CN1911205A - Aqueous hair detergent - Google Patents

Aqueous hair detergent Download PDF

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CN1911205A
CN1911205A CN 200610110691 CN200610110691A CN1911205A CN 1911205 A CN1911205 A CN 1911205A CN 200610110691 CN200610110691 CN 200610110691 CN 200610110691 A CN200610110691 A CN 200610110691A CN 1911205 A CN1911205 A CN 1911205A
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CN1911205B (en
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寺田英治
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Kao Corp
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Abstract

The invention provideds a hair cleanser giving good foamability and foam quality of good slipperiness in shampooing and giving smooth touch feeling in rinsing, and also giving the finished hair both gloss and trimness. The water-based hair cleanser comprises (A) 1-30 mass% of an anionic surfactant, (B) 0.01-10 mass% of a block copolymer of amino-modified organopolysiloxane chain and polyoxyalkylene chain, (C) 0.01-5 mass% of a water-soluble cationic polymer 100,000-1,900,000 in molecular weight and 0.6-4 meq/g in cationic charge density and (D) 0.1-10 mass% of a pearlizing agent comprising at least one kind selected from ethylene glycol monoalkyl ester, ethylene glycol dialkyl ester, ethylene glycol monoalkyl ether and ethylene glycol dialkyl ether.

Description

Aqueous hair cleansing agent
Technical field
The present invention relates to a kind of aqueous hair cleansing agent, it has good foaming characteristic and the good alveolar substance of slickness when hair washing, has when cleaning along sliding sense of touch, gives gloss and orderliness, excellent in stability for the hair after washing.
Background technology
For the purpose of giving hair care effect to hair, in hair cleansing, be extensive use of water-soluble cationic polymer, but the hair that sustains damage for chemical treatment owing to hair dye and agent for permanent hair waving etc., its hair care effect is abundant inadequately.As the method that addresses this is that, put down in writing the hair cleansing that contains high-molecular weight amino modified silicone and ammonium modified silicone in the patent documentation 1.But the amino modified silicone of putting down in writing in the patent documentation 1 etc. are the structures that has alkylene amines or alkylidene ammonium salt on the polysiloxanes side chain, and, the hydrophobicity height, its result lacks dissolubility, dispersibility in hair cleansing, so have problems on stability.And make the foaming characteristic of hair cleansing descend the problem of hardening during cleaning, being clamminess in addition.
In addition, in patent documentation 2, proposed to contain the hair cleansing of the copolymer of block chain with amino modified polysiloxane chain and polyoxyalkylene chain.But though the dispersibility of this block copolymer in hair cleansing is improved, stability is abundant inadequately, and still exists the problem of hardening, being clamminess when cleaning.
Patent documentation 1: Japanese kokai publication hei 5-85918 communique
Patent documentation 2: TOHKEMY 2002-326914 communique
Summary of the invention
The object of the present invention is to provide a kind of aqueous hair cleansing agent, it has good foaming characteristic and the good alveolar substance of slickness when hair washing, has during cleaning along sliding sense of touch, gives gloss and orderliness, excellent in stability for the hair after washing.
The present inventor finds, using anion surfactant, containing block copolymer, the water-soluble cationic polymer of amino modified polysiloxane chain and polyoxyalkylene chain and contain under the situation of pearling agent of special component, can be met the hair cleansing of above-mentioned requirements.
That is, aqueous hair cleansing agent provided by the invention contains following composition (A), (B), (C) and (D): (A) anion surfactant 1~30 quality %; (B) contain copolymer 0.01~10 quality % of the block chain of amino modified polysiloxane chain and polyoxyalkylene chain; (C) molecular weight is 100,000~1,900,000, cationic charge density is water-soluble cationic polymer 0.01~5 quality % of 0.6~4meq/g; (D) contain pearling agent 0.1~10 quality % of at least one that is selected from glycol monoalkyl ester, ethylene glycol bisthioglycolate Arrcostab, ethylene glycol monoalkyl ether and ethylene glycol bisthioglycolate alkyl ether.
Hair cleansing of the present invention has good foaming characteristic and the good alveolar substance of slickness when hair washing, have during cleaning along sliding sense of touch, and give gloss and orderliness for the hair after washing.
Description of drawings
Fig. 1 is the figure of expression detergent evaluating apparatus.
Fig. 2 is a sectional view (b figure) of implanting the plectane of the top view (a figure) of plectane of hair and implantation hair.
Symbol description
1 hair; 10 containers; 20 lids; 21 first thrusts; 22 second thrusts; 23 bubbles are induced wall; 24 prevent the bar that hair is involved in; 25 hand-holes; 30 electromotors; 50 quantifiers; 51 water injection holes; 60 change apart from detector.
The specific embodiment
As the anion surfactant of composition of the present invention (A), the material of preferably sulfuric acid salt system, sulfonate system, carboxylate system.Can enumerate for example alkyl sulfate, polyoxyalkylene alkyl sulfate, polyoxyalkylene alkenyl ether sulfate, 2-Sulfosuccinic acid alkyl ester salt, 2-Sulfosuccinic acid alkylidene alkyl phenyl ether sulfate, paraffin sulfonate, higher fatty acid salt etc., alkyl ether carboxylic acid or its salt etc.Wherein, preferred polyoxyalkylene alkyl sulfate, alkyl sulfate, the especially preferably material of representing with following general formula (2) or (3).
R′O(CH 2CH 2O) nSO 3M (2)
R′OSO 3M (3)
[in the formula, R ' expression carbon number is 8~18 alkyl or alkenyl, and M represents alkali metal, alkaline-earth metal, ammonium, and n is expressed as 1~5 number with weight average.]
