CN101313884B - Hair cosmetic composition - Google Patents
Hair cosmetic composition Download PDFInfo
- Publication number
- CN101313884B CN101313884B CN2008100984147A CN200810098414A CN101313884B CN 101313884 B CN101313884 B CN 101313884B CN 2008100984147 A CN2008100984147 A CN 2008100984147A CN 200810098414 A CN200810098414 A CN 200810098414A CN 101313884 B CN101313884 B CN 101313884B
- Authority
- CN
- China
- Prior art keywords
- expression
- carbon number
- acid
- alkyl
- hair
- 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.)
- Active
Links
Landscapes
- Cosmetics (AREA)
Abstract
Provided is a hair cosmetic composition containing (A) an amidoamine (1) or an etheramine (2), or a salt thereof, (B) a branched fatty acid (3) or a salt thereof, (C) a silicone, and water: in the formula (1), R<1> represents an aliphatic C11-23 hydrocarbon group, R<2> represents H or a C1-4 alkyl group, and m stands for a number from 2 to 4; in the formula (2), R<3> represents a C6-24 alkyl or alkenyl group, and R<4> and R<5> each represents a C1-6 alkyl group or a group -(AO)nH, in which A represents a C2-4 alkylene group and n stands for a number from 1 to 6; and in the formula (3), R<6> represents a methyl or ethyl group, and p stands for a number from 3 to 36.
Description
Technical field
The present invention relates to contain the specific amines or the hair cosmetic composition of its salt.
Background technology
Hair often receives the influence of solar ultraviolet and heat, drying etc., and because the hair washing of every day and with hair brush comb one's hair, the heat of hair-dryer etc., be dry fluffy mostly.Particularly hair washing back is implemented dry with hair-dryer and hair that the cause dry fluffy equivalent damage that tarnishes, becomes, and is found its reason and is to have caused the inner cavityization of hair by the heat of hair-dryer.In addition, in recent years, people freely or change color development (dyeing) or change hair style (hair-waving) etc., being happy to the outward appearance of variation hair becomes popularly, and the frequency that carries out these modifications uprises.Like this, carry out the hair that dyeing is handled and hair-waving is handled, produced the cavityization of inside owing to the chemical factor of employed hair dye and agent for permanent hair waving.And the behavior (hair washing process, with hands combing hair, with hair brush combing hair) of maintaining hair every day is considered to the constantly in addition little crooked behavior of hair, this make growth such as the inner be full of cracks of hair, gap, crack, disconnection, develop.
Therefore, various trials have been carried out in order to repair hair damages.For example; As repairing or suppressing hair damages and give the technology of good sense of touch; Proposed and with the hair cosmetic composition (TOHKEMY 2003-81780 communique, TOHKEMY 2004-67534 communique) of specific amines or its salt, higher alcohol and organic solvent, contained the hair cosmetic composition (japanese kokai publication hei 4-173719 communique with and corresponding patent documentation EP-0483689-A1 and USP5476649) of branched chain fatty acid class etc.
But these hair cosmetic compositions are inadequate for the action effect that waits the hair that is badly damaged to give good sense of touch, repair or suppress fatigue rupture aspects such as (hair jag hair breakage) that dyes repeatedly.In addition, the crude sense in the time of can not reducing hair washing.
Summary of the invention
The present invention provides the invention of the hair cosmetic composition that contains composition (A), (B), (C) and water.
(A) be with general formula (1) expression amino amides, with the ether amine of general formula (2) expression or their salt.
R
1-CONH-(CH
2)
m-N(R
2)
2 (1)
[in the formula, R
1The expression carbon number is 11～23 aliphatic alkyl, R
2Identical or different, expression hydrogen atom or carbon number are 1～4 alkyl, and m representes 2～4 number.]
[in the formula, R
3The expression carbon number is the alkyl or alkenyl of 6～24 straight or branched, R
4And R
5Represent identical or different carbon number be 1～6 alkyl or-(AO)
nH (A representes that carbon number is that 2～4 alkylidene, n represent that number, a n AO of 1～6 can be the same or different, and its arrangement mode is arbitrarily).]
(B) be branched chain fatty acid or its salt of representing with general formula (3),
[in the formula, R
6Expression methyl or ethyl, p representes 3～36 integer.]
(C) polysiloxane-based.
The specific embodiment
The present invention relates to a kind of hair cosmetic composition; It can repaired or suppress because the damage and the fatigue rupture of the hair that chemical treatment, hair-dryer behavior dry, that maintain hair every day causes, and can be from moistening good flexibility of hair and the elastic tactility after drying, given.
Present inventors find: through and with the amines or their salt that are selected from amino amides and ether amine, branched chain fatty acid class and polysiloxane-based, can be met the hair cosmetic composition of above-mentioned requirements.
In the amino amides of the composition (A) that uses in the present invention, as in the general formula (1) with R
1The fatty acid residue that CO representes (acyl group) for example can be enumerated lauroyl, myristoyl, palmityl, stearyl, oleoyl, 22 carbonic acyl radicals etc.In addition, from considering from the moistening angle of after drying, giving good flexibility and improving its lubricity, with R to hair
1The fatty acid residue that CO representes consists of; Carbon number in all fatty acids residue is that the ratio of the fatty acid residue more than 20 accounts for more than the 60 weight %; Preferred carbon number is that the ratio of 20 fatty acid residue is more than the 3 weight %, and carbon number is that 22 fatty acid residue ratio is 50～95 weight %.If consider dried lubricity again; Carbon number be the fatty acid residue more than 20 ratio preferably 75 weight % above, be more preferably more than the 90 weight %; But carbon number be 20 fatty acid residue ratio preferably 4 weight % above, be more preferably more than the 5 weight %, carbon number is ratio preferably 55～95 weight %, more preferably 70～95 weight %, further 80～95 weight % preferably of 22 fatty acid residue.R
2Be methyl, ethyl or propyl group, preferable methyl wherein, m preferably 2 and 3.
