GB2255101A - Shampoo composition - Google Patents
Shampoo composition Download PDFInfo
- Publication number
- GB2255101A GB2255101A GB9208945A GB9208945A GB2255101A GB 2255101 A GB2255101 A GB 2255101A GB 9208945 A GB9208945 A GB 9208945A GB 9208945 A GB9208945 A GB 9208945A GB 2255101 A GB2255101 A GB 2255101A
- Authority
- GB
- United Kingdom
- Prior art keywords
- surfactant
- weight
- shampoo composition
- alkyl
- amphoteric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- 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
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
-
- 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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
-
- 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
- A61K8/60—Sugars; Derivatives thereof
- A61K8/604—Alkylpolyglycosides; Derivatives thereof, e.g. esters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/731—Cellulose; Quaternized cellulose derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
- A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
- A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
- A61K2800/5426—Polymers characterized by specific structures/properties characterized by the charge cationic
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
- Detergent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A shampoo composition comprises: (a) from 1 to 60% by weight of an anion surfactant, an amphoteric surfactant or a mixture of an anionic surfactant and an amphoteric surfactant; (b) from 0.2 to 5% by weight of an alkyl saccharide surfactant; and (c) from 0.05 to 3% by weight of a silicone derivative. wherein the weight ratio of component (a) to component (b) is from 2/1 to 150/1. The shampoo composition has an excellent foaming property, gives a good feel at the time of hair washing and rinsing, and has a very excellent style retention property after washing and drying the hair.
Description
SHAMPOO COMPOSITION
FIELD OF THE INVENTION
This invention relates to a shampoo composition.
More specifically, it relates to a shampoo composition having an excellent foaming property at the time of hair washing, giving foam of excellent feel and an excellent feel at the time of rinsing, and imparting a good hair style retention property after washing and drying the hair.
BACKGROUND OF THE INVENTION
Heretofore, nonionic surfactants have been used in detergent compositions for the skin and the hair and tableware because of their low irritating property, but the nonionic surfactants have the defect of inferior foaming property. As nonionic surfactants having excellent foaming property, alkyl saccharide surfactants were developed, and a detergent composition comprising this type of surfactant and an anionic surfactant such as an alkyl sulfate was proposed as disclosed in JP-A-58-104625 (the term JP-A as used herein means an lunexamined published Japanese Patent
Application"). This composition has excellent foaming property, but when it is used for washing hair, a squeak feel arises at the time of hair washing, and it is not suitable as a shampoo.
On the other hand, JP-A-2-231412 discloses a detergent composition comprising an alkyl saccharide surfactant and a sulfosuccinic acid surfactant in combi nation, which have an excellent foaming property and gives creamy foam, an excellent smoothness to the skin at the time of foaming, and a good feel to the hair or the skin after washing with less irritating.
However, generally, even when an anionic surfactant is used in combination with an alkyl saccharide surfactant, a squeak feel at the time of hair washing caused by the alkyl saccharide surfactant is difficult to reduce, so that when the amount of the alkyl saccharide surfactant is increased to an extent that gives sufficient foaming property, an increase in the squeak feel cannot be avoided.
Hence, while making good use of excellent properties of the alkyl saccharide surfactant having high foaming property, a shampoo composition having good feel without a squeak feel at the time of washing the hair has been desired to be developed.
SUMMARY OF THE INVENTION
In the circumstances, the present inventors have conducted extensive investigations, and found that by combining an anionic surfactant and/or amphoteric surfactant, an alkyl saccharide surfactant and a silicone derivatives a specific weight ratio, a shampoo composition having an excellent foaming property with high foam quality and excellent hair style retention property after washing and drying the hair can be obtained. This completed the preser.
invention.
The present invention provides a shampoo composition comprising the following components (a), (b) and (c):
(a) from 1 to 60% by weight of an anionic surfactant, an amphoteric surfactant or a mixture of an anionic surfactant and an amphoteric surfactant;
(b) from 0.2 to 5% by weight of an alkyl saccharide surfactant; and
(c) from 0.05 to 3% by weight of a silicone derivative,
wherein a weight ratio of component (a) to component (b) is from 2/1 to 150/1.
DETAILED DESCRIPTION OF THE INVENTION
The anionic surfactant and the amphoteric surfactant to be used as component (a) in the present invention may not be particularly restricted so long as those generally used in conventional shampoo compositions.
Examples of the anionic surfactant include alkylsulfate ester salts, polyoxyethylene alkylsulfate ester salts, alkylbenzenesulfonic acid salts, a-olefin sulfonic acid salts, a-sulfofatty acid ester salts, alkyl phosphate ester salts and sulfosuccinic acid ester salts. Of these, the alkylsulfate ester salts, polyoxyethylene alkylsulfate ester salts, and sulfosuccinic acid ester salts are preferred. Especially, from the view-point of low irritating property, the sulfosuccinic acid ester salts are preferred.
Specific examples of the alkylbenzenesulfonic acid salt include those having a straight-chain or branched alkyl group containing 10 to 16 carbon atoms on the average.