Wherein, from sense of touch that makes rapid foaming and good bubble and the viewpoint of depositing, to be 12~14 alkyl, n be expressed as 1 number, M with weight average to the R ' expression carbon number in the special preferred formula (2) represents ammonium or sodium, polyoxyethylene alkyl ether sulfate salt.
Composition (A) can be used alone or two or more kinds may be used.And from bubble, the fluidity when using, the viewpoint of detergency, its amount is preferably 1~30 quality % in the cleansing composition of the present invention, more preferably 5~25 quality %, preferred especially 8~20 quality %.
Composition of the present invention (B) is the copolymer that contains the block chain of amino modified polysiloxane chain and polyoxyalkylene chain, preferably uses the copolymer of general formula (1) expression.
Figure A20061011069100061
[in the formula, R 1Expression hydrogen atom or carbon number are 1~6 1 valency alkyl; R 2Expression R 1Or any one of E; E is usefulness-R 3-Z (R here, 3The divalent alkyl of representing direct bonded key or carbon number 1~20; Z represents to contain primary, secondary, group that uncle is amino or contain the group of ammonium) group of expression; Y represents the divalent group; A represents the number more than 2; B represents the number more than 1; N represents 2~10 number; C represents the number more than 4; D represents the number more than 2.And, a plurality of R 1, R 2Can be the same or different with E.]
In general formula (1), R 1Be preferably the alkyl or phenyl of hydrogen atom or carbon number 1~6 independently of each other, more preferably methyl, ethyl, preferable methyl especially.
R 3Be preferably the alkylidene chain of the straight or branched of carbon number 1~6, can enumerate methylene, ethylidene, trimethylene, propylidene, tetramethylene etc., more preferably trimethylene or propylidene.
Z is preferably the group that contains amino or ammonium with general formula (4) or (5) expression.
[R in the formula 4Expression-OCH 2CH 2-,
Figure A20061011069100071
, R 5And R 6The alkyl of the carbon number 1~3 of expression hydrogen atom or 1 valency, R separately 5And R 6Can be identical, also can be different.E and f represent 0~6 integer respectively.T -Expression halide ion or organic anion.
Preferred E base is-(CH in the general formula (1) 2) 3-NH 2,-(CH 2) 3-N (CH 3) 2,-(CH 2) 3-NH-(CH 2) 2-NH 2,-(CH 2) 2-NH-(CH 2) 2-N (CH 3) 2,-(CH 2) 3-N +-(CH 3) 3Cl -, more preferably-(CH 2) 3-NH-(CH 2) 2-NH 2As T -Object lesson, can enumerate halide ions such as chlorine element, I, bromo element, organic anions such as Methylsulfate, sulfovinate, methyl phosphate, ethyl phosphate.
In general formula (1), the preference of the divalent group of representing with Y is alkylidene or fragrant rare base, and preferred especially ethylidene, propylidene, trimethylene, positive butylidene or isobutylene most preferably are positive butylidene or isobutylene.
In the general formula (1), preferred a is 2~1000 number, and b is 1~50 number, and c is 4~200 number, and d is 2~100 number.
In the block copolymer with general formula (1) expression, the ratio of siloxane blocks is preferably 25~97 all quality % of copolymer, more preferably 35~90 quality %, preferred especially 50~80 quality %.This block copolymer preferably has 1200 mean molecule quantity at least.And the mean molecule quantity in this description all is to use GPC, use chloroform as eluant, use the value according to conventional method measured of polystyrene as standard substance.
Here, siloxane blocks is meant usefulness-[Si (R 1) 2-O]-expression have 2 R 1The siloxanes of group, the ratio of siloxane blocks are meant the ratio of the molecular weight of the molecular weight of the siloxane blocks of representing with quality % and block copolymer (1).If in above-mentioned scope, dissolving or the favorable dispersibility of block copolymer (1) in hair cleansing, and also high to the residual of hair, thus preferred.
Preferred example is for having the amino modified polysiloxane-polyalkylene block copolymers with the polymerized unit of general formula (6) expression.
Figure A20061011069100081
[in the formula, a, b and d represent the meaning same as described above.G represents the number more than 4.H represents 0~30 number.] in general formula (6), preferred a represents 2~1000 number, b represents 1~50 number, and g represents 4~200 number, and d represents 2~100 number.And ,-O (C 2H 4O) g(C 3H 6O) h-can be any one of block copolymer and random copolymer.Can enumerate FZ-3789, the silicone SS-3588 that eastern beautiful DOW CORNING silicone company (strain) produces as its example.
The kinetic viscosity of (B) composition that uses among the present invention preferably has 10mm 2The viscosity that/s is above, more preferably 100mm 2More than/the s, be preferably 1000mm especially 2More than/the s, most preferably be 5000mm 2More than/the s.And be preferably 1,000,000 mm 2Below/the s, 100,000 mm more preferably 2Below/the s.In this scope, (B) dissolving or the favorable dispersibility of composition in hair cleansing, and also high to the residual of hair, preferred.
And this viscosity is to use Brookfield viscometer, under 25 ℃ temperature, measures under 6rpm/ minute condition with rotor No.2.
The amine equivalent of (B) composition that uses among the present invention is preferably more than the 300g/mol, more preferably 600g/mol.And be preferably 10, below the 000g/mol, more preferably 5, preferred especially 2 below the 000g/mol, below the 500g/mol.In this scope, (B) dissolving or the favorable dispersibility of composition in hair cleansing, and the friction sense of hair when reduce cleaning improve flexibility, and be therefore preferred.