The object lesson of amino amides can be enumerated stearoyl amido ethyl dimethyl tertiary amine, stearoyl amido propyl-dimethyl tertiary amine, stearoyl amido ethyl diethyl tertiary amine, stearoyl amido propyl group diethyl tertiary amine, stearoyl amido ethyl dipropyl tertiary amine, stearoyl amido propyl group dipropyl tertiary amine, palmityl amido ethyl dimethyl tertiary amine, palmityl amido propyl-dimethyl tertiary amine, myristoyl amido ethyl dimethyl tertiary amine, myristoyl amido propyl-dimethyl tertiary amine, behenic acid amido-ethyl dimethyl tertiary amine, behenic acid amidopropyl dimethyl tertiary amine, arachic acid amido-ethyl dimethyl tertiary amine, arachic acid amidopropyl dimethyl tertiary amine etc.Wherein, consider preferred stearoyl amido ethyl diethyl tertiary amine, stearoyl amido propyl-dimethyl tertiary amine from aspects such as performance, stability, property up for grabs.
In the ether amine of the composition (A) that uses in the present invention, the R in the general formula (2)
3Be that carbon number is 6～24 straight or branched alkyl or alkenyl; From can be to hair from moistening good flexibility and lubricity, the particularly excellent aspect of dried lubricity of after drying, giving; Preferred carbon number be 12～24, more preferably carbon number is the alkyl or alkenyl of 14～22 straight or branched, more preferably alkyl.
R
4And R
5Represent independently respectively carbon number be 1～6 alkyl or-(AO)
nH (implication of A and n is same as described above), from can be to hair from moistening good flexibility and lubricity, the particularly excellent aspect of dried lubricity of after drying, giving, preferably carbon number be 1～6 alkyl or-(CH
2CH
2O)
nH (n preferably 1～3, be more preferably 1), more preferably R
4And R
5In at least one be that carbon number is 1～6 alkyl, wherein preferably methyl or ethyl, it is identical to be more preferably both sides.
The preferred object lesson of ether amine; Can enumerate N, and N-dimethyl-3-cetyl oxygen propyl group tertiary amine (N, N-dimethyl-3-hexadecyloxypropylamine), N; N-dimethyl-3-octadecyl oxygen propyl group tertiary amine (N, N-dimethyl-3-octadecyloxypropylamine).In addition, the amino amides and the ether amine that use in the present invention, its all or part of preferably neutralized by mineral acid or organic acid.
Can enumerate hydrochloric acid, sulphuric acid, phosphoric acid etc. as mineral acid.Can enumerate monoacid such as acetic acid, propanoic acid as organic acid; Binary acid such as malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, maleic acid, fumaric acid, phthalic acid; Polybasic carboxylic acids such as polyglutamic acid; Hydroxy carboxylic acid such as glycolic, lactic acid, hydroxy acrylic acid, glyceric acid, malic acid, tartaric acid, citric acid; Acidic amino acid such as glutamic acid, aspartic acid etc.Wherein, preferred mineral acid, dicarboxylic acids, hydroxy carboxylic acid, acidic amino acid, the preferred hydrochloric acid of mineral acid.The preferred maleic acid of dicarboxylic acids, succinic acid.The acid of hydroxy carboxylic acid preferred alcohol, lactic acid, malic acid.The preferred glutamic acid of acidic amino acid.
Here, organic acid also can use the branched chain fatty acid of composition (B).In addition, also can be pre-mixed amino amides and/or ether amine and branched chain fatty acid, will be wherein with, use as acid-addition salts.In addition, in hair cosmetic composition of the present invention, composition (A) and composition (B) are estimated to be and form hydrophobic complex.
Smelly from can effectively reducing amine; And the viewpoint of the conditioning effect of the flexibility of raising hair and lubricity etc. is set out; Above-mentioned mineral acid and/or organic acid use level do; With respect to composition (A), promptly with respect to amino amides and/or ether amine, preferably 0.1～10 times of mole is more preferably 0.3～4 times of mole.
The amino amides of composition (A), ether amine or their salt can be also with more than 2 kinds; In addition; From giving the good flexibility and the viewpoint of lubricity to hair in use; Its content does, in amine (being scaled amine under the situation of salt), preferred 0.1～20 weight %, more preferably 0.3～15 weight %, be more preferably 0.5～10 weight %.
The branched chain fatty acid of composition (B), for example according to LIPIDS, vol.23, No.9,878～881 (1988) or the record of WO98/30532, can separate, extract from hair etc., but also can synthesize according to the record of japanese kokai publication hei 4-173719 communique.Branched chain fatty acid is the fatty acid with general formula (3) expression; Preferred the total number of carbon atoms is 7～40, more preferably 8～30, is more preferably 10～22; Particularly, can enumerate 18-methyl arachic acid, 14-methyl pentadecanoic acid, 14-methyl hexadecanoic acid, 15-methyl hexadecanoic acid, 15-methylheptadecanoic acid, 16-methylheptadecanoic acid, 16-methyl octadecanoid acid, 17-methyl octadecanoid acid, 17-methyl nonadecylic acid etc.In addition, as the salt of this branched chain fatty acid, can enumerate alkali metal salts such as sodium salt, lithium salts, potassium salt; Alkali earth metal salt such as calcium salt, magnesium salt; Ammonium salt; Organic amine salts such as triethanolamine salt, diethanolamine salt, monoethanolamine salt; Alkaline amino acid salt such as lysinate, arginine salt.
Can enumerate extract as extract, i.e. lanolin fatty acid and salt thereof from lanoline.Lanolin fatty acid contains being called different fatty acid, stablizing the methyl branch LCFA of different fatty acid about 50 weight %.Particularly, can enumerate CRODACID18-MEA (Croda Japan manufactured), SKLIRO (Croda Japan manufactured), FA-NH (Nippon FineChemical manufactured).
The branched chain fatty acid of composition (B) or its salt also can be also with more than 2 kinds.In addition, also can mix use composite and extract.From recovering or suppress the viewpoint of the damage effect of hair, its content preferably 0.01～10 weight %, more preferably 0.05～5 weight % in the hair cosmetic composition of the present invention.
In addition, in hair cosmetic composition of the present invention the contained water yield preferably 50～95 weight %, be more preferably 60～90 weight %.
Can enumerate following material as the polysiloxane-based of composition (C).
(i) high polymerization dimethyl polysiloxane
For example, can enumerate BY11-026, BY22-19 (manufacturing of Dong Li Dow Corning Corporation), FZ-3125 (Nippon Unicar Company Limited manufacturing) etc.
