyl-dimethyl Padil trimethyl-glycine, so in the presence of oil content, whipability is low.
(embodiment 32)
Modulate face cleaning milk according to the prescription shown in following.
Cooperate (weight %)
(a3) acyl taurate type anionic surfactant
1)20
(a3) acyl taurate type anionic surfactant
2)3
(b) CTFA type amphoterics 5
Vinylcarbinol 2
Two stearic acid ethylene glycol 2
Sweet oil 0.5
Spices 0.3
The pure water remainder part
1): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be potassium.
2): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be hydrogen atom, M
2Be sodium.
With carrying out this clean evaluation with composition with embodiment 14 same methods.But, in the evaluation of the foaming power in the presence of (12) oil content, use lipstick (forming: Viscotrol C 75 weight %, glycerine three ricinoleate acid cetyl 20 weight %, pigment 4.7 weight %, spices 0.3 weight %) to replace artificial dirt as oil content.The result is as shown in table 10.Even this clean with composition be in the presence of lipstick, also demonstrate high whipability, low to the pungency of skin, last the cleansing composition that has good stability.
(embodiment 33)
Modulate shampoo according to the prescription shown in following.
Cooperate (weight %)
(a3) acyl taurate type anionic surfactant
1)10
(b) CTFA type amphoterics 5
Two stearic acid ethylene glycol 2
Polychlorostyrene dimethyl vinyl piperidines 0.3
Citric acid 0.3
Spices 0.3
The pure water remainder part
1): the R of formula (3)
2CO is the coco-nut oil fatty acid residue, R
3Be methyl, M
2Be N methyl taurine sodium.
2): " MERQUAT100 " that uses CALGON CORPORATION system.
With carrying out the evaluation of this hair-washing composition with embodiment 14 same methods.But, in the evaluation of the foaming power in the presence of (12) oil content, use high polymerization methyl polysiloxane (" SH200-1,000, the 000cs " of TORAYDOW CORNING SILICONE (strain) system) to replace artificial dirt as oil content.The result is as shown in table 10.Even this hair-washing composition be in the presence of high polymerization methyl polysiloxane, also demonstrate high whipability, low to the pungency of skin, last the cleansing composition that has good stability.
(embodiment 34)
Modulate the tableware cleansing composition according to the prescription shown in following.
Cooperate (weight %)
(a3) acyl taurate type anionic surfactant
1)20
(b) the CTFA amphoterics 10
Polyoxyethylene glycol (molecular-weight average 1000) 3
Alcohol 5
The pure water remainder part
1): the R of formula (3)
2CO is a lauroyl, R
3Be methyl, M
2Be sodium.
With carrying out of the evaluation of this tableware with cleansing composition with embodiment 14 same methods.The result is as shown in table 10.Even this tableware cleansing composition be in the presence of oil content, also demonstrate high whipability, low to the pungency of skin, last the cleansing composition that has good stability.
(embodiment 35)
Modulate Liquid soap according to the prescription shown in following.
Cooperate (weight %)
(a3) acyl taurate type anionic surfactant
1)12
(a3) acyl taurate type anionic surfactant
2)3
(b) undecylene amido propyl betaine type amphoterics 6
Glycerine 3
Distearyl acid ethylene glycol 2
Sweet oil 0.3
Spices 0.3
The pure water remainder part
1): the R of formula (3)
2CO palm kernel oil fatty acid residue, R
3Be methyl, M
2Be sodium.
2): the R of formula (3)
2CO palm kernel oil fatty acid residue, R
3Be methyl, M
2Be 1/2 magnesium.
With carrying out the evaluation of this Liquid soap composition with embodiment 14 same methods.The result is as shown in table 10.Even this Liquid soap composition be in the presence of oil content, also demonstrate high whipability, low to the pungency of skin, last the cleansing composition that has good stability.
(embodiment 36)
Modulate bathing agents according to the prescription shown in following.
Cooperate (weight %)
(a3) acyl taurate type anionic surfactant
1)18
(b) CTFA type amphoterics 6
Lauric acid diethanolamine 3
Propylene glycol 2
Two stearic acid ethylene glycol 2
Squalane 0.3
Spices 0.5
The pure water remainder part
1): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be sodium.
With carrying out the evaluation of this bathing liquid composition with embodiment 14 same methods.The result is as shown in table 10.Even this bathing liquid composition be in the presence of oil content, also demonstrate high whipability, low to the pungency of skin, last the cleansing composition that has good stability.
(embodiment 37)
Modulate transparent shampoo composite according to the prescription shown in following with refrigerant sense.
Cooperate (weight %)
(a3) acyl taurate type anionic surfactant
1)4
(a3) acyl taurate type anionic surfactant
2)3
(b) CTFA type amphoterics 5
Ether of cellulose type anionic property macromolecular compound 0.5
5-methyl-2-isopropyl cyclohexanol 0.4
Citric acid 0.3
Spices 0.3
The pure water remainder part
1): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be arginine.
2): the R of formula (3)
2CO coco-nut oil fatty acid residue, R
3Be methyl, M
2Be Sodium taurine salt.
3): " the Gelner QH300 " that uses Daicel chemical industry (strain) system.
With carrying out the evaluation of this shampoo composite with embodiment 14 same methods.But, in the evaluation of the foaming power in the presence of (12) oil content, use high polymerization methyl polysiloxane (" SH200-1,000, the 000cs " of TORAYDOW CORNING SILICONE (strain) system) to replace artificial dirt as oil content.The result is as shown in table 10.Even this shampoo composite be in the presence of high polymerization methyl polysiloxane, also demonstrate high whipability, low to the pungency of skin, last the cleansing composition that has good stability.