And amine equivalent (g/mol) can be tried to achieve by the alcoholic solution with the salt acidometric titration block copolymer of concentration known.
These (B) compositions can use a kind of independent use, or make up more than 2 kinds and use.The viewpoint of the friction sense of hair when cleaning from reducing, the amount of (B) composition in the hair cleansing of the present invention is the scope of 0.01~10 quality %, is preferably 0.02~5 quality %, preferred especially 0.03~2 quality %.
And (B) composition that the present invention uses can be made with the method that for example Japanese kokai publication hei 9-183854 communique is put down in writing.
The cationic polymer of composition of the present invention (C) is molecular weight 100,000~1,900,000, cationic charge density 0.6~4meq/g, is water-soluble polymer.Slickness during particularly from foaming, the viewpoint of the smoothness when cleaning, preferred molecular weight is 200,000~1,800,000, preferred especially 300,000~1,700,000; And the preferred 0.6~3.8meq/g of cationic charge density, preferred especially 0.7~3.5meq/g.About the charge density of water-soluble cationic fluidized polymer, can measure as the colloidal titration method of volumetric soiutions by for example using polyvinyl sulfuric acid potassium.
Concrete example as water-soluble cationic polymer, can enumerate: the Poise C-80M derivant, cationic starch, cationization guar gum derivant, diallyl quaternary amine/acrylamide copolymer, vinyl imidazole terchoride/vinylpyrrolidone copolymer (vinylimidazolium trichloride/vinylpyrrolidone copolymers), hydroxyethyl-cellulose/dimethyl diallyl ammonium chloride copolymer, vinyl pyrrolidone/quaternized dimethylamino ethyl methacrylic acid salt copolymer (vinylpyrrolidone/quaternizeddimethylaminoethyl methacrylate copolymers), polyvinyl pyrrolidone/alkylamino radical acrylate copolymer (polyvinylpyrrolidone/alkylamino acrylate copolymers), polyvinyl pyrrolidone/alkylamino radical acrylate/caprolactam copolymer, the rare amido propyl chlorination of vinyl pyrrolidone/methyl-prop trimethyl ammonium copolymer (vinylpyrrolidone/methacrylamidopropyl trimethylammonium chloridecopolymers), alkyl acrylamide/acrylate/alkyl amino alkyl acrylamide/polyethylene glycol methacrylate-styrene polymer copolymer, (U.S. Sandoz company produces adipic acid/dimethylamino hydroxypropyl ethylidene triamine copolymer, " Cartaretin "), Japanese kokai publication sho 53-139734 communique, the cation property copolymer of being put down in writing in the Japanese kokai publication sho 60-36407 communique etc., special preferred cationic cellulose derivative, cationization guar gum derivant, diallyl quaternary amine/acrylamide copolymer.
In addition, for example can use " Merquat 550 " (Ondeo Nalco Co., copolymer of acrylamide and diallyl diformazan ammonium salt; CTFA is called " Polyquatemium-7 "), " LuviquatFC370 " (BASF AG, copolymer of l-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazole salt; CTFA is called " polyquaternium-16 "), " Gafquat 755N " (ISP company, copolymer of l-vinyl-2-pyrrolidone and dimethylamino ethyl methacrylate; CTFA is called " polyquaternium-11 "), Ucare polymer JR and with LR series (Amerchol company, the salt of the reactant of trimethyl ammonium substituted epoxide and hydroxyethyl-cellulose; CTFA is called " polyquaternium-10 "), " POIZ C-60H ", " POIZ C-80M ", " POIZ C-150L " (KAO. Corp. SA, salt of the reactant of trimethyl ammonium substituted epoxide and hydroxyethyl-cellulose; CTFA is called " polyquaternium-10 "), " Jaguar series " commercially available products such as (Rhodia, Guar beans hydroxypropyl tri-chlorination ammoniums (guar hydroxypropyl trimoniumchloride)).
Composition (C) can use separately a kind or and with more than 2 kinds, and its amount is 0.01~5 quality % in cleansing composition of the present invention, but the viewpoint of the smoothness when beginning to cleaning during from hair washing is preferably 0.05~2 quality %, preferred especially 0.1~1 quality %.
Composition of the present invention (D) is for containing the pearling agent of at least one that is selected from glycol monoalkyl ester, ethylene glycol bisthioglycolate Arrcostab, ethylene glycol monoalkyl ether and ethylene glycol bisthioglycolate alkyl ether.As the glycol monoalkyl ester, can enumerate ethylene glycol (one) stearyl, ethylene glycol (one) docosyl ester.In addition, as the ethylene glycol bisthioglycolate Arrcostab, can enumerate ethylene glycol (two) stearyl, ethylene glycol (two) docosyl ester.As ethylene glycol monoalkyl ether, can enumerate ethylene glycol (one) octadecyl ether etc.; As the ethylene glycol bisthioglycolate alkyl ether, can enumerate ethylene glycol (two) octadecyl ether etc.Two or more kinds may be used for these materials, in addition from the stability that improves abluent and improve when bubbling, the viewpoint of the slickness in when cleaning, its amount is 0.1~10 quality % in aqueous hair cleansing agent of the present invention, more preferably 0.5~5 quality %, preferred especially 1~4 quality %.
In order further to improve washing (-)off properties, can make and contain non-ionic surface active agent or amphoteric surfactant in the aqueous hair cleansing agent of the present invention.