High polymerization dimethyl polysiloxane can use dissolving or dispersive dimethyl polysiloxane in unthickened fuel (aqueous hydrocarbon ils such as for example following (ii) dimethyl polysiloxane oil, (iii) aqueous polysiloxane oil such as cyclic polysiloxanes, and isoparaffin).
The dimethyl polysiloxane oil of (ii) representing with formula
[in the formula, c representes 0～650 integer.]
Particularly, comprise that SH200C series, viscosity are 1cs, 50cs, 200cs, 1000cs, 5000cs commercially available article such as (manufacturings of Dong Li Dow Corning Corporation).
The cyclic polysiloxanes of (iii) representing with formula
[in the formula, d representes 3～7 integer.]
Particularly, can enumerate ten diformazan basic rings, six siloxanes, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane etc.In addition, commercially available article can be enumerated SH244 and SH245 (manufacturing of Dong Li Dow Corning Corporation).
The amino modified polysiloxane of (iv) representing with formula
[in the formula, R
7Expression and R
8Identical base or methyl or hydroxyl, R
8Expression is with-R
9-Q (R here,
9The expression carbon number is that 3～6 divalent alkyl, Q represent to contain primary, the group of secondary, tertiary amine groups or contain the group of ammonium) reactive functional group of expression, e and f are respectively positive integers, e+f depends on molecular weight.Preferred mean molecule quantity is 3000～100000.]
For example, can enumerate SS-3551, SF8452C, DC929, DC8500 (manufacturing of Dong Li Dow Corning Corporation), KT-1989 (Momentive Performance Materials Inc. manufactured) etc.When amino modified polysiloxane was used as water-based emulsion, the amount of contained amino modified polysiloxane was preferably 20～60 weight %, more preferably 30～50 weight % in this water-based emulsion.Preferred amino modified polysiloxane water-based emulsion can be enumerated SM8704C (manufacturing of Dong Li Dow Corning Corporation).
(v) other is polysiloxane-based
Except that above-mentioned, can enumerate polyether-modified polysiloxanes, methyl phenyl silicone, fatty acid modified polysiloxanes, pure modified polyorganosiloxane, alkoxy-modified polysiloxanes, epoxy-modified polysiloxane, fluorine modified polyorganosiloxane, alkyl-modified polysiloxanes etc.
The content of the polysiloxane compound in the hair cosmetic composition of the present invention is preferably 0.1～15 weight %, 0.5～10 weight % more preferably.
In order to improve, can also contain amphipathic amide lipid in the hair cosmetic composition of the present invention as composition (D) from the outside repair efficiency of hair.As amphipathic amide lipid, can enumerate being selected from the diamide compound of general formula (4) expression with the material of the ceramide type of general formula (5) expression.
(i) diamide compound of representing with general formula (4)
[in the formula, R
10The carbon number that expression has or do not have hydroxyl and/or an alkoxy substituent is the alkyl of 1～12 straight or branched, R
11The expression carbon number is the divalent alkyl of 1～5 straight or branched, R
12The expression carbon number is the divalent alkyl of 1～22 straight or branched.]
In general formula (4), R
10Preferably having or do not have 1～3, to be selected from hydroxyl and carbon number be that the substituent carbon number of 1～6 alkoxyl is the alkyl of 1～12 straight or branched.Wherein, more preferably not having substituent carbon number is 1～12 alkyl, or to have 1～2 hydroxyl, 1 carbon number be 1～6 alkoxyl or respectively have 1 hydroxyl and carbon number is that the carbon number of 1～6 alkoxyl is 2～12 alkyl.Particularly; Can enumerate methyl, ethyl, propyl group, butyl, hexyl, dodecyl, 2-methyl-propyl, 2-ethylhexyl, 2-hydroxyethyl, 9-hydroxyl nonyl, 2; 3-dihydroxypropyl, 2-methoxy ethyl, 2-hydroxyl-3-methoxy-propyl, 9-methoxyl group nonyl etc.; Wherein, preferred 2-hydroxyethyl, methyl, dodecyl, 2-methoxy ethyl.
In general formula (4), R
11Preferred carbon number is 2～5, more preferably carbon number is 2～3 straight or branched alkylidene.Particularly; Can enumerate ethylidene, propylidene, butylidene, pentylidene, 1-methyl ethylidene, 2-methyl ethylidene, 1-methyl propylidene, 2-methyl propylidene, 1; 1-dimethyl ethylidene, 2-ethyl propylidene etc., wherein, preferred ethylidene and propylidene.
In general formula (4), R
12Preferred carbon number is the divalent alkyl of 2～22 straight or branched, more preferably carbon number is the alkylidene of 11～22 straight or branched and the alkenylene with 1～4 two key.Particularly; Can enumerate ethylidene, propylidene, butylidene, hexylidene, inferior heptyl, octylene, inferior decyl, inferior undecyl, inferior dodecyl, inferior tridecyl, inferior myristyl, inferior cetyl, inferior octadecyl, 1-methyl ethylidene, 2-ethyl propylidene, the inferior heptyl of 1-methyl, the inferior heptyl of 2-methyl, 1-butyl hexylidene, the inferior heptyl, 2 of 2-methyl-5-ethyl; 3; The inferior heptyl of 6-trimethyl, the inferior decyl of 6-ethyl, the inferior myristyl of 7-methyl, the inferior cetyl, 7 of 7-ethyl, the inferior octadecyl, 8 of 12-dimethyl, the inferior octadecyl, 7 of 11-dimethyl; The inferior cetyl of 10-dimethyl-7-ethyl, 1-octadecyl ethylidene, ethenylidene, 1-octadecylene base ethylidene, 7; 11-18 alkadienylenes, the inferior cetyl, 7 of 7-vinyl-9-, 12-dimethyl-7,11-18 alkadienylenes, 8; 11-dimethyl-7,11-18 alkadienylenes etc.Wherein, preferred 7, the inferior octadecyl, 7 of 12-dimethyl, 12-dimethyl-7,11-18 alkadienylenes, inferior octadecyl, inferior undecyl, inferior tridecyl.
Preferred diamide compound (4) is as R
10, R
11And R
12The chemical compound of the preferred group of having enumerated above having made up respectively can be enumerated following chemical compound as its concrete example.