Specific examples of the a-olefine sulfonic acid salt include those containing 10 to 20 carbon atoms in one molecule thereof and the a-sulfofatty acid ester salts include salts or esters of an a-sulfofatty acid having an alkyl or alkenyl group containing 10 to 20 carbon atoms on the average.
Specific examples of the sulfosuccinic acid ester salt include salts of a sulfosuccinic acid ester of a higher alcohol containing 8 to 22 carbon atoms or an ethoxylate thereof and salts of a sulfosuccinic acid ester derived from a higher fatty acid amide.
Examples of the amphoteric surfactant include amideamine amphoteric surfactants, imidazoline amphoteric surfactants, betaine amphoteric surfactants, alkylbetaines, aminobetaines, and sulfobetaines. Of these, the amideamide amphoteric surfactants are especially preferred.
Specific examples of these amphoteric surfactants include cr-position addition, secondary amide, and tertiary amide imidazoline amphoteric surfactants; carbobetaine, amidobetaine, sulfobetaine, hydroxysulfobetaine and amidosulfobetaine amphoteric surfactants each having an alkyl, alkenyl or acyl group containing 6 to 24 carbon atoms; and the like. Among the imidazoline amphoteric surfactants, amideamine acid amphoteric surfactants which had been desalted so as to increase solubility of the polymer, as disclosed in JP-A-63-128100 for example, are preferred.
Examples of the counter ion for the anionic group of these surfactants include alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; ammonium ion; alkanol amines having 1 to 3 alkanol groups containing 2 or 3 carbon atoms such as monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine; and the like.
Among the aninonic surfactants and amphoteric surfactants, sodium polyoxyethylene lauryl eter sulfates (2 to 3 mols on the average of ethylene oxide are added), laurylsulfate triethanolamine, cocofatty acid amide ether sulfates, lauroyl-N-methyltaurine, lauroyl-N-methyl-ss- alanine, sodium polyoxyethylene lauryl sulfosuccinates (3 to 7 E.O) and the like are preferred as the anionic surfactant, and N-laruroyl-N'-carboxymethyl-N'-(2-hydroxyethyl)ethylenediamine triethanolamine salts, sodium N-lauroyl-N-(2 hydroxyethyl ) -N, N' -bis (carboxymethyl ) ethylene diamine salt and the like are preferred as the amphoteric surfactant.
In the present invention, either one or two or more of these anionic surfactants or amphoteric surfactants or a mixture thereof may be used. They are used in a total amount of from 1 to 60% by weight, preferably from 2 to 30% by weight, based on the total weight of the composition. If the amount is less than 1% by weight, an amount of form tends to be insufficient. If it exceeds 60% by weight, the viscosity of the shampoo tends to be too high and problems on practical use will be caused.
Examples of the alkyl saccharide surfactant to be used as component (b) in the present invention include those shown by formula (1): Rl-O-(R2O) -(G)p (1) wherein R1 is a straight-chain or branched alkyl, alkenyl or alkylphenyl group; R2 is an alkylene group having 2 to 4 carbon atoms; G is a residue of reducing sugar having 5 to 6 carbon atoms; t is a number of 0 to 10; and p is a number cf 1 to 10.
Of the alkyl saccharide surfactants of formula (1), those in which Rl is an alkyl group having 6 to 18 carbon atoms, particularly 6 to 12 carbon atoms (e.g., octyl group, decyl group and lauryl group) are preferred. The value c; t shows the degree of condensation of the alkylene oxide and is a number of 0 to 10. The value of t is preferably 0 to 4, and more preferably 0. As the reducing sugar represented by
G, glucose, galactose, and fructose are preferred. The average degree of polymerization of the saccharide, i.e., the value of p, is 1 to 10, preferably 1 to 4. The average degree of polymerization, i.e., the value of p, may preferably be selected with taking the hydrophobic property depending on the group of R1 into consideration.For example, when Rl is a hydrophobic group having an average carbon number of 8 to 11, the value of p is preferably 1 to 1.4, and if Rl is a hydrophobic group having an average carbon number of 12 to 14, p is preferably selected among 1.5 to 4.0. The average degree of polymerization of the sugar may be determined by proton NMR.
The alkyl saccharide surfactant as component (b) may be employed in the shampoo composition of the present invention in an amount of from 0.2 to 5% by weight, preferably from 0.5 to 3% by weight, based on the total weight of the composition. If the amount is less than 0.2% by weight, an excellent foaming property is not fully exhibited. If it exceeds 5% by weight, deterioration in feeling such as squeaking of the hair, will be caused. The amount within this range is also preferred from the standpoint of hair style retention property as one advantage of the present invention.
Furthermore, in the present invention, the weight ratio of the anionic surfactant or amphoteric surfactant or a mixture thereof as component (a) to the alkyl saccharide surfactant as component (b) (i.e., the (a)/(b) weight ratio) must be from 2/1 to 150/1. If the (a)/(b) ratio is less than 2/1, the squeak feel will become large. If it exceeds 150/1, the foaming will become small. The preferred (a)/(b) ratio is in the range of from 2/1 to 50/1.
Examples of the silicone derivative to be used as component (c) of the present invention include the following compounds (i) to (xi).