As non-ionic surface active agent, can enumerate polyoxyalkylene sorbitan alcohol acid anhydride fatty acid ester, polyoxyalkylene Sorbitol fatty acid ester, polyoxyalkylene glycerol fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl class, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene (sclerosis) Semen Ricini oils, sucrose-fatty esters, polyglycerol alkyl ether, polyglycerol fatty acid ester, Marlamid class, alkyl polyglucoside class, monoalkyl glyceryl ethers, mono-alkenyl glyceryl ethers.Wherein, preferred alkyl glucosides class, polyoxyalkylene (C 8~C 20) fatty acid ester, the rare sorbitan fatty acid ester class of polyoxy second, polyoxyethylene hardened castor oil class, Marlamid class, monoalkyl glyceryl ethers, mono-alkenyl glyceryl ethers.
As the Marlamid class, can be in strand alkanolamide, two alkanolamides any one, preferably have carbon number 8~18, the particularly material of the acyl group of carbon number 10~16.The material that especially preferably has the hydroxy alkyl of carbon number 2~3, for example oleic acid diethyl amide, palm-kernel oil fatty diglycollic amide, cocoanut fatty acid diethanolamide, lauric acid diethyl amide, polyethylene glycol oxide coconut oil fatty acid monoethanolamide, coconut oil fatty acid monoethanolamide, lauric isopropropanolamide, lauric monoethanolamide etc.
As alkyl or the alkenyl in monoalkyl glyceryl ethers or the mono-alkenyl glyceryl ethers, be preferably carbon number 4~10, particularly 8~10 straight or branched alkyl.Particularly, can enumerate normal-butyl, isobutyl group, n-pentyl, 2-methyl butyl, isopentyl, n-hexyl, isohesyl, n-heptyl, n-octyl, 2-ethylhexyl, positive decyl, isodecyl etc., preferred especially 2-ethylhexyl, isodecyl.
As amphoteric surfactant, can enumerate the betaines surfactant.Wherein, betanins such as preferred alkyl dimethylamino acetic acid betanin, fatty amide propyl betanin, alkyl hydroxy sulfobetaines are surfactant, special preferred fat amido propyl betaine.The fatty amide propyl betanin be preferably have carbon number 8~18, the acyl group of carbon number 10~16 particularly, preferred especially dodecanamide propyl betanin, palm-kernel oil fatty amide propyl betanin, cocinic acid fat amido propyl betaine etc.
These nonionics or amphoteric surfactant, can in aqueous hair cleansing agent, use a kind or and with more than 2 kinds.But with aqueous hair cleansing agent of the present invention during as the form of waterborne liquid detergent, use under the situation of fatty amide propyl betanin, Marlamid or monoalkyl glyceryl ether with composition (A), not only foamability becomes better, and it is the liquid state that can obtain suiting, thereby preferred especially.
The nonionic in the hair cleansing of the present invention or the amount of amphoteric surfactant are considered from the viewpoint that can obtain good foam enhancing effect, are preferably 0.1~15 quality %, more preferably 0.5~8 quality %, be preferably 1~6 quality % especially.
In order to improve the dried effect of finishing, can in aqueous hair cleansing agent of the present invention, cooperate the represented silicone of general formula (7).
R(CH 3) 2SiO-[(CH 3) 2SiO] m-Si(CH 3) 2R (7)
[in the formula, R represents methyl or hydroxyl, and m represents 1~20,000 number.]
The mean diameter of the dispersed particle of silicone is preferably less than 100 μ m, more preferably below the 50 μ m, below the preferred especially 4 μ m, further below the preferred 2 μ m.In addition, consider usability and hair care (conditioning) effect, mean diameter is preferably more than the 0.1 μ m.
As this silicone oil, can for example use the m that contains in (7) formula is 300~6,500 dimethyl polysiloxane oil, 60 quality %, mean diameter are " the silicone CF2450 " of the eastern beautiful DOW CORNING silicone company of 0.8 μ m, or to contain m be that 300~6,500 dimethyl polysiloxane oil, 50 quality %, mean diameter are the commercially available products such as " silicone CF2460 " of the eastern beautiful DOW CORNING silicone company of 50 μ m.
Bubble sense of touch, dried sense of touch and glossy viewpoint when having one's hair wash from improving, preferably in aqueous hair cleansing agent of the present invention, contain this silicone oil 0.01~10 quality %, more preferably 0.05~6 quality %, preferred especially 0.3~3 quality %, especially preferred 0.5~2 quality %.
In order to improve the dried effect of finishing, can in aqueous hair cleansing agent of the present invention, cooperate cationic surfactant and composition (B) modified silicone in addition etc. again.
As cationic surfactant, preferred for example following (i)~(material vi) that uses.
(i) alkyl trimethyl ammonium salt
For example can enumerate the material of representing with following general formula.
R 11-N +(Me) 3X -
[in the formula, R 11The alkyl of expression carbon number 12~22, Me represents methyl, X -Expression halogen (chlorine or bromine) ion.]
(ii) alkoxyl leptodactyline
For example can enumerate the material of representing with following general formula.
R 12-O-R 13-N +(Me) 3X -
[in the formula, R 12The alkyl of expression carbon number 12~22, R 13Expression ethylidene or propylidene, Me represents methyl, X -Same as described above.]
(iii) dialkyl dimethyl ammonium salt
For example can enumerate the material of representing with following general formula.
R 14 2-N +(Me) 2X -
[in the formula, R 14The alkyl or the benzyl of expression carbon number 12~22, Me represents methyl, X -Same as described above.]
(iv) alkyl dimethylamine and salt thereof
For example can enumerate the material of representing with following general formula.
R 15-N(Me) 2
[in the formula, R 15The alkyl of expression carbon number 12~22, Me represents methyl.]
(v) alkoxyl dimethylamine and salt thereof
For example can enumerate the material of representing with following general formula.