The ceramide type of (ii) representing with general formula (5)
[in the formula, R
13It is 4～30 straight chain, side chain or cyclic saturated or unsaturated alkyl that expression has or do not have hydroxyl, oxo base or amino substituent carbon number, and W representes methylene, methine or oxygen atom, and dotted line representes to exist or do not exist π key, X
1Represent hydrogen atom, acetyl group or glyceryl or form oxo base, X together with the adjacent oxygen atom that is connected
2, X
3And X
4Represent independently respectively hydrogen atom, hydroxyl or acetoxyl group (when W is methine, X
2And X
3In one be hydrogen atom and another does not exist; When-O-X
1When being the oxo base, X
4Do not exist), R
14And R
15Represent hydrogen atom, hydroxyl, methylol or acetoxy-methyl, R respectively independently
16It is 5～35 straight chain, side chain or cyclic alkyl that expression has or do not have hydroxyl or amino substituent carbon number; Or be that 8～22 straight chain, side chain or cyclic saturated or unsaturated fatty acid are with ester bond or the bonded base of amido link, R with the carbon number that has or do not have hydroxyl substituent in the ω position of this alkyl
17Expression hydrogen atom or expression have or do not have the saturated or unsaturated alkyl that the substituent the total number of carbon atoms that is selected from hydroxyl, hydroxy alkoxy base, alkoxyl and acetoxyl group is 1～8 straight or branched.]
In general formula (5), R
13The carbon number that preferably has or do not have hydroxyl substituent is 7～22 straight chain, side chain or cyclic saturated or undersaturated alkyl.X
1Preferably hydrogen atom, glyceryl.X
2, X
3And X
4Preferably, wherein 0～1 be hydroxyl, all the other are for hydrogen atom.R
14And R
15Preferably, one is hydrogen atom or methylol, another hydrogen atom.At R
16In the ω position of alkyl with ester bond or the bonded fatty acid of amido link, preferably isostearic acid, 12-hydroxy stearic acid, linoleic acid.R
17Preferred hydrogen atom, or to have or do not have 1～3 substituent the total number of carbon atoms that is selected from hydroxyl, hydroxy alkoxy base and alkoxyl be 1～8 alkyl.
As preferred ceramide type (5); Can enumerate with the natural ceramide of formula (5a) expression or natural type ceramide type and derivant thereof (below be recited as " natural type ceramide type (5a) ") and with the false vitalility of general formula (5b) expression through amide-type (below be recited as " false vitalility is through amide-type (5b) ").
(ii-1) natural type ceramide type (5a)
[in the formula, R
13aThe carbon number that expression has or do not have a hydroxyl substituent is 7～19 straight chain, side chain or cyclic saturated or unsaturated alkyl, W
1Expression methylene or methine, dotted line is represented the existence of π key or is not had X
1aRepresent hydrogen atom or form oxo base, X with adjacent oxygen atom
2a, X
3aAnd X
4aRepresent independently that respectively hydrogen atom, hydroxyl or acetoxyl group (work as W
1When being methine, X
2aAnd X
3aIn one be hydrogen atom and another does not exist ,-O-X
1aX when being the oxo base
4aDo not exist), R
14aExpression methylol or acetoxy-methyl, R
16aThe carbon number that expression has or do not have a hydroxyl substituent is 5～30 straight chain, side chain or cyclic alkyl; Or terminal at the ω of this alkyl, as to have or do not have hydroxyl substituent carbon number is that the saturated or unsaturated fatty acid of 8～22 straight chain, side chain is with the bonded base of ester bond, R
17aExpression hydrogen atom or carbon number are 1～4 alkyl.]
The chemical compound that preferably can be listed below: R
13aBe that carbon number is 7～19 straight chained alkyl, more preferably carbon number is 13～15 straight chained alkyl; W
1Be methine, X
2aAnd X
3aIn one be hydrogen atom; R
16aBe that carbon number is 9～27 the straight chained alkyl that has or do not have hydroxyl substituent.In addition, X
1aBe hydrogen atom or preferably form the oxo base with oxygen atom.X
16aPreferably tricosyl, 1-hydroxyl pentadecyl, 1-hydroxyl tricosyl, pentadecyl, 1-hydroxyl undecyl, linoleic acid is with the bonded nonacosyl of ester bond in the ω position.
Object lesson as the natural type ceramide type; Structure shown in can being listed below; Sphingosine, dihydrosphingosine, phytosphingosine (phytosphingosine) or sphingadienine by amidated ceramide type 1～7 (for example at J.Lipid Res.; Fig. 2 of 24:759 (1983) and at J.Lipid Res., pig of putting down in writing among Fig. 4 of 35:2069 (1994) and people's ceramide type), can also enumerate their N-alkylates (for example N-methyl body).These can be from any one of natural extract and composite, also can use commercially available article.
(ii-2) false vitalility is through amide-type (5b)
[in the formula, R
13bThe carbon number that expression has or do not have a hydroxyl substituent is 10～22 straight chain, side chain or cyclic, saturated or unsaturated alkyl; X
1bExpression hydrogen atom, acetyl group or glyceryl; R
16bBe that to have or do not have hydroxyl or amino substituent carbon number be 5～22 straight chain, side chain or cyclic alkyl, or be that the saturated or unsaturated fatty acid of 8～22 straight chain, side chain is with ester bond or the bonded base of amido link at the ω of this alkyl carbon number terminal, that have or do not have hydroxyl substituent; R
17bSubstituent the total number of carbon atoms that expression hydrogen atom or expression have or do not have hydroxyl, hydroxy alkoxy base, alkoxyl and an acetoxyl group is 1～8 alkyl.]
R
16bPreferred nonyl, tridecyl, pentadecyl, in the ω position linoleic acid with the bonded undecyl of ester bond, in the ω position linoleic acid with the bonded pentadecyl of ester bond, in the ω position 12-hydroxy stearic acid isostearic acid of methyl branch is with the bonded undecyl of amido link with the bonded pentadecyl of ester bond, in the ω position.R
17bHydroxy alkoxy base or the preferred carbon number of alkoxyl be 1～8.
Preferred as the false vitalility: R through amide-type (5b)
13bBe cetyl, X
1bBe hydrogen atom, R
16bBe pentadecyl, R
17bThe false vitalility who is ethoxy is through amide-type; R
13bBe cetyl, X
1bBe hydrogen atom, R
16bBe nonyl, R
17bThe false vitalility who is ethoxy is through amide-type; Perhaps, R
13bBe cetyl, X
1bBe glyceryl, R
16bBe tridecyl, R
17bThe false vitalility who is the 3-methoxy-propyl is through amide-type; More preferably: the R of general formula (5b)
13bBe cetyl, X
1bBe hydrogen atom, R
16bBe pentadecyl, R
17bThe false vitalility who is ethoxy is through amide-type.Can enumerate following false vitalility through amide-type as preferred object lesson.