Table 10
| Embodiment | |||||||
| 32 | 33 | 34 | 35 | 36 | 37 | ||
| A3 adds up to | 23 | 10 | 20 | 15 | 18 | 7 | |
| B adds up to | 5 | 5 | 10 | 6 | 6 | 5 | |
| a2/b | 4.6 | 2 | 2 | 2.5 | 3 | 1.4 | |
| Estimate | (12) foaming power (cm) under oil content exists | High | High | High | High | High | High |
| 9.4 | 9.5 | 9.6 | 9.4 | 9.5 | 9.5 | ||
| (13) skin irritation | A little less than | A little less than | A little less than | A little less than | A little less than | A little less than | |
| 0.3 | 0.2 | 0.3 | 0.2 | 0.2 | 0.2 | ||
| (14) last stability | ○ | ○ | ○ | ○ | ○ | ○ | |
The possibility of industrial utilization
Even because cleansing composition of the present invention also demonstrates high foaming characteristic in the presence of oil content, foam is many, alveolar substance good, when clean and the sensation after washing salubrious, in a good humor, even the frequent drying that also can not cause skin of using, and can keep the moistening of skin, last and have good stability. Can be used for clean with composition, shampoo compositions, cleansing composition for kitchen use, hand cleanser composition, bathing liquid composition etc.
Claims (5)
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP340162/00 | 2000-11-08 | ||
| JP2000340161A JP4649724B2 (en) | 2000-11-08 | 2000-11-08 | Cleaning composition |
| JP2000340162A JP4649725B2 (en) | 2000-11-08 | 2000-11-08 | Cleaning composition |
| JP340163/00 | 2000-11-08 | ||
| JP340163/2000 | 2000-11-08 | ||
| JP340161/2000 | 2000-11-08 | ||
| JP340161/00 | 2000-11-08 | ||
| JP2000340163A JP4649726B2 (en) | 2000-11-08 | 2000-11-08 | Cleaning composition |
| JP340162/2000 | 2000-11-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1537158A CN1537158A (en) | 2004-10-13 |
| CN1242037C true CN1242037C (en) | 2006-02-15 |
Family
ID=27345140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018185452A Expired - Fee Related CN1242037C (en) | 2000-11-08 | 2001-11-07 | detergent composition |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100815069B1 (en) |
| CN (1) | CN1242037C (en) |
| TW (1) | TWI257425B (en) |
| WO (1) | WO2002038714A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102178612A (en) * | 2011-04-29 | 2011-09-14 | 杨北平 | Preparation method of individual washing and nursing composition |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5591436B2 (en) | 2006-07-07 | 2014-09-17 | 味の素株式会社 | Low temperature stable cream detergent composition |
| KR101006067B1 (en) * | 2009-02-18 | 2011-01-06 | 김동엽 | Body cleaner composition for industrial workers with excellent moisturizing power |
| CN102451109A (en) * | 2010-10-28 | 2012-05-16 | 四川久大制盐有限责任公司 | Mineral salt facial cleanser and preparation method thereof |
| CN102429833B (en) * | 2011-12-29 | 2014-05-14 | 北京绿伞化学股份有限公司 | Environmentally-friendly hand sanitizer and preparation method thereof |
| CN103422343B (en) * | 2013-08-02 | 2015-05-20 | 苏州爱立方服饰有限公司 | Woolen sweater treating liquid with potassium myristate |
| KR101977287B1 (en) * | 2016-06-08 | 2019-05-10 | 주식회사 엘지생활건강 | Skin Cleansing Composition |
| EP4253510A1 (en) | 2022-03-31 | 2023-10-04 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08245982A (en) * | 1995-03-13 | 1996-09-24 | Mitsui Toatsu Chem Inc | Detergent composition |
| JPH08311489A (en) * | 1995-05-19 | 1996-11-26 | Nippon Oil & Fats Co Ltd | Detergent composition |
| JPH10237495A (en) * | 1997-02-25 | 1998-09-08 | Kao Corp | Detergent composition |
| FR2774900B1 (en) * | 1998-02-13 | 2000-03-31 | Ceca Sa | TRANSPARENT ANTI-DANDRUFF SHAMPOO |
| FR2792195B1 (en) * | 1999-04-19 | 2003-02-21 | Ceca Sa | METHOD FOR FORMULATING A NON-IRRITATING AND NON-TOXIC ANTIFUNGAL AGENT IN SURFACTANT AND AQUEOUS COMPOSITIONS FOR CLEANING THE SKIN |
| JP2007090007A (en) * | 2005-09-26 | 2007-04-12 | Mutsuhiro Kuboyama | Handmade triangular bandage |
-
2001
- 2001-11-07 KR KR1020037006247A patent/KR100815069B1/en not_active Expired - Fee Related
- 2001-11-07 CN CNB018185452A patent/CN1242037C/en not_active Expired - Fee Related
- 2001-11-07 WO PCT/JP2001/009752 patent/WO2002038714A1/en not_active Ceased
- 2001-11-08 TW TW090127732A patent/TWI257425B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102178612A (en) * | 2011-04-29 | 2011-09-14 | 杨北平 | Preparation method of individual washing and nursing composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030048461A (en) | 2003-06-19 |
| KR100815069B1 (en) | 2008-03-20 |
| CN1537158A (en) | 2004-10-13 |
| WO2002038714A1 (en) | 2002-05-16 |
| TWI257425B (en) | 2006-07-01 |
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