R 16-O-R 17-N(Me) 2
[in the formula, R 16The alkyl of expression carbon number 12~22, R 17Expression ethylidene or propylidene, Me represents methyl.]
(vi) alkylamide dimethylamine and salt thereof
For example can enumerate the material of representing with following general formula.
R 18-C(=O)NH-R 19-N(Me) 2
[in the formula, R 18The alkyl of expression carbon number 11~21, R 19Expression ethylidene or propylidene, Me represents methyl.]
As above-mentioned (i)~(vi) Yi Wai cationic surfactant, can enumerate ethyl sulfuric acid Pilus Caprae seu Ovis fatty acid aminopropyl ethyl Dimethyl Ammonium (sulfovinate, the silane alcohol base of the amino propyl-dimethyl ethyl ammonium of alkanol are derived from lanoline), ethyl sulfuric acid Pilus Caprae seu Ovis fatty acid amino-ethyl three second ammoniums, ethyl sulfuric acid lanolin fatty acid aminopropyl three second ammoniums, methylsulfuric acid Pilus Caprae seu Ovis fatty acid amino-ethyl trimethylammonium, methylsulfuric acid Pilus Caprae seu Ovis fatty acid aminopropyl ethyl dimethylammonium, the different alkanoic acid (C of ethyl sulfuric acid 14~C 20) aminopropyl ethyl dimethylammonium, the different alkanoic acid (C of ethyl sulfuric acid 18~C 22) aminopropyl ethyl dimethylammonium, ethyl sulfuric acid isostearic acid aminopropyl ethyl dimethylammonium, the different n-nonanoic acid aminopropyl of ethyl sulfuric acid ethyl dimethylammonium, and the alkyltrimethylammonium glucide etc.
Two or more kinds may be used for cationic surfactant, the viewpoint of the smoothness when beginning during from hair washing to cleaning, its amount in aqueous hair cleansing agent of the present invention is preferably 0.01~10 quality %, more preferably 0.05~6 quality %, preferred especially 0.3~3 quality %, especially preferred 0.5~2 quality %.
As composition (B) modified silicone class in addition, for example can enumerate the material of following expression.
(a) amino modified silicone
Though can use various modified silicones, but preferred especially mean molecule quantity about 3,000~100,000 in CTFA dictionary (U.S., Cosmetic Ingredient Dictionary) the 3rd edition with the material of the title record of amino dimethicone (Amodimethicone).As commercially available product, can enumerate " SM 8704C " (eastern beautiful DOW CORNING silicone company), " DC 929 " (Dow Corning Corporation), " KT 1989 " (silicone company of GE Toshiba), " 8500 ConditioningAgent " (eastern beautiful DOW CORNING silicone company) etc.
(b) other silicone
Except that above-mentioned, can enumerate polyether modified silicone, methyl phenyl silicone, fatty acid modified silicone, ethanol modified silicone, alkoxy-modified silicone, epoxide modified silicone, fluorine element modified silicone, ring-type silicone, alkyl-modified silicone etc.
Two or more kinds may be used for these silicones, the viewpoint of the smoothness when beginning during from hair washing to cleaning, its amount in aqueous hair cleansing agent of the present invention is preferably 0.01~10 quality %, more preferably 0.05~6 quality %, preferred especially 0.3~3 quality %, especially preferred 0.5~2 quality %.
In addition, the hair care agent as other can contain oil preparation.As oil preparation, can enumerate Squalene, three decanes, liquid paraffinic hydrocarbon, liquid isomerization alkanes, hydrocarbons such as loop chain alkane, Oleum Ricini, cupu oil, mink oil, American Avocado Tree oil, Fructus Canarii albi wet goods glyceride type, Cera Flava, spermaceti, lanoline, wax classes such as Brazil wax, myristyl alcohol, spermol, oleyl alcohol, hard ester alcohol, different hard ester alcohol, the 2-octyldodecanol, alcohols such as glycerol, isopropyl palmitate, isopropyl myristate, myristic acid octyl group dodecane ester, the own ester of cinnamic acid, cetyl lactate, the single-stearic acid propylene glycol ester, oleic acid oleic alcohol ester, 2 ethyl hexanoic acid hexadecane ester, isononyl isononanoate, esters such as different n-nonanoic acid tridecane ester, capric acid, lauric acid, myristic acid, Palmic acid, hard ester acid behenic acid, oleic acid, coco-nut oil fatty acid, iso stearate, senior fatty acid such as different Palmic acid, other different hard ester group glyceryl ether, polyoxy propylidene butyl ether etc.Wherein, preferred higher alcohols, preferred especially myristyl alcohol, hexadecanol, hard ester alcohol.These oil preparationes can use a kind, and also two or more kinds may be used, and its amount in aqueous hair cleansing agent of the present invention is preferably 0.2~2 quality %, more preferably 0.3~1.8 quality %, preferred especially 0.5~1.5 quality %.
Also can contain viscosity modifier in the aqueous hair cleansing agent of the present invention.As viscosity modifier, can enumerate hydroxyethyl-cellulose, methylcellulose, Polyethylene Glycol, polypropylene glycol, ethylene glycol, propylene glycol, isoamyl glycol, ethanol, benzyl alcohol, Bian ethoxy-ethanol, phenyl phenol, clay mineral, salt (sodium chloride, ammonium chloride, sodium citrate etc.) etc., wherein, preferred benzyl alcohol, ethanol, polypropylene glycol, sodium chloride, sodium citrate.Two or more kinds may be used for viscosity modifier, and from the viewpoint of bubble amount, alveolar substance, its use amount in aqueous hair cleansing agent of the present invention is preferably 0.01~5 quality %, more preferably 0.05~4 quality %, preferred especially 0.1~3 quality %.