Amphipathic amide lipid can and with more than 2 kinds, from the effect aspect of recovering or suppressing to damage, its content in hair cosmetic composition of the present invention preferably 0.01～10 weight %, be more preferably 0.05～5 weight %.
In order further to improve the sense of touch of giving, in hair cosmetic composition of the present invention, can add aromatic alcohol, oiliness composition, cationic surfactant etc. to hair.
As aromatic alcohol can enumerate benzyl alcohol, cinnamyl alcohol, phenethanol, to anise alcohol, to methylbenzyl alcohol, phenyl phenol, 2-benzyloxy ethanol etc.
In addition, in addition higher fatty acids, liquid paraffin of the composition (B) that can enumerate capric acid, lauric acid, myristic acid, Palmic acid, stearic acid, behenic acid, oleic acid, coco-nut oil fatty acid etc. as the oiliness composition, the hydrocarbon ils of isoparaffin, vaseline, squalene, three decanes etc. etc. flows.In addition, can enumerate Camellia oil, macadimia nut oil, Semen Maydis oil, olive oil, American Avocado Tree oil, Semen Ricini oil, safflower oil, Jojoba oil, Oleum helianthi, Oleum Brassicae campestris, Oleum sesami, soybean oil, Ramulus et Folium Spiraeae Salicifolia wet goods oils and fats; Myristic acid isopropyl alcohol ester; Palmic acid isopropyl alcohol ester; Myristic acid Semen Myristicae alcohol ester; Octyl palmitate; Geoceric acid stearyl alcohol ester; Stearic acid 2-Methylpentadecane alcohol ester; Different n-nonanoic acid isononyl alcohol ester; The different tridecane alcohol ester of different n-nonanoic acid; Stearic acid sclerosis Semen Ricini grease; Hydroxy stearic acid sclerosis Semen Ricini grease; Three 2 ethyl hexanoic acid glyceride; Four 2 ethyl hexanoic acid pentaerythritol esters; Two capric acid DOPCPs; Two isostearic acids, two glyceride; The ester oil of the ester of the fatty acid mixed of dipentaerythritol and hydroxy stearic acid/stearic acid/rosin acid etc. etc.
Cationic surfactant for example can be enumerated following (i)～(chemical compound vi) etc.
(i) alkyl trimethyl ammonium salt
For example, can enumerate the chemical compound of representing with formula.
R
18-N
+(CH
3)
3X
-
[in the formula, R
18The expression carbon number is 12～22 alkyl, X
-Expression halogen (chlorine or bromine) change thing ion or carbon number are 1～2 alkylsurfuric acid ion.]
(ii) alkoxyl leptodactyline
For example, can enumerate the chemical compound of representing with formula.
R
19-O-R
20-N
+(CH
3)
3X
-
[in the formula, R
19The expression carbon number is 12～22 alkyl, R
20Expression ethylidene or propylidene, X
-Implication same as described above.]
(iii) dialkyl dimethyl ammonium salt
For example, can enumerate the chemical compound of representing with formula.
(R
21)
2-N
+(CH
3)
2X
-
[in the formula, R
21The expression carbon number is 12～22 alkyl or benzyl, X
-Implication same as described above.]
(iv) alkyl dimethyl tertiary amide (and salt)
For example, can enumerate chemical compound and the salt of representing with formula thereof.
R
22-N(CH
3)
2
[in the formula, R
22The expression carbon number is 12～22 alkyl.]
(v) hydroxy ether amine (and salt)
For example, can enumerate chemical compound and the salt of representing with formula thereof.
[in the formula, R
23The expression carbon number is alkyl or alkenyl, the R of 6～24 straight or branched
24And R
25Represent identical or different carbon number be 1～6 alkyl or-(A
1O)
bH (A
1The expression carbon number is that 2～4 alkylidene, b represent 1～6 number, a b A
1O both can be the same or different, its arrangement is arbitrarily).A representes 1～5 number.]
(vi) ether amine (and salt)
For example, can enumerate chemical compound and the salt of representing with formula thereof.
[in the formula, R
26The expression carbon number is 6～24 straight or branched alkyl or alkenyl, R
27The expression carbon number is alkylidene, the R of 2～5 straight or branched
28And R
29Represent respectively hydrogen atom, carbon number be 1～6 alkyl or-(A
2O)
hH (A
2The expression carbon number is that 2～4 alkylidene, h represent 1～6 number, a h A
2O both can be the same or different, its arrangement is arbitrarily).G representes 2～8 number.]
As above-mentioned (i)～(cationic surfactant vi) can be enumerated ethyl sulfuric acid Pilus Caprae seu Ovis acylamino-propyl group ethyl Dimethyl Ammonium, ethyl sulfuric acid Pilus Caprae seu Ovis acylamino-ethyl triethyl ammonium, ethyl sulfuric acid Pilus Caprae seu Ovis acylamino-propyl group triethyl ammonium, methylsulfuric acid Pilus Caprae seu Ovis acylamino-ethyl trimethyl ammonium, methylsulfuric acid Pilus Caprae seu Ovis acylamino-propyl group ethyl Dimethyl Ammonium, the different alkanoic acid acyl of ethyl sulfuric acid (C
14～C
20) aminopropyl ethyl Dimethyl Ammonium, the different alkanoic acid acyl of ethyl sulfuric acid (C
18～C
22) aminopropyl ethyl Dimethyl Ammonium, ethyl sulfuric acid isostearoyl aminopropyl ethyl Dimethyl Ammonium, ethyl sulfuric acid isononane acylamino-propyl group ethyl Dimethyl Ammonium, alkyl trimethyl sucramin etc.
Cationic surfactant can and with more than 2 kinds, in addition, from giving the good flexibility and the aspect of lubricity to hair in use, preferred 0.01～20 weight % of its content, more preferably 0.1～15 weight %, be more preferably 0.5～10 weight %.