(i) Dimethylpolysiloxanes represented by formula (2): (CH3)3SiOf(CH3)2SiO]lSi(CH3)3 (2) wherein nl is an integer of 3 to 9,000.
As the methylpolysiloxane represented by formula (2), one available under the trade name KF96 from Shinets
Chemical Co., Ltd. may be used, for example.
(ii) Methylphenyl polysiloxane represented by formula (3):
wherein a is a number of 1 to 9,000; b is a number of S to 9,000; and c is a number of 0 to 9,000; provided that the sum of a, b and c is from 1 to 9,000.
The methylphenyl polysiloxanes of formula (3) are widely known, and, for example, a product available under the trade name KF50 from Shinetsu Chemical Co., Ltd. may be used.
(iii) Amino-modified silicones represented by formula (4): (R') dA(3-d)Si-(OSi(A)2)n2[OSi(A)@R'(2-@)]n3-OSi(R')dA(3-d) (4) wherein A is a group selected from a hydrogen atom, a phenyl group, a hydroxyl group and alkyl groups having 1 to 8 carbon atoms; d is 0 or an integer of 1 to 3; e is 0 or 1; n2 is 0 or an integer of 1 to 1999 and n3 is an integer of 1 to 2,000, provided that the sum of n2 and n3 is an integer of 1 to 2,000; and R' represents a group of formula -CfH2fL in which f is an integer of 2 to 8 and L is a group of the following formula:
wherein Z is a selected from a hydrogen atom, a phenyl group, a benzyl group, and alkyl groups having 1 to 20 carbon atoms; and B- is a halogen atom selected from C1-, Br, I- and F-.
Examples of the amino-modified silicones of formula (4) include those marketed under the trade names SF8417,
DC536 and the like from Toray Silicone Co., Ltd. and that marketed under the trade name Aminoalkylsilicone Emulsion
SM8702 from Toray Silicone Co., Ltd.
(iv) Fatty acid-modified polysiloxanes represented by formula (5):
wherein each of g, h and i is a number of 1 to 350; j is a number of 0 to 10; and R3 represents an alkyl group having 9 to 21 carbon atoms.
(v) Alcohol-modified silicones represented by formula (6-a) or formula (6-b):
wherein each of k and Q is a number of 1 to 500, preferably 1 to 200; and R4 represents a group of Cn4H2n4 in which n4 is a number of 0 to 4.
(vi) Aliphatic alcohol-modified silicones represented by formula (7):
wherein m is a number of 0 to 300; o is a number of 0 to 300; q is a number of 0 to 300; r is a number of 0 to 5; and R5 is a group of Cn5H2n5+1 in which n5 is a number of 4 to 22; provided that the sum of m, n and q is 1 to 300.
(vii) Polyether-modified silicones represented by formula (8-a) or (8-b):
wherein s is a number of 0 to 35; u is a number of 1 to 45; v is a number of 0 to 400; and R6 is a group of Cn6H2n6+1 in which n6 is a number of 1 to 4.
wherein w is a number of 2 to 110, preferably 20 to 80; x is a number of 1 to 50, preferably 3 to 30; y is a number of 0 to 50, preferably 5 to 30; z is a number of 0 to 50, preferably 0 to 35; and D is an alkyl group having 1 to 12 carbon atoms or a group of the formula OCn7H2n7+1 in which n7 is a number of 0 to 6.
The polyether-modified silicones of formulae (8-a) and (8-b) are widely known, and, for example, those obtained under the trade names KF351 and KF352 from Shinetsu Chemical Co., Ltd. may be used.
(viii) Epoxy-modified silicones represented by the formula (9):
wherein α is a number of 1 to 500, preferably 1 to 250; Th is a number of 1 to 50, preferably 1 to 30; and R7 is an alkylene group having 1 to 3 carbon atoms.
(ix) Fluorine-modified silicones represented by formula (10):
wherein 7 is a number of 1 to 400; preferably 1 to 250.
(x) Cyclic silicones represented by formula (11):
wherein 6 is a number of 3 to 8; and R8 is an alkyl group having l to 3 carbon atoms.
(xi) Alkyl-modified silicones represented by formula (12-a) or (12-b):
wherein each of and n is a number of 1 to 500, preferably 1 to 200; R9 is an alkyl group having 2 to 18 carbon atoms; and
R10 represents 48H > 8 in which n8 is a number of C to 4.
wherein each of e and K is a number of 1 to 500, preferably 1 to 200; and R11 is an alkyl group having 10 to 16 carbon atoms.
Any one or a mixture of these silicone derivatives can sufficiently develop the effect of the present invention.
From the viewpoint of improving good hair style retention property after washing and drying the hair, it is preferred to use the methyl-polysiloxanes (i), the amino-modified silicones (iii), the polyether-modified silicones (vii) and the cyclic silicones (x). It is more preferred to use tne amino-modified silicones (iii) and the polyether-modified silicones (vii) in combination.