Except that mentioned component,, can in aqueous hair cleansing agent of the present invention, suitably cooperate the composition that uses in the common hair cleansing according to purpose.As this composition, for example can enumerate: the antidandruff agent; Vitamin agent; Antibacterial; Anti-inflammatory agent; Antiseptic; Chelating agen; Wetting agents such as Sorbitol, pantothenic acid alcohol; Coloring agent such as dyestuff, pigment; The protein that the polar solvent extract of Eucalyptus, the protein that obtains from shell with nacreous layer or Margarita or its add the water decomposition thing, obtain from silkworm silk or its add the water decomposition thing, contain extract classes such as proteic extract, Korean ginseng extract, Rice plumule extract, Fucus Vesiculosus extract, Aloe extract, shellflower leaf extract, chlorella extract from what fabaceous seed obtained; Pearling agents such as titanium oxide, spice; The color element; UV absorbent; Antioxidant; Other one-tenth of being put down in writing in shampoo composition encyclopedia (ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLEPRESS)) grade.
From the gloss that improves hair and the viewpoint of orderliness, the pH when aqueous hair cleansing agent of the present invention is used for hair (dilute with water 20 times of weight, 25 ℃) is preferably pH2~6, and more preferably 3~5, preferred especially pH3.5~4.5.Adjust agent as pH, preferably use organic acid, particularly 'alpha '-hydroxy acids, particularly preferably apple acid, citric acid, lactic acid, glycolic.Two or more kinds may be used for these organic acid, and, the viewpoint of hair flexibility during from raising alveolar substance and hair washing, its use amount in aqueous hair cleansing agent of the present invention is preferably 0.01~5 quality %, more preferably 0.1~3 quality %, preferred especially 0.3~2 quality %.In addition, adjust agent, can mix with these organic acid and use alkali such as sodium hydroxide, potassium hydroxide, ammonium chloride as other pH.
The state of aqueous hair cleansing agent of the present invention can suitably be chosen as liquid state, colloidal state etc., is preferably as solvent and makes water and/or lower alcohol, particularly makes the liquid state of water.
Embodiment
Evaluation methodology
(1) blistered speed
By device shown in Figure 1 (the disclosed device of Japanese kokai publication hei 10-73584 communique) and following method, with estimating sample 1.5mL, model sebum 0.3mL, measure foam number, the time that reaches 25mL according to the bubble amount is estimated.
In device illustrated in figures 1 and 2, use at diameter and omit the hair 30g of the 90mm that implants on the plectane 11 of 160mm as hair 1.Container 10 uses the container cylindraceous of diameter 160mm, height 220mm, lid 20 uses have the cylindrical protrusion thing of 3 diameter 15mm as first thrust 21, height 12mm thereon and have the lid of the thrust of 9 long 10mm as second thrust 22, wide 2mm, height 12mm.In addition, the rotation number with the container 10 of engine rotation is set at per minute 70 times.
In the foaming characteristic evaluation methodology of using this device to carry out, at first water 30g behind the adding model sebum, adds hair wet to estimate sample, and hair 1 and thrust 21,22 are slided, and foam is collected in the quantifier 50.At this moment, the per 50 seconds once foamy collecting amounts of record in back have just been begun from sliding.Evaluation criterion is as follows.
<evaluation criterion 〉
◎: less than 100 seconds
Above, less than was 200 seconds in zero: 100
△: more than 200, less than 300 seconds
*: more than 300 seconds
Smooth feeling when (2) cleaning
Wash gently with 40 ℃ warm water after people's hair bundle of length 25cm, width 5.5cm, weight 10g, remove redundant moisture, fully bubble about 30 seconds with the hair cleansing of 0.5g.Then, on one side with the frothy hair bundle of 40 ℃ warm water cleaning tape of 2L/min flow velocity, on one side with the sensory evaluation smooth feeling.Evaluation is undertaken by 5 people, has represented the aggregate value of this evaluation.In addition, evaluation criterion is as follows.
4: very along sliding
3: relatively along sliding
2: not too along sliding
1: cunning has some setbacks
(3) dried gloss and orderliness
The hair bundle of similarly handling in the time of will estimating with suitable cunning after 40 ℃ flowing water (2L/min) washing, is fully wiped moisture, natural drying away with towel.After the drying, visual valuation gloss and orderliness.Evaluation is undertaken by 5 people, has represented the aggregate value of this evaluation.
4: good
3: relatively good
2: not so good
1: bad
(4) stability
Hair cleansing 100ml is packed in the bottle of 110ml specification, estimate after preserving 1 month at 50 ℃.
Zero: can't see variation by preservation
△: see minor variations (in allowed band) by preservation
*: see significant change (outside allowed band) by preservation
Embodiment 1~6 and comparative example 1~4
Hair cleansing shown in the modulomenter 1 is used commentary valency method and is estimated.And, pH be after dilute with water 20 times of weight 25 ℃ value.