In hair cosmetic composition of the present invention, can also be engaged in normally used other composition in the hair cosmetic composition according to application target.For example, can enumerate macromolecular compounds such as Poise C-80M, hydroxylating cellulose, high polymerization PEO; Non-ionic surface active agents such as polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid esters, fatty acid glyceride, polyglyceryl fatty acid ester, polyoxyethylene liquefaction Semen Ricini oil, sucrose fatty acid ester, polyglycerol alkyl ether, fatty acid alkanol amides, alkyl polyglucoside; Dandruff removing agents such as pyridine sulfidion copper zinc, Benasept; Vitamin agent; Antibacterial; Anti-inflammatory agent; Antiseptic; Chelating agen; Wetting agents such as panthenol; Coloring agent such as dyestuff, pigment; The extract class that contains proteic extract, Radix Ginseng extract, Rice plumule extract, Sargassum extract, Camellia extract, Aloe extract, Alpinia nutaus leaf extract, chlorella extract etc. that 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, obtain from seeds of leguminous plant; Pearly-lustre powder body such as mica titanium; Spice; Color is plain; UV absorbent; Antioxidant; The composition of record in other (ENCYCLOPEDIA OF SHAMPOOINGREDIENTS (MICELLE PRESS)).
PH (25 ℃) when hair cosmetic composition of the present invention preferably is 20 times of weight with the water dilution is 1～5.5.If in this scope, just have the function of the injury recovery of hair dyeing of making etc., be to give the hair cosmetic composition of good flexibility and elastic tactility function when moistening after the drying to the hair handled.From the viewpoint of the hair recovery effects damaged, pH value more preferably is adjusted into 2～5, be more preferably and be adjusted into 2.5～4.5.In the adjustment of pH, can and with acidic materials such as mineral acid, organic acid, more can be used as alkaline matter and and use sodium hydroxide.Be included in employed mineral acid and organic acid in the neutralization of amino amides or ether amine of mentioned component (A) in mineral acid and the organic acid.
Hair cosmetic composition of the present invention is through making in the solvent that composition (A), (B), (C) and other any composition is dissolved in water and the ethanol that uses as required, 2-propanol, glycerol, propylene glycol etc.As its goods form, can enumerate hair care agent (hair rinse), hair conditioner (hair conditioner), disposable hair conditioner (out-bath hair treatment) etc.
Embodiment
Below the pH of hair cosmetic composition of expression be when being diluted to 20 times of weight with water, the value in the time of 25 ℃.
Embodiment 1～16 and comparative example 1～6
Be manufactured on shown in table 1 and the table 2 hair conditioner of forming, according to following method and standard evaluation " flexibility ", " flatness ", " moist feeling ", " elasticity ".In addition, fatigue durability test and contact angle determination have been carried out.In addition, comparative example 1 is same compositionss with comparative example 4, but in table 1 (amino amides) and table 2 (ether amine) comparison separately, estimates respectively.
Evaluation methodology
(about 15～20cm) have carried out the Japanese women's of cosmetic treatments such as cold wave, decolouring hair to constraint 20g, clean with shampoo.On this topknot, be coated with each hair conditioner of 2g equably, then washed for 30 seconds with flowing water after, towel off driedly, the reuse hair-dryer carries out drying, and " flexibility ", " flatness ", " moist feeling ", " elasticity " have been carried out the sense evaluation.Estimate by 5 people, represent the aggregate value of its evaluation.
Metewand
" flexibility "
4: very soft
3: soft slightly
2: not too soft
1: not soft
" flatness "
4: very level and smooth
3: level and smooth slightly
2: not too level and smooth
1: unsmooth
" moist feeling "
4: very moistening
3: moistening slightly
2: not too moistening
1: not moistening
" elasticity "
4: very flexible
3: flexible slightly
2: not too flexible
1: do not have elasticity
" fatigue durability test "
According at Y.K.Kamath, S.B.Hornby, H.D.Weigmann and S.Ruetsch, J.Cos.Sci., 50, the method for record among the 198-200 (1999) gives the load of 50g/l root hair repeatedly, count down to the number of occurrence till the fracture.Data to obtain are the basis, calculate fatigue durability parameter (characteristic life-span) according to following method.
For the fatigue rupture phenomenon is carried out statistical disposition, use can be estimated " Weibull distribution " of the irregular characteristic of measured value in broad range.In the formula (a) of Weibull distribution, the formula of the natural logrithm on twice both sides of treating the preponderant disease instead of the secondary disease (b) is obtained parameter θ (characteristic life-span).Be lnx, be ln ln{1/ [1-F (x)] with the X axle with the Y axle }, mark and draw each data, obtain near linear, calculate parameter θ (formula (c)) from intercept=b ln θ, slope=b.
F(x)＝1-exp[-(x/θ)
b] (a)
ln?ln{1/[1-F(x)]}＝b?ln?x-b?lnθ (b)
θ (characteristic life-span)=exp (intercept/slope) (c)
X: the number of times during fracture
F (x): the numbering of fracture/sample number
B: form parameter
θ: the characteristic life-span (sample number purpose 63.2% go to pot till the time number of times)
" measurement of contact angle "
According to crossing portion, JSCCJ, the methods of record are handled back+shampoo to hair cosmetic composition and are handled hair (N=10) the mensuration contact angle after 1 time in 29 (1), 64～68 (1995).
Table 1
*1:18-MEA (Croda Japan manufactured)
*2:SH200C (viscosity 100,000 mm
2/ s, Dong Li Dow Corning Corporation makes)
*3:SM8704C (manufacturing of Dong Li Dow Corning Corporation)
*4: amphipathic amide lipid A
*5: amphipathic amide lipid B
Table 2
*1:18-MEA (Croda Japan manufactured)
*2:SH200C (viscosity 100,000 mm
2/ s, Dong Li Dow Corning Corporation makes)
*3:SM8704C (manufacturing of Dong Li Dow Corning Corporation)
*4: amphipathic amide lipid A
*5: amphipathic amide lipid B
Embodiment 17 hair conditioner (hair conditioner) (pH4.5)
(weight %)
Stearoyl amido propyl-dimethyl tertiary amine 0.5
Stearyl alcohol 3.0
2-BOE 0.3
Stearyl trimethyl ammonium chloride 1.0
Myristic acid 0.2
The different tridecane alcohol ester 0.5 of myristic acid
Aminoethyl aminopropyl siloxanes dimethylsiloxane copolymer emulsion 0.5
Dimethyl polysiloxane 3.0
Propylene glycol 1.0
Malic acid 0.1
18-methyl arachic acid 0.5
Amphipathic amide lipid B 0.1
Spice 0.4
Methyl parahydroxybenzoate 0.3
Sodium hydroxide is an amount of
The ion exchange water surplus
The damage and the fatigue rupture of hair can repaired or suppress to above-mentioned hair conditioner, and can after drying, give good flexibility and elastic sense of touch when moistening to hair.