The value of nl in the methyl polysiloxane (i) can be selected from 0 to 900 according to the finishing feel. To obtain a light finishing feel, it is preferably about 10 to about 1,000, and to impart sufficient tension and resilience to the hair, it is preferably at least 2,000, more preferably about 4,000 to about 7,000. As the amino-modified silicones (iii), those in which d is 0, e is 1, f is 3, A is a hydroxyl group or a methyl group, and L is -NHCH2CH2NH2, which is called amodimethycone in the CTFA dictionary of U.S.A., is especially preferred.
In the present invention, one or two or more of silicone derivative may be used as the component (c). They are used in a total amount of from 0.05 to 3% by weight, preferably from 0.1 to 2% by weight, in the shampoo composition of the present invention. If the amount is less than 0.05% by weight, the feel at the time of rinsing and the hair style retention property after washing and drying the hair will become deteriorated. If it exceeds 3% by weight, deterioration of foaming property such as the decrease in the amount of foam will be caused.
The shampoo composition of the present invention can be prepared by mixing the above essential components with water in a conventional manner. If required, the other components may be added in amounts which do not impair the effect of the invention. For example, an anionic surfactant and a cationic surfactant may be incorporated. Furthermore, foam increasing agents, ultraviolet absorbers, antiseptics, various solvents, anti-dandruff agents, antioxidants, coloring agents and perfumes may be incorporated according to the object.
If a cationic polymer is incorporated in the shampoo composition of the present invention, a better effect can be obtained. Examples of the cationic polymer include cationized cellulose derivatives, cationized starches, diallyl quaternary ammonium salt/acrylamide copolymer, quaternized polyvinyl pyrrolidone derivatives, polyglycols, polyamine condensates, and poly(dimethylmethylenepiperidinium chloride). They may preferably be incorporated in an amount of from 0.05 to 2% by weight, preferably from 0.1 to 1 by weight, in the shampoo composition of the present invention.
As cationized cellulose derivatives, those represented by general formula (13) are preferable:
wherein A represents a residue of an anhydrous glucose unit; fl is an integer of from 50 to 20,000; and each Rl2 represents a group represented by the following general formula (14)::
wherein R13 and RX4 each represent an alkylene group containing 2 or 3 carbon atoms; gl is an integer of from 0 to 10; hl is an integer of from 0 to 3;
il is an integer of from 0 to 10; Rl5 represents an alkylene or hydroxyalkylene group
each containing from 1 to 3 carbon atoms; Rl6, R17 and Rl8 may be the same or different and each
represents an alkyl, aryl or aralkyl group containing
from not more than 10 carbon atoms, or R15, R17 and R18
may form a heterocyclic group together with the
adjacent nitrogen atom; and Xl represents an anion (for example, an ion of
chlorine, bromine, iodine, sulfuric acid, sulfonic
acid, methylsulfuric acid, phosphoric acid or nitric
acid).
The degree of substitution of the cation in the cationized cellulose is from 0.01 to 1. Namely, the average of hl per anhydrous glucose unit is from 0.01 to 1, preferably from 0.02 to 0.5. The average of gl + il is from 1 to 3. A degree of substitution of the cation smaller than 0.01 is insufficient. Although the degree of substitution of the cation may exceed 1, it is preferably not larger than 1, in view of the reaction yield. The molecular weight of the cationized cellulose derivative used herein ranges from approximately 100,000 to 3,000,000.
As the cationic starch, those represented by the following general formula (15) are preferable:
wherein B represents a starch residue; Rl9 represents an alkylene or a hydroxyalkylene
group;
R20, R21 and R22 may be either the same or different
and each represents an alkyl, aryl or aralkyl group
containing not more than 10 carbon atoms; or R20, R-- and R22 may form a heterocyclic group together with
the adjacent nitrogen atom;
X2 represents an anion (for example, an ion of
chlorine, bromine, iodine, sulfuric acid, sulfon c acid, methylsulfuric acid, phosphoric acid or nitric acid); and
el is a positive integer.
The degree of substitution of the cation in the cationic starch is from 0.01 to 1. Namely, those wherein 0.01 to 1, in particular 0.02 to 0.5, cation group is introduced per anhydrous glucose unit are preferable. A degree of substitution of the cation smaller than 0.01 is insufficient. Although the degree of substitution of the cation may exceed I, it is preferably not larger than 1 by in view of the reaction yield.
As the cationized guar gum derivative, those represented by the following general formula (16) are preferable:
wherein D represents a guar gum residue;
R23 represents an alkylene or a hydroxyalkylene
group;
R24, R25 and R26 may be either the same or different
and each represents an alkyl, aryl or aralkyl group
containing not more than 10 carbon atoms or R24, R25
and R26 may form a heterocyclic group together with
the adjacent nitrogen atom;
X3 represents an anion (for example, an ion of
chlorine, bromine, iodine, sulfuric acid, sulfonic
acid, methylsulfuric acid, phosphoric acid or nitric
acid); and kl is a positive integer.