Table 1
Embodiment Comparative example
1 2 3 4 5 6 1 2 3 4
Composition (A) Laurel ether (1) ammonium sulfate * 1 12 12 12 12 8 15 12 12 12 12
Composition (B) Block copolymer * 2 with amino modified polysiloxane and polyoxyalkylene chain 0.3 0.3 0.1 0.3 0.3 0.3 - 0.3 0.3 0.3
Composition (B ') Amino modified silicone * 3 - - - - - - 0.3 - - -
Composition (C) Cationization hydroxyethyl-cellulose * 4 0.5 - 0.5 0.5 0.4 0.4 0.5 - - 0.5
Diallyl dimethyl ammonium chloride/acrylamide copolymer * 5 - 6 - - 1.2 1.2 - - - -
Composition (C ') Cationization hydroxyethyl-cellulose * 6 - - - - - - - 0.5 - -
Dimethyl diallyl ammonium chloride copolymer * 7 - - - - - - - - 2 -
Composition (D) Glycol distearate 2 2 2 2 2 2 2 2 2
Other compositions The isodecyl glycerin ether 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
The lauryl amido propyl betaine 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Myristyl alcohol 1 1 1 1 1 1 1 1 1 1
The coco group single ethanol amide 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Dimethicone 1*8 1 1 1 - 1 1 1 1 1 1
Dimethicone 2*9 - - - 1 - - - - - -
Benzyl alcohol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Sodium chloride 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Malic acid 0.7 0.7 0.7 0.2 1.0 1.0 0.7 0.7 0.7 0.7
Purified Water Surplus Surplus Surplus Surplus Surplus Surplus Surplus Surplus Surplus Surplus
Add up to 100 100 100 100 100 100 100 100 100 100
Estimate pH 3.9 3.9 3.9 5.5 3.5 3.5 3.9 3.9 3.9 3.9
Blistered speed
Smooth feeling during cleaning 19 17 18 16 20 18 8 8 6 7
Dried gloss and orderliness 18 17 17 15 19 19 14 15 14 13
Stability × ×
*1: Laurel ether (1) ammonium sulfate; The oxirane weight average adds molal quantity 1;
*2: the block copolymer of amino modified polysiloxane and polyoxyalkylene chain; " silicone SS-3588 ", eastern beautiful DOW CORNING silicone company (strain) (kinetic viscosity 65,000mm 2/ s, amine equivalent 1250g/mol);
*3: amino modified silicone; " silicone KT 1989 ", silicone company of GE Toshiba
*4: the cationization hydroxyethyl-cellulose; " POIZ M-80 ", KAO. Corp. SA, molecular weight 800,000, cationic charge density 1.0meq/g;
*5: diallyldimethylammonium chloride/acrylamide copolymer, " Merquat 550 ", and Ondeo Nalco Co., molecular weight 1,500,000, cationic charge density 3.1meq/g, polymer is part 8.5% effectively;
*6: the cationization hydroxyethyl-cellulose; " カ チ Na one Le HC-200 ", chemical industry society of eastern nation, molecular weight 2,000,000, cationic charge density 0.8meq/g;
*7: dimethyl diallyl ammonium chloride copolymer; " Merquat 100 ", Ondeo Nalco Co., molecular weight 50,000, cationic charge density 6.2meq/g, polymer is part 40.0% effectively;
*8: dimethicone 1, the mixture of viscosity 10,000 cs/10cs=95/5, mean diameter 0.5 μ m;
*9: dimethicone 2, silicone CF2460, eastern beautiful DOW CORNING silicone company, mean diameter 50 μ m.
Embodiment 7
Conditioning shampoo (quality %)
Laurel ether (1) ammonium sulfate (oxirane on average adds molal quantity 1) 12.0
The copolymer 0.1 of amino modified polysiloxane-polyoxyalkylene
(SS-3587, eastern beautiful DOW CORNING silicone company)
Cationization hydroxyethyl-cellulose (Polymer JR-400, Amerchol company) 0.3
Cationization guar gum (Jaguar C-13S, Rhodia) 0.3
Dimethyl two allyl ammonium/acrylamide copolymers 1.2
(Merquat 550, Ondeo Nalco Co.)
Glycol distearate 2.0
2-ethylhexyl glycerin ether 0.5
Dodecanamide propyl betanin 1.0
Myristyl alcohol 0.3
Hexadecanol 0.3
Coco group single ethanol amide 0.8
Polyoxygenated ethylidene (16) lauryl ether 0.7
Methyl polysiloxane latex 1.0
(silicone viscosity 10,000cs, particle diameter 0.2~0.8 μ m)
Amino modified silicone 0.3
(8500 Conditioning Agent, eastern beautiful DOW CORNING silicone company)
Polypropylene glycol (Mw=400) 0.5
Benzyl alcohol 0.3
Ethanol 3.0
Pantothenic acid alcohol 0.05
Silkworm silk extract 0.05
Sodium chloride 1.0
Spice is an amount of
Malic acid 0.5
Lactic acid reaches the amount of pH3.9
The ion exchange water surplus
Embodiment 8
Conditioning shampoo (quality %)
Laurel ether (2) sodium sulfate (oxirane on average adds molal quantity 2) 13.0
The copolymer 0.8 of amino modified polysiloxane-polyoxyalkylene
(FZ-3789, eastern beautiful DOW CORNING silicone company)
Cationization hydroxyethyl-cellulose (POIZ C-80M, KAO. Corp. SA) 0.5
Diallyl quaternary ammonium salt/acrylamide copolymer 2.5
(Merquat 550, Ondeo Nalco Co.)