Embodiment 18 hair conditioners (hair treatment) (pH4.0)
(weight %)
Behenic acid amidopropyl dimethyl tertiary amine 2.0
INCROQUAT TMC-80 ECONOL TM22 0.3
Stearyl alcohol 4.5
Tadenan 1.5
Different n-nonanoic acid isononyl alcohol ester 0.5
Methyl polysiloxane mixed liquor 2.5
Aminoethyl aminopropyl siloxanes dimethylsiloxane copolymer emulsion 0.5
Hydroxyacetic acid 0.5
Malic acid 0.1
Dipropylene glycol 3.0
Benzyl alcohol 0.3
Amphipathic amide lipid B 0.1
Arginine 0.2
16-methyl octadecanoid acid 0.5
Pantoyl benzyl ethyl ether 0.1
Spice 0.4
Methyl parahydroxybenzoate 0.1
Sodium hydroxide is an amount of
The ion exchange water surplus
The damage and the fatigue rupture of hair can repaired or suppress to above-mentioned hair conditioner, and can after drying, give good flexibility and elastic sense of touch when moistening to hair.
Embodiment 19 hair conditioner (hair conditioner) (pH3.3)
(weight %)
N, N-dimethyl-3-octadecyl oxygen propyl group tertiary amine 2.0
Stearyl alcohol 5.0
Dipropylene glycol 1.0
Benzyl alcohol 0.5
Phenyl phenol 0.1
Glycerol 5.0
Polypropylene glycol 2.5
18-methyl arachic acid 0.5
Amphipathic amide lipid B 0.1
Oleum helianthi 0.5
Methyl polysiloxane mixed liquor 2.5
Lactic acid 1.5
Spice 0.4
Sodium hydroxide is an amount of
The ion exchange water surplus
The damage and the fatigue rupture of hair can repaired or suppress to above-mentioned hair conditioner, and can after drying, give good flexibility and elastic sense of touch when moistening to hair.
Embodiment 20 hair conditioner (hair conditioner) (pH3.3)
(weight %)
N, N-dimethyl-3-octadecyl oxygen propyl group tertiary amine 2.0
Stearoyl amido propyl-dimethyl tertiary amine 2.0
Stearyl alcohol 5.0
Dipropylene glycol 1.0
Benzyl alcohol 0.5
Phenyl phenol 0.1
Glycerol 5.0
Polypropylene glycol 2.5
18-methyl arachic acid 0.5
Amphipathic amide lipid B 0.1
Oleum helianthi 0.5
Methyl polysiloxane mixed liquor 2.5
Lactic acid 1.5
Spice 0.4
Sodium hydroxide is an amount of
The ion exchange water surplus
The damage and the fatigue rupture of hair can repaired or suppress to above-mentioned hair conditioner, and can after drying, give good flexibility and elastic sense of touch when moistening to hair.
Embodiment 21 hair conditioner (pH3.3)
(weight %)
Cetyl oxo (2-hydroxypropyl) DMA 0.5
N, N, N-trimethyl ammonium chloride 2.0
Stearyl alcohol 5.0
Dipropylene glycol 1.0
Benzyl alcohol 0.5
Phenyl phenol 0.1
Glycerol 5.0
Polypropylene glycol 2.5
18-methyl arachic acid 0.5
Amphipathic amide lipid B 0.1
Oleum helianthi 0.5
Methyl polysiloxane mixed liquor 2.5
Lactic acid 1.5
Spice 0.4
Sodium hydroxide is an amount of
The ion exchange water surplus
The damage and the fatigue rupture of hair can repaired or suppress to above-mentioned hair conditioner, and can after drying, give good flexibility and elastic sense of touch when moistening to hair.
Embodiment 22 hair conditioners (hair treatment) (pH3.3)
(weight %)
N, N-dimethyl-3-octadecyl oxygen propyl group tertiary amine 2.0
Stearyl alcohol 9.0
Glutamic acid 1.5
BOE 1.0
Dipropylene glycol 2.0
Phenyl phenol 0.1
Amphipathic amide lipid B 0.1
Dipentaerythritol fatty acid ester 0.2
16-methyl octadecanoid acid 0.5
Methyl polysiloxane mixed liquor 2.5
High polymerization methyl polysiloxane decamethyl Pentamethylene. mixture of siloxanes 2.5
Aminoethyl aminopropyl siloxanes dimethylsiloxane copolymer emulsion 0.5
Hydroxyethyl-cellulose 0.3
Paraffin 0.5
Spice 0.3
Sodium hydroxide is an amount of
The ion exchange water surplus
The damage and the fatigue rupture of hair can repaired or suppress to above-mentioned hair conditioner, and can after drying, give good flexibility and elastic sense of touch when moistening to hair.
Claims (7)
1. a hair cosmetic composition is characterized in that,
Contain composition (A), (B), (C) and water,
(A) ether amine or its salt represented with general formula (2),
In the formula, R
3The expression carbon number is the alkyl or alkenyl of 6～24 straight or branched, R
4And R
5Represent identical or different carbon number be 1～6 alkyl or-(AO)
nH, wherein, A representes that carbon number is that 2～4 alkylidene, n represent that number, a n AO of 1～6 can be the same or different, its arrangement is arbitrarily,
(B) branched chain fatty acid or its salt represented with general formula (3),
In the formula, R
6Expression methyl or ethyl, p representes 3～36 integer,
(C) polysiloxane-based.
2. hair cosmetic composition as claimed in claim 1 is characterized in that,
The content of said composition (A) is to calculate 0.1～20 weight % with amine.
3. hair cosmetic composition as claimed in claim 1 is characterized in that,
The content of said composition (B) is 0.01～10 weight %.
4. hair cosmetic composition as claimed in claim 1 is characterized in that,
The content of said composition (C) is 0.1～15 weight %.