The degree of substitution of the cation in the cationized guar gum derivative is from 0.01 to 1. Namely, those wherein 0.01 to 1, in particular 0.02 to 0.5, cation group is introduced per sugar unit are preferable. Cationic polymers of this type are described, for example, in JP-B-5835640, JP-B-60-46158 and JP-A-58-53996 (the term "JP-B" as used herein means an "examined Japanese patent publication") and marketed, for example, from Cellanese Stein-Fohl Co.
under the trade name, JAGUAR.
As the diallyl quaternary ammonium salt polymer or diallyl quaternary ammonium salt/acrylamide copolymer, those represented by the following general formula (17) or (18) are preferable:
wherein R27 and R28 may be the same or different and each represents a hydrogen atom, an alkyl group
having 1 to 18 carbon atoms, a phenyl group, an aryl
group, a hydroxyalkyl group, an amidoalkyl group, a
cyanoalkyl group, an alkoxyalkyl group or a
carboalkoxyalkyl group;
R29, R30, R31 and R32 may be either the same or
different and each represents a hydrogen atom, a
lower alkyl group containing from 1 to 3 carbon atoms
or a phenyl group;
X4 represents an anion (for example, an ion of
chlorine, bromine, iodine, sulfuric acid, sulfonic
acid, methylsulfuric acid or nitric acid);
pl is an integer of from 1 to 50;
ql is an integer of from 0 to 50; and
rl is an integer of from 150 to 8,000.
The molecular weight of the diallyl quaternary ammonium salt/acrylamide copolymer may range from approximately 30,000 to 2,000,000, preferably from 100,000 to 1,000,000.
As the quaternarized polyvinylpyrrolidone derivative, those represented by the following general formula (19) are preferable:
wherein R33 represents a hydrogen atom or an alkyl
group having 1 to 3 carbon atoms; R34, R35 and R36 may be either the same or different
and each represents a hydrogen atom, an alkyl group,
a hydroxyalkyl group, an amidoalkyl group, a
cyanoalkyl group, an alkoxyalkyl group or a
carboalkoxyalkyl group, each containing from 1 to 4
carbon atoms; Y1 represents an oxygen atom or an NH group in an
amide bond;; X5 represents an anion (for example, an ion of
chlorine, bromine, iodine, sulfuric acid, sul5onc acid, an alkylsulfuric acid containing from, t 8 carbon atoms, phosphoric acid or nitric acid);
ul is an integer of from 1 to 10; and
sl + tl is an integer of from 20 to 8,000.
The molecular weight of the quaternarized polyvinylpyrrolidone derivative may range from approximately 10,000 to 2,000,000, preferably from 50,000 to 1,500,000.
The shampoo composition of the present invention has an excellent foaming property, gives a good feel at time of washing and rinsing the hair, and has very superior hair style retention property after washing and drying the hair.
The following Examples are given to further illustrate the invention, but the invention should not be limited to these examples.
In the following Examples, each of the compositions were evaluated by the following methods.
(Evaluation Method 1)
One gram of the shampoo composition was applied to a
Japanese hair bundle having a length of 20 cm and a weight of 25 g, foamed and rinsed. The foaming property, feels of the foam and the hair, and a hair style retention property were evaluated by five skilled panelists.
(Evaluation Method 2)
Five grams of the shampoo composition was applied to the hairs of 10 Japanese women. A skilled hairdresser foamed and rinsed the shampoo composition, and evaluated foaming property, a feel of the foam and a hair style retention property.
Evaluation Standards (common to both Evaluation Methods 1 and A2 Foaming Pronertv: A: Well foaming during shampooing
B: Slightly poor foaming during shampooing
C: Poor foaming during shampooing
Feel:
A: Good smoothness and finger passing during shampooing
and rinsing
B: Slightly poor smoothness and finger passing during
shampooing and rinsing
C: Poor smoothness and finger passing during shampooing
and rinsing
Hair Style Retention Property:
A: Less hopping hairs after drying
B: Slightly many hopping hairs after drying
C: Many hopping hairs after drying
EXAMPLE 1
The shampoo compositions shown in Table 1 were prepared, and the foaming property, a feel of foam and the hair and the hair style retention property were examined in accordance with the above evaluation method 1. The results are shown in Table 1.
In Table 1, the abbreviations used are the fllci?g meanings.
SS: Lauryl disodium polyoxyethylenesulfosuccinate (e E.O.)
AS: Laurylsulfuric acid triethanolamine
ES: Sodium polyoxyethylenelauryl ether sulfate (2 E.O.) AA: 2-Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium
betaine
AG: Alkyl polyglycoside (the alkyl group is a mixture
a dodecyl group and a tridecyl group having an
average number of carbon atoms of 12.5 with the
glucoside having an average sugar polymerization
degree of 1.4)
The numerals in Table 1 are % by weight of each component based on the total weight of the composition. TABLE 1
Comparative Products Products of the Invention
1 2 3 4 1 2 3 4 5 6 7
SS 10 - - - 10 - - - 10 -
AS - 20 - - - 20 - - - -
ES - - 10 - - - 10 - - 10
AA - - - 10 - - - 10 - - 10
AG 1 2 2 1 1 2 2 1 1 2 1
Silicone
Derivative: :
Amino- - - - - 1 - - 1 1 0.5 0.5
modified
silicone)
Polyether- - - - - - 2 2 - 1 2 1
modified
silicone)
Purified balance balance balance balance balance balance balance balance balance balance balance water
Foaming B A A A A A A A A A A property
Feel (at the time of washing B B B B A A A A A A A and rinsing)
Style reten- B B B B A A A A A A A tion property 1) Amino-modified silicone: Amodimethicone emulsion (amino-modified emulsion SM8702C, Toray-Dow Corning
Silicone Co., Ltd.) 2) Polyether-modified silicone: Dimethylsiloxane/methyl(polyoxyethylene) siloxane copolymer (Silicone KF
6005, Shinetsu Chemical Co., Ltd.) EXAMPLE 2
The shampoo compositions shown in Table 2 were prepared, and the foaming property, a feel of the foam and the hair and a hair style retention property were examined in accordance with the evaluation method 2.The results are shown in Table 2.
The abbreviations used in Table 2 are the same meanings as in Example 1, and the numerals in Table 2 are % by weight of each component based on the total weight of the composition.
TABLE 2
Compar
ative
Product Products of the Invention
5 8 9 10 11 12 13 14 15 16 17 18
AA 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 10.0 10.0 10.0
SS 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 10.0 10.0 10.0
AG 7.0 1.0 2.0 3.0 1.0 1.0 1.0 1.0 1.0 2.0 1.0 2.0
Silicone
Derivative:
Amino
modified - 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.3 0.3 0.3 0.3
silicone)
Polyether
modified - - - - - - - - 0.5 0.5 0.5 0.5
silicone)
Cationic
Polymer::
Cationized 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
cellulose )
Merquat4) - - - - 0.05 0.2 0.4 0.2 0.2 0.2 0.2 0.2
Lauric acid diethanol 3.0 3.0 3.0 3.0 3.0 3.0 3.0 5.0 5.0 5.0 5.0 3.0 amide TABLE 2 (cont'd)
Compar
ative
Product Products of the Invention
5 8 9 10 11 12 13 14 15 16 17 18
Color and trace trace trace trace trace trace trace trace trace trace trace trace perfume
Purified balance balance balance balance balance balance balance balance balance balance balance balance water
Foaming A A A A A A A A A A A A property
Feel (squeak C A A A A A A A A A A A feel)
Style reten- B A A A A A A A A A A A tion property 3) Cationized cellulose: hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether (Polymer JR-400,
manufactured by UCC Co.) 4) Merquat: poly(dimethylmethylenepiperidinium chloride) (Merquat 100, manufactured by Merck & Co.) While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (9)
1. A shampoo composition comprising the following components (a), (b) and (c):
(a) from 1 to 60% by weight of an anionic surfactant, an amphoteric surfactant, or a mixture of an anionic surfactant and an amphoteric surfactant;
(b) from 0.2 to 5% by weight of an alkyl saccharide surfactant; and
(c) from 0.05 to 3% by weight of a silicone derivative;
wherein a weight ratio of component (a) to component (b) is 2/1 to 150/1.
2. A shampoo composition of claim 1, wherein said component (a) amounts from 2 to 30 % by weight, said component (b) amounts from 0.5 to 3 % by weight, and said component (c) amounts from 0.1 to 2 % by weight.
3. A shampoo composition of claim 1, wherein said weight ratio of component (a) to component (b) is 2/1 to 50/1.
4. A shampoo composition of claim 1, wherein said anionic surfactant is selected from alkylsulfate ester salts, polyoxyethylene alkylsulf ate ester salts, alkylbenzenesulfonic acid salts, a-olefin sulfonic acid salts, a-sulfofatty acid ester salts, alkyl phosphate ester salts and sulfosuccinic acid ester salts, and said amphoteric surfactant is selected from amideamine amphoteric surfactants, imidazoline amphoteric surfactants, betaine amphoteric surfactants, alkylbetaines, aminobetaines and sulfobetaines.
5. A shampoo composition of claim 1, wherein said alkyl saccharide surfactant is represented by formula (-W: R-O-(RȎ)t-(G)p (1) wherein Rl is a straight chain or branched chain alkyl, alkenyl or alkylphenyl group; R2 is an alkylene group having 2 to 4 carbon atoms; G is a residue of reducing sugar having 5 to 6 carbon atoms; t is a number of 0 to 10; and p is a number of 1 to 10.
6. A shampoo composition of claim 1, wherein said silicone derivative is selected from dimethylpolysiloxanes, methylphenyl polysiloxane, amino-modified silicones, fatty acid-modified polysiloxanes, alcohol-modified silicones, aliphatic alcohol-modified silicones, polyether-modified silicones, epoxy-modified silicones, fluorine-modified silicones, cyclic silicones and alkyl-modified silicones.
7. A shampoo composition of claim 1, wherein said composition further comprises from 0.05 to 2 % by weight of a cationic polymer.
8. A shampoo composition of claim 7, wherein said cationic polymer is selected from cationized cellulose derivatives, cationized starches, diallyl quaternary ammonium salt/acrylamide copolymer, quaternized polyvinyl pyrrolidone derivatives, polyglycols, polyamine condensates, and poly(dimethylmethylenepiperidinium chloride).
9. A method for improving a feel to the hair or the skin of a shampoo composition comprising an alkyl saccharide surfactant and an anionic surfactant, an amphoteric surfactant or a mixture of an anionic surfactant and an amphoteric surfactant, which compries the step of mixing a silicone derivative into said shampoo composition, wherein said anionic surfactant, amphoteric surfactant or said mixture of an anionic surfactant and an amphoteric surfactant amounts from 1 to 60% by weight in said shampoo composition, said alkyl saccharide surfactant amounts from 0.2 to 5% by weight in said shampoo composition, said silicone derivative amounts from 0.05 to 3% by weight in said shampoo composition, and a weight ratio of said anionic surfactant, amphoteric surfactant or said mixture of an anionic surfactant and an amphoteric surfactant to said alkyl saccharide surfactant is from 2/1 to 150/1.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3096873A JP2613135B2 (en) | 1991-04-26 | 1991-04-26 | Shampoo composition |
Publications (3)
Publication Number | Publication Date |
---|---|
GB9208945D0 GB9208945D0 (en) | 1992-06-10 |
GB2255101A true GB2255101A (en) | 1992-10-28 |
GB2255101B GB2255101B (en) | 1995-01-11 |
Family
ID=14176548
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9208945A Expired - Fee Related GB2255101B (en) | 1991-04-26 | 1992-04-24 | Shampoo composition |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP2613135B2 (en) |
GB (1) | GB2255101B (en) |
HK (1) | HK58595A (en) |
MY (1) | MY108096A (en) |
SG (1) | SG30568G (en) |
TW (1) | TW228476B (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994016678A1 (en) * | 1993-01-28 | 1994-08-04 | Henkel Kommanditgesellschaft Auf Aktien | Surfactant mixtures |
WO1994028861A1 (en) * | 1993-06-15 | 1994-12-22 | L'oreal | Hair treatment composition containing a polyalkylarylsiloxane or a polyorganosiloxane oil with hydroxyalkyl functionality and a cationic cellulose ether |
WO2002022105A2 (en) * | 2000-09-15 | 2002-03-21 | Stepan Company | Shampoo and body wash composition |
EP1502585A1 (en) * | 2003-07-28 | 2005-02-02 | L'oreal | Cosmetic composition containing a surfactant mixture, a cationic polymers mixture and a silicone |
WO2006007945A1 (en) * | 2004-07-20 | 2006-01-26 | Unilever Plc | Mild, moisturizing cleansing compositions |
US7514091B2 (en) | 1998-07-23 | 2009-04-07 | L'oreal S.A. | Aminated silicone detergent cosmetic composition and use |
US7811552B2 (en) | 2003-07-28 | 2010-10-12 | L'oreal S.A. | Cosmetic composition comprising a mixture of surfactants, a mixture of cationic polymers and a silicone |
US7850950B2 (en) | 2003-11-21 | 2010-12-14 | L'oreal S.A. | Composition for washing and conditioning keratin fibers, comprising a particular amphiphilic diblock copolymer |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08257391A (en) * | 1995-03-23 | 1996-10-08 | Sanyo Chem Ind Ltd | Cationic surfactant |
ID18376A (en) | 1996-01-29 | 1998-04-02 | Johnson & Johnson Consumer | DETERGENT COMPOSITIONS |
US6090773A (en) | 1996-01-29 | 2000-07-18 | Johnson & Johnson Consumer Products, Inc. | Personal cleansing |
FR2862529B1 (en) * | 2003-11-21 | 2006-04-28 | Oreal | COMPOSITION FOR WASHING AND PACKAGING KERATIN FIBERS COMPRISING A PARTICULAR DIBLOC AMPHIPHILIC COPOLYMER. |
JP4982048B2 (en) * | 2005-02-25 | 2012-07-25 | 花王株式会社 | Hair cleaning composition |
JP6910190B2 (en) * | 2017-04-25 | 2021-07-28 | ライオン株式会社 | Liquid detergent composition |
JP2020007437A (en) * | 2018-07-06 | 2020-01-16 | 木村石鹸工業株式会社 | High draining detergent |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0190010A2 (en) * | 1985-01-25 | 1986-08-06 | The Procter & Gamble Company | Shampoo compositions and method |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4559227A (en) * | 1984-10-31 | 1985-12-17 | Dow Corning Corporation | Conditioning shampoo containing amine functional polydiorganosiloxane |
JPH01168613A (en) * | 1987-12-24 | 1989-07-04 | Shiseido Co Ltd | Detergent composition |
JP2587262B2 (en) * | 1988-01-06 | 1997-03-05 | 株式会社資生堂 | Detergent composition |
JP2511690B2 (en) * | 1988-01-06 | 1996-07-03 | 株式会社資生堂 | Detergent composition |
GB8808157D0 (en) * | 1988-04-07 | 1988-05-11 | Dow Corning Ltd | Clear shampoo composition |
JPH0768115B2 (en) * | 1989-05-17 | 1995-07-26 | 花王株式会社 | Cleaning composition |
JPH03174498A (en) * | 1989-12-01 | 1991-07-29 | Lion Corp | Detergent composition |
JP2822519B2 (en) * | 1989-12-25 | 1998-11-11 | ライオン株式会社 | Hair cosmetics |
JP2819184B2 (en) * | 1990-05-29 | 1998-10-30 | 花王株式会社 | Hypoallergenic detergent composition |
-
1991
- 1991-04-26 JP JP3096873A patent/JP2613135B2/en not_active Expired - Fee Related
-
1992
- 1992-04-24 SG SG1995904439A patent/SG30568G/en unknown
- 1992-04-24 GB GB9208945A patent/GB2255101B/en not_active Expired - Fee Related
- 1992-04-24 MY MYPI92000702A patent/MY108096A/en unknown
- 1992-04-24 TW TW081103238A patent/TW228476B/zh active
-
1995
- 1995-04-20 HK HK58595A patent/HK58595A/en not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0190010A2 (en) * | 1985-01-25 | 1986-08-06 | The Procter & Gamble Company | Shampoo compositions and method |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994016678A1 (en) * | 1993-01-28 | 1994-08-04 | Henkel Kommanditgesellschaft Auf Aktien | Surfactant mixtures |
WO1994028861A1 (en) * | 1993-06-15 | 1994-12-22 | L'oreal | Hair treatment composition containing a polyalkylarylsiloxane or a polyorganosiloxane oil with hydroxyalkyl functionality and a cationic cellulose ether |
FR2706296A1 (en) * | 1993-06-15 | 1994-12-23 | Oreal | A hair gloss cosmetic composition containing a polyalkylarylsiloxane or hydroalkyl functional polyorganosiloxane oil and a cationic cellulose ether. |
US7514091B2 (en) | 1998-07-23 | 2009-04-07 | L'oreal S.A. | Aminated silicone detergent cosmetic composition and use |
WO2002022105A2 (en) * | 2000-09-15 | 2002-03-21 | Stepan Company | Shampoo and body wash composition |
WO2002022105A3 (en) * | 2000-09-15 | 2002-07-11 | Stepan Co | Shampoo and body wash composition |
EP1502585A1 (en) * | 2003-07-28 | 2005-02-02 | L'oreal | Cosmetic composition containing a surfactant mixture, a cationic polymers mixture and a silicone |
FR2858217A1 (en) * | 2003-07-28 | 2005-02-04 | Oreal | COSMETIC COMPOSITION CONTAINING A MIXTURE OF SURFACTANTS A MIXTURE OF CATIONIC POLYMERS AND A SILICONE |
US7811552B2 (en) | 2003-07-28 | 2010-10-12 | L'oreal S.A. | Cosmetic composition comprising a mixture of surfactants, a mixture of cationic polymers and a silicone |
US7850950B2 (en) | 2003-11-21 | 2010-12-14 | L'oreal S.A. | Composition for washing and conditioning keratin fibers, comprising a particular amphiphilic diblock copolymer |
WO2006007945A1 (en) * | 2004-07-20 | 2006-01-26 | Unilever Plc | Mild, moisturizing cleansing compositions |
US7259131B2 (en) | 2004-07-20 | 2007-08-21 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Mild, moisturizing cleansing compositions |
Also Published As
Publication number | Publication date |
---|---|
TW228476B (en) | 1994-08-21 |
SG30568G (en) | 1995-09-18 |
GB2255101B (en) | 1995-01-11 |
JP2613135B2 (en) | 1997-05-21 |
JPH04327520A (en) | 1992-11-17 |
MY108096A (en) | 1996-08-15 |
GB9208945D0 (en) | 1992-06-10 |
HK58595A (en) | 1995-04-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1531783B1 (en) | Detergent compositions | |
US5077041A (en) | Shampoo composition | |
JP3208382B2 (en) | Hair cleanser | |
GB2255101A (en) | Shampoo composition | |
JPH0768115B2 (en) | Cleaning composition | |
EP1531789B1 (en) | Hair detergent compositions | |
PL193034B1 (en) | Detergent-type cosmetic compositions and their application | |
US5211883A (en) | Shampoo composition | |
JP2003064102A (en) | Cationic polymer having conditioning effect | |
EP1013754B1 (en) | Detergent composition | |
US5534248A (en) | Toiletry composition for hair care | |
JP4291717B2 (en) | Cleaning composition | |
JP5052164B2 (en) | Hair cleanser | |
JP2000319139A (en) | Washing agent composition for hair | |
JP3417893B2 (en) | Detergent composition | |
JP3929967B2 (en) | Aqueous hair cleanser | |
JP2020029434A (en) | Hair washing agent composition | |
JPH0436225A (en) | Detergent composition | |
JP3354779B2 (en) | Pearl glossy composition | |
JPH0687721A (en) | Hair cosmetic | |
JP2992366B2 (en) | Detergent composition | |
JP2608499B2 (en) | Shampoo composition | |
EP0777466A1 (en) | Detergent compositions | |
JPH0656636A (en) | Shampoo composition | |
JPH09175952A (en) | Conditioning shampoo composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20090424 |