Glycol distearate 3.0
Isodecyl glycerin ether 0.7
Dodecanamide propyl betanin 2.0
Coco group single ethanol amide 0.5
Myristyl alcohol 1.5
Polyoxygenated ethylidene (16) lauryl ether 1.0
Amino modified silicone (SM 8704C, eastern beautiful DOW CORNING silicone company) 1.2
High polymerization methyl polysiloxane latex 1.0
(silicone CF2450, particle diameter 0.2~0.8 μ m, eastern beautiful DOW CORNING silicone company)
Benzyl alcohol 1.0
Polypropylene glycol (Mw=400) 0.2
Sodium chloride 1.0
Add water decomposition conchiolin liquid (dry parts 3 quality %) 0.05
Korean ginseng extract (dry parts 3 quality %) 0.05
Soybean extract (dry parts 0.4 quality %) 0.05
Eucalyptus extracts (dry parts 0.2 quality %) 0.05
Rice germ oil 0.05
Glycolic 1.0
Spice is an amount of
Sodium hydroxide reaches the amount of pH3.9
The ion exchange water surplus
Embodiment 9
Conditioning shampoo (quality %)
Laurel ether (1) sodium sulfate (oxirane on average adds molal quantity 1) 16.0
The copolymer 1 .0 of amino modified polysiloxane-polyoxyalkylene
(silicone SS-3588, eastern beautiful DOW CORNING silicone company)
Cationization hydroxyethyl-cellulose (Polymer JR-30M, Amerchol society) 0.5
Ethylene glycol bisthioglycolate stearyl ether 3.0
Isodecyl glycerin ether 0.3
Coco group single ethanol amide 0.5
Stearyl alcohol 1.0
Glycerol 1.0
High polymerization methyl polysiloxane latex 0.5
(silicone CF2460, particle diameter 20~80 μ m, eastern beautiful DOW CORNING silicone company)
Sodium chloride 0.2
Bian ethoxy-ethanol 0.5
Malic acid 0.7
Spice is an amount of
Lactic acid 0.1
Citric acid reaches the amount of pH5.5
The ion exchange water surplus
Embodiment 10
Conditioning shampoo (quality %)
Laurel ether (2.5) sodium sulfate (oxirane on average adds molal quantity 2.5) 15.0
The copolymer 0.4 of amino modified polysiloxane-polyoxyalkylene
(silicone SS-3588, eastern beautiful DOW CORNING silicone company)
Cationization guar gum (Jaguar C-14S, Rhodia) 0.5
Glycol distearate 2.0
Dodecanamide propyl betanin 3.0
Coco group single ethanol amide 0.8
Polyoxygenated ethylidene (16) lauryl ether 2.0
Stearic oxygen propyl group dimethylamine malate 0.5
Methyl polysiloxane latex (silicone viscosity 5,000cs, particle diameter 0.2~0.8 μ m) 1.0
Polypropylene glycol (Mw=400) 0.5
Sodium chloride 1.0
Malic acid 0.8
Citric acid 0.75
Sodium hydroxide reaches the amount of pH3.5
The ion exchange water surplus
Embodiment 11
Modulation shampoo (quality %)
Laurel ether (1) ammonium sulfate (oxirane on average adds molal quantity 1) 14.0
The copolymer 0.5 of amino modified polysiloxane-polyoxyalkylene
(silicone SS-3588, eastern beautiful DOW CORNING silicone company)
Cationization hydroxyethyl-cellulose (Polymer JR-400, Amerchol society) 0.4
Glycol distearate 2.0
Isodecyl glyceryl ether 1.5
Coconut monoethanolamide CAB 1.0
Lauryl hydroxyl sulfo betaine 1.0
Lauric acid 0.5
Oleic acid 0.7
Coco group benzalkonium chloride 0.5
Ethanol 0.5
Fucus Vesiculosus extract 0.05
Malic acid 0.7
Spice is an amount of
Sodium hydroxide reaches the amount of pH5.5
The ion exchange water surplus
When the hair cleansing of embodiment 7~11 has foaming characteristic rapidly and good foaming and the smoothness in when cleaning, and the gloss and the logic of the hair after washing are good, excellent in stability.
Aqueous hair cleansing agent of the present invention has good foaming characteristic and the good alveolar substance of slickness when hair washing, have during cleaning along sliding sense of touch, and give gloss and orderliness for the hair after washing.

Claims (3)

1. an aqueous hair cleansing agent is characterized in that, contains following composition (A), (B), (C) and (D):
(A) anion surfactant 1~30 quality %;
(B) has copolymer 0.01~10 quality % of the block chain of amino modified polysiloxane chain and polyoxyalkylene chain;
(C) molecular weight is 100,000~1,900,000, cationic charge density is water-soluble cationic polymer 0.01~5 quality % of 0.6~4meq/g;
(D) contain pearling agent 0.1~10 quality % of at least one that is selected from glycol monoalkyl ester, ethylene glycol bisthioglycolate Arrcostab, ethylene glycol monoalkyl ether and ethylene glycol bisthioglycolate alkyl ether.
2. aqueous hair cleansing agent as claimed in claim 1 is characterized in that:
Composition (B) is the copolymer with general formula (1) expression,
Figure A2006101106910002C1
In the formula, R 1Expression hydrogen atom or carbon number are 1~6 1 valency alkyl; R 2Expression R 1Or any one of E; E is usefulness-R 3The group that-Z represents, here, R 3The divalent alkyl of representing direct bonded key or carbon number 1~20, Z represent to contain primary, secondary, group that uncle is amino or contain the group of ammonium; Y represents the divalent group; A represents the number more than 2; B represents the number more than 1; N represents 2~10 number; C represents the number more than 4; D represents the number more than 2; And a plurality of R 1, R 2And E can be the same or different.
3. aqueous hair cleansing agent as claimed in claim 1 or 2 is characterized in that:
(A) anion surfactant is polyoxyalkylene alkyl sulfate or alkyl sulfate with general formula (2) or (3) expression,
R′O(CH 2CH 2O) nSO 3M (2)
R′OSO 3M (3)
In the formula, R ' expression carbon number is 8~18 alkyl or alkenyl; M represents alkali metal, alkaline-earth metal, ammonium; N represents 1~5 number with weight average.
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