5. hair cosmetic composition as claimed in claim 1 is characterized in that,
Also contain amphipathic amide lipid as composition (D).
6. hair cosmetic composition as claimed in claim 5 is characterized in that,
Said composition (D) is the diamide compound with general formula (4) expression,
In the formula, R
10The carbon number that expression has or do not have hydroxyl and/or an alkoxy substituent is the alkyl of 1～12 straight or branched, R
11The expression carbon number is the divalent alkyl of 1～5 straight or branched, R
12The expression carbon number is the divalent alkyl of 1～22 straight or branched.
7. hair cosmetic composition as claimed in claim 5 is characterized in that,
Said composition (D) is the ceramide type with general formula (5) expression,
In the formula, R
13It is 4～30 straight chain, side chain or cyclic saturated or unsaturated alkyl that expression has or do not have hydroxyl, oxo base or amino substituent carbon number, and W representes methylene, methine or oxygen atom, and dotted line representes to exist or do not exist π key, X
1Represent hydrogen atom, acetyl group or glyceryl or form oxo base, X together with the adjacent oxygen atom that is connected
2, X
3And X
4Represent hydrogen atom, hydroxyl or acetoxyl group respectively independently, still, when W is methine, X
2And X
3In one be hydrogen atom and another does not exist; When-O-X
1When being the oxo base, X
4Do not exist,
R
14And R
15Represent hydrogen atom, hydroxyl, methylol or acetoxy-methyl respectively independently,
R
16It is 5～35 straight chain, side chain or cyclic alkyl that expression has or do not have hydroxyl or amino substituent carbon number; Or be that 8～22 straight chain, side chain or cyclic saturated or unsaturated fatty acid are with ester bond or the bonded base of amido link with the carbon number that has or do not have hydroxyl substituent in the ω position of this alkyl
R
17Expression hydrogen atom or expression have or do not have the saturated or unsaturated alkyl that the substituent the total number of carbon atoms that is selected from hydroxyl, hydroxy alkoxy base, alkoxyl and acetoxyl group is 1～8 straight or branched.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007146270 | 2007-05-31 | ||
| JP2007-146271 | 2007-05-31 | ||
| JP2007146270A JP4469874B2 (en) | 2007-05-31 | 2007-05-31 | Hair cosmetics |
| JP2007146271A JP4469875B2 (en) | 2007-05-31 | 2007-05-31 | Hair cosmetics |
| JP2007-146270 | 2007-05-31 | ||
| JP2007146271 | 2007-05-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101313884A CN101313884A (en) | 2008-12-03 |
| CN101313884B true CN101313884B (en) | 2012-01-18 |
Family
ID=40105130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100984147A Active CN101313884B (en) | 2007-05-31 | 2008-05-26 | Hair cosmetic composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4469874B2 (en) |
| CN (1) | CN101313884B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5751808B2 (en) * | 2010-11-18 | 2015-07-22 | 花王株式会社 | Hair cosmetics |
| JP5751807B2 (en) * | 2010-11-18 | 2015-07-22 | 花王株式会社 | Hair cosmetics |
| JP5663320B2 (en) * | 2011-01-19 | 2015-02-04 | 花王株式会社 | Method for producing vesicle composition |
| JP5969272B2 (en) * | 2012-06-08 | 2016-08-17 | 東邦化学工業株式会社 | Hair composition |
| JP6490449B2 (en) * | 2015-02-27 | 2019-03-27 | 花王株式会社 | Hair cosmetics |
| WO2018003625A1 (en) | 2016-06-29 | 2018-01-04 | 日光ケミカルズ株式会社 | Damaged hair-improving agent and damaged hair-improving cosmetic containing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476649A (en) * | 1990-11-02 | 1995-12-19 | Kao Corporation | Hair cosmetic composition |
| CN1347312A (en) * | 1999-04-08 | 2002-05-01 | 花王株式会社 | Skin preparations |
| CN1404813A (en) * | 2001-08-06 | 2003-03-26 | 花王株式会社 | Conditioner |
-
2007
- 2007-05-31 JP JP2007146270A patent/JP4469874B2/en active Active
-
2008
- 2008-05-26 CN CN2008100984147A patent/CN101313884B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476649A (en) * | 1990-11-02 | 1995-12-19 | Kao Corporation | Hair cosmetic composition |
| CN1347312A (en) * | 1999-04-08 | 2002-05-01 | 花王株式会社 | Skin preparations |
| CN1404813A (en) * | 2001-08-06 | 2003-03-26 | 花王株式会社 | Conditioner |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008297262A (en) | 2008-12-11 |
| CN101313884A (en) | 2008-12-03 |
| JP4469874B2 (en) | 2010-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101321512B (en) | Aqueous hair cosmetic composition | |
| CN101313884B (en) | Hair cosmetic composition | |
| CN101155575B (en) | Hair cosmetic | |
| KR101561177B1 (en) | Oily hair cosmetic | |
| CN1891189B (en) | Hair cosmetic composition | |
| TWI442942B (en) | Hair cosmetic compositions and process for producing the same | |
| CN101129303B (en) | Aqueous hair cosmetic | |
| US8562957B2 (en) | Oily hair cosmetics | |
| JP5325494B2 (en) | Hair cosmetics | |
| CN101617996A (en) | Cosmetic composition and cosmetic treatment method using said composition | |
| KR20090056321A (en) | Transparent shampoo composition containing natural oil | |
| JP4589820B2 (en) | Hair cosmetics | |
| CN101848697B (en) | Hair cosmetic composition | |
| JP4563083B2 (en) | Hair cosmetics | |
| JP2006290795A (en) | Hair cosmetic | |
| CN1320877C (en) | Hair cosmetics | |
| JP6686905B2 (en) | Hair cosmetic composition containing an acyl basic amino acid derivative | |
| JP5751808B2 (en) | Hair cosmetics | |
| MX2013002047A (en) | Hair conditioning composition. | |
| CN111867556B (en) | Liquid lipid complex composition for improving hair state | |
| JP2010070507A (en) | Hair cosmetic | |
| JP4080991B2 (en) | Hair cosmetics | |
| CN100417372C (en) | Hair cleaner | |
| CN101433501A (en) | Method for durable treatment of fibre in four stages | |
| JP5698528B2 (en) | Hair cosmetics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |