CN1254227C - Reducing composition for treating keratinous materials comprising cationic poly (vinyllactam) - Google Patents
Reducing composition for treating keratinous materials comprising cationic poly (vinyllactam) Download PDFInfo
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- CN1254227C CN1254227C CN 02800867 CN02800867A CN1254227C CN 1254227 C CN1254227 C CN 1254227C CN 02800867 CN02800867 CN 02800867 CN 02800867 A CN02800867 A CN 02800867A CN 1254227 C CN1254227 C CN 1254227C
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/04—Preparations for permanent waving or straightening the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/08—Preparations for bleaching the hair
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Abstract
The invention concerns a cosmetic composition for treating keratinous materials comprising in a carrier suited for the keratinous materials: (i) at least a reducing agent and (ii) at least a cationic poly(vinyllactam), and its used for bleaching and permanent waving of keratinous fibres. The invention also concerns methods and devices for bleaching and permanent waving of keratinous fibres using said composition.
Description
The application relates to the make-up composition that is used for horn that contains following chemical compound in the carrier that is suitable for the horn use:
(i) at least a Reducing agent and
(ii) at least a cationic polyvinyl base lactams.
The present invention relates to be used for the processing angle pledge contain cationic polyvinyl base lactams gelation reducing composition and the human cutin fiber, the particularly application of head decolouring and lasting (long-acting) distortion aspect.
Give cutin fiber with the decolorizing composition that contains one or more oxidants, particularly human hair's decolouring is known.In the conventional oxidation agent of using, hydrogen peroxide can be enumerated or the chemical compound of hydrogen peroxide can be produced by hydrolysis, such as urea peroxide or persalt, as perborate, percarbonate and persulfate, hydrogen peroxide and persulfate are particularly preferred.
And by means of Reducing agent such as ascorbic acid or as the mercaptan of cysteine, make that it also is known carrying out with the external source coloring agent that artificially colored human cutin fiber such as hair decolour.
It also is known making hair generation permanently shaping, this is to contain one or more Reducing agents by coating on hair, the hair of this moment preferably is under the stress by means of machinery such as curler especially in advance, again reductive hair like this oxidation again under desirable shape, after the rinsing of being everlasting, carry out oxidation by means of airborne oxygen, but be more typically by preferred oxidant from oxygenated water or alkaline bromate.
The preferred Reducing agent that uses is selected from thio-alcohol in the field of hair permanently shaping, such as thioglycol acid (l ' acide thioglycolique) and salt and ester, 2-mercaptopropionic acid and salt thereof, cysteine or cysteamine, and sulphite.
The form that mainly is instant available compositions by means of Reducing agent to the compositions of hair decolouring, form by the anhydrous product that contains one or more Reducing agents (powder or mastic), carve in use, Reducing agent and the optional Aquo-composition that contains pH value reagent are mixed.Decolorizing composition also is and contains the form of promptly using Aquo-composition that one or more are in Reducing agent under the suitable pH value.
The reducing composition of hair permanently shaping generally is promptly with the Aquo-composition form or is anhydrous powder compositions or forms of liquid compositions, carves in use it is mixed with the Aquo-composition of suitable pH value.
Do not flow to for decolouring or the chemical compound of permanently shaping being coated on the hair beyond the scope that maybe should handle on the face, we use traditional thickening agent always up to now, such as crosslinked polyacrylic acid, hydroxyethyl-cellulose, some polyurethane, wax, and under the situation of decolorizing composition, use the non-ionic surface active agent of HLB (hydrophilic-lipophilic balance), it generally selects can produce the effect of gel when water and/or surface activity dilution agent.
In addition, the cosmetic prescription that is transparent gel form years of researches have been carried out.Because control attractive in appearance and easy is used, this series products is well suited for consumer and uses.
The form of gel the most often is equivalent to the actual care of user: take out easily product from its packing, do not have tangible loss, limits product in the diffusion of the regional area of handling and use enough amounts, to obtain required dressing effect.For the original formulation of going back that uses in hair decolouring or the permanently shaping, this target is very important.This should be able to be very equably smears and distributes along cutin fiber, can not flow to forehead, face, neck or flow into eyes.
The applicant finds that the thickening system that prior art is used can not obtain ability enough strong and decolouring uniformly and permanently shaping.
Also find in addition, contain the instant available decolouring or the permanently shaping compositions of one or more Reducing agents and prior art thickening agent, neither can accurately be coated with satisfactorily and do not drip, can not allow viscosity reduce along with the progress of time.
After this problem has been carried out big quantity research, the applicant finds now, if in compositions, introduce the cationic polyvinyl base lactams of effective dose, just can obtain being hair decolouring instant available gel form, that contain at least a Reducing agent or permanently shaping compositions, this compositions is not trickled, therefore can be kept at well on the application point, can also obtain the effect of decolouring by force and uniformly or permanently shaping.
These discoveries are bases of the present invention.
Therefore, the objective of the invention is a kind of cosmetic and/or skin composition that is used for the processing angle pledge, said composition contains in being suitable for the carrier of horn:
(i) at least a Reducing agent and
(ii) at least a cationic polyvinyl base lactams.
The invention still further relates to the application as thickening agent and/or gelating agent in cosmetic that contains at least a Reducing agent and/or dermatological composition of this cationic polyvinyl base lactams.
A further object of the present invention is the application of this type of cationic polyvinyl base lactams in a kind of instant available set compound, this compositions is used for the human cutin fiber, the particularly decolouring of hair or permanently shaping, its be suitable for decolouring or the medium of permanently shaping in, contain at least a Reducing agent.
So-called " instant available compositions ", referring to said composition on the meaning in the present invention can former state be coated on the cutin fiber, is using or is obtaining can in statu quo storing before the instant mixture of preparing of two or more compositionss in other words.
When instant available combination thing is when being obtained by the instant preparation of multiple compositions, polymer of the present invention may reside in one or more compositionss, perhaps is present in whole compositionss.
Therefore, cationic polyvinyl base lactams of the present invention can be with powder, and the form of preferred fine powder or the form of mastic are present in the anhydrous composition and/or are present in one or more Aquo-compositions.
According to the present invention, cationic polyvinyl base lactams of the present invention preferably is present at least a Aquo-composition, carve in use, with its with contain at least a Reducing agent and be the aqueous fluid form, or the compositions that is Powdered or paste (butterfat) anhydrous form is mixed.
The preferred form of another kind of the present invention is the unique compositions that contains one or more Reducing agents and one or more cationic polyvinyl base lactams of the present invention.
Another object of the present invention is the application of this polymer in containing the anhydrous composition of at least a Reducing agent, and described compositions can be diluted before being applied on the fiber.
The present invention also provides use instant available decolorizing composition or permanently shaping compositions as previously described to make the human cutin fiber, the particularly method of hair decolouring or the method for permanently shaping, under the situation of permanently shaping, after the described compositions of coating, choose wantonly after rinsing, be coated with a kind of oxidising composition.
The present invention also provides the device of decolouring, perhaps contains the packing " external member " of so instant available set compound.
Such as, a kind of device with 2 boxes comprises at least a powder or mastic is housed, perhaps first box of Aquo-composition and second box that a kind of Aquo-composition is housed, at least one contains at least a Reducing agent in two boxes, and in two boxes at least one contains at least a cationic polyvinyl base lactams of the present invention.
In the middle of below the narration and embodiment, other features of the present invention, aspect, purpose and advantage all will show clearlyer.
Do not wish to interrelate with any theory, obviously relevant with the advantage of being brought as the following cationic polyvinyl base lactams that will define with the characteristic of the polymer viscosifier of conjunction type according to the present invention.
The conjunction type polymer is, in the medium of prescription, and the base polymer that its molecule can interosculate or combine with the molecule of other chemical compounds.
Its chemical constitution generally also comprises at least one hydrophilic area and at least one hydrophobic region, and these one or more hydrophobic regions contain at least one aliphatic chain.
According to cationic polyvinyl base lactams of the present invention
Contain according to cationic polyvinyl base lactams of the present invention:
-a) the monomer of at least a vinyl lactam type or alkyl vinyl lactams type;
-b) at least a following structure (I) or monomer (II):
Wherein:
X represents oxygen atom or group NR
6,
R
1And R
6Represent hydrogen atom or C independently of one another
1～C
5The alkyl of straight or branched,
R
2Expression C
1～C
4The alkyl of straight or branched,
R
3, R
4And R
5Represent hydrogen atom, C independently of one another
1～C
30Straight or branched alkyl or as the group of general formula (III):
-(Y
2)
r-(CH
2-CH(R
7)-O)
x-R
8 (III)
Y, Y
1And Y
2Represent C independently of one another
2～C
16The alkylidene of straight or branched,
R
7Expression hydrogen atom or C
1～C
4The alkyl of straight or branched, perhaps C
1～C
4The hydroxy alkyl of straight or branched,
R
8Expression hydrogen atom or C
1～C
30The alkyl of straight or branched,
P, q and r represent 0 or 1 numeral independently of one another,
M and n represent 0～100 integer independently of one another,
X represents 1～100 integer,
Z represents the anion of organic acid or mineral acid,
Condition is:
-substituent R
3, R
4, R
5Or R
8In at least one the expression C
9～C
30The alkyl of straight or branched,
If-m or n are not 0, then q equals 1,
If-m or n equal 0, then p or q equal 0.
Can be crosslinked or not have crosslinkedly according to cationic polyvinyl base lactams of the present invention, also can be block polymer.
The monomeric counter ion counterionsl gegenions Z of general formula (I)
-Preferably from halide ion, phosphate anion, methylsulfuric acid radical ion (l ' ion m é thosulfate) and toluenesulfonic acid radical ion.
R
3, R
4And R
5Preferably represent hydrogen atom or C independently of one another
1～C
30The alkyl of straight or branched.
Monomer b) be more preferably the monomer of general formula (I), wherein more preferably m and n equal 0.
The chemical compound of the preferably following structure of vinyl lactam or alkyl vinyl lactam monomers (IV):
Wherein:
S represents 3～6 numeral,
R
9Expression hydrogen atom or C
1～C
5Alkyl,
R
10Expression hydrogen atom or C
1～C
5Alkyl,
Condition is R
9And R
10In at least one the expression hydrogen atom.
Monomer (IV) is more preferably vinyl pyrrolidone.
Can also contain one or more other monomers according to cationic ethylene base lactam polymer of the present invention, preferably cationic or non-ionic.
As the preferred chemical compound of the present invention, can enumerate following terpolymer, this copolymer contains following at least composition:
A) monomer of a kind of general formula (IV);
B) monomer of a kind of general formula (I), p=1 wherein, q=0, R
3And R
4Represent hydrogen atom or C independently of one another
1～C
5Alkyl, and R
5Expression C
9～C
24Alkyl, and
C) monomer of a kind of general formula (II), wherein R
3And R
4Represent hydrogen atom or C independently of one another
1～C
5Alkyl.
More preferably use the monomer (a) that contains 40～95wt%, the terpolymer of the monomer (b) of the monomer of 0.1～55wt% (c) and 0.25～50wt%.
At patent WO-00/68, narrated such terpolymer in 282, its content is as ingredient of the present invention.
As cationic polyvinyl base lactam polymer of the present invention, use vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/toluenesulfonic acid dodecyl dimethyl methacryl amido propyl ammonium salt terpolymer, vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/toluenesulfonic acid cocoyl dimethylmethacryl amide base propyl group ammonium salt terpolymer, vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/toluenesulfonic acid or chlorination lauryl dimethyl methacryl amido propyl ammonium terpolymer especially.
According to cationic polyvinyl base lactam polymer of the present invention, its weight average molecular weight is preferably 500～20000000.More preferably 200000～2000000, more preferably 400000～800000.
According to the concentration of cationic polyvinyl base lactam polymer of the present invention in said composition is 0.01～30wt%, more preferably is 0.1～10wt%, more especially 0.5～2wt%.
Reducing agent
According to the operable Reducing agent of the present invention preferably from sulfur alcohol compound, such as cysteine, thioglycol acid, 2-mercaptopropionic acid, their salt and their ester, cysteamine and salt thereof or sulphite.
Under the situation of the compositions that is used to decolour, also can use ascorbic acid, its salt and its ester, arabo-ascorbic acid, its salt and its ester, sulfinate such as hydroxyl methane sulfinic acid sodium.
In the present composition, the concentration of these Reducing agents is counted about 0.1～30wt% with composition total weight, preferably about 0.5～20wt%.
Compositions of the present invention, the more special cationic polymer that also contains at least a amphiphilic polymers or be different from cationic polyvinyl base lactams of the present invention.
Cationic polymer
On meaning of the present invention, so-called " cationic polymer " expression is various to be contained cation group and/or dissociablely is the polymer of cationic group.
Can be selected from according to the operable cationic polymer of the present invention and to have known those that itself can be used as the agent of hair cosmetic improvement in performance, promptly particularly at EP-A-337,354 and at French Patent (FRP) Fr-2,270,846,2,383,660,2,598,611,2,470,596 and 2, those materials of narration in 519,863.
The preferred cation polymer is selected from and contains the polymer that comprises primary amine, secondary amine, tertiary amine and/or quaternary ammonium group chain link, can constitute the main chain of polymer, also can constitute the side chain substituents that directly links to each other with main chain.
The number-average molecular weight of the cationic polymer that uses is generally about 500～5 * 10
6, be preferably about 10
3～3 * 10
6
In cationic polymer, more particularly can enumerate polyamines base polymer, polyamino acylamide polymer and polyquaternary ammonium salt.
These are known products.In French Patent (FRP) 2,505, these products have been narrated especially in 348 and 2,542,997.In the middle of described polymer, can enumerate:
(1), contain at least a following general formula (I), (II), (III) or chain link (IV) (unit) from the homopolymer or the copolymer of acrylate or acrylamide or methacrylate or Methacrylamide:
Wherein:
R
3Identical or different, expression hydrogen atom or methyl;
A is identical or different, and expression contains 1～6 carbon atom, the alkyl of the straight or branched of preferred 2 or 3 carbon atoms, or have the hydroxy alkyl of 1～4 carbon atom;
R
4, R
5, R
6Identical or different, expression has the alkyl or the benzyl of 1～18 carbon atom, preferably has the alkyl of 1～6 carbon atom;
R
1And R
2Identical or different, expression hydrogen atom or have the alkyl of 1～6 carbon atom, preferably methyl or ethyl;
X represents from mineral acid or organic acid anion, such as methylsulfate anion or halide ion, such as chlorine or bromine.
(1) polymer of class can also contain one or more from the chain link that can be selected from following comonomer: acrylamide, Methacrylamide, diacetone acrylamide, on nitrogen-atoms by C
1～C
4Acrylamide and Methacrylamide that low alkyl group replaces, acrylic or methacrylic acid or their ester, vinyl lactam such as vinyl pyrrolidone or caprolactam, vinyl esters.Therefore, in these (1) base polymers, can enumerate:
-by the copolymer of dimethyl sulfate or quaternised acrylamide of dimethyl halogenide and dimethylaminoethyl methacrylate, such as the polymer of Hercules company with trade name Hercofloc sale;
The copolymer of-acrylamide and methacryloxyethyl trimethyl ammonium chloride, this polymer is narrated in EP-A-080976, and is sold with the trade name of Bina Quat P100 by Ciba Geigy company;
The copolymer of-acrylamide and methacryloxyethyl trimethyl-methylsulfuric acid ammonium is sold with trade name Reten by Hercules company;
The copolymer of-quaternized or not quaternised vinyl pyrrolidone/acrylic or methacrylic acid dialkyl aminoalkyl ester, such as the polymer of ISP company with trade name Gafquat sale, as Gafquat 734 or Gafquat 755, perhaps commodity are called the polymer of Copolymer845 , 958 and 937 .These polymer are in French Patent (FRP) 2,077, narration are arranged in 143 and 2,393,573;
The ter-polymers of-dimethylaminoethyl methacrylate/caprolactam/vinyl pyrrolidone, such as ISP company with trade name Gaffix VC713 product sold;
-vinyl pyrrolidone/methacryl amido propyl-dimethyl amine copolymer is sold with trade name Styleze CC10 by ISP company;
-by the quaternised vinyl pyrrolidone/methacrylamide copolymer of dimethylaminopropyl, such as the commodity of ISP company with trade name Gafquat HS 100 sales;
(2) in French Patent (FRP) 1,492, the commodity that the cellulose ether derivative that contains quaternary ammonium group, particularly Union Carbide company of narration are sold with trade name JR (JR 400, JR 125, JR 30M) or LR (LR 400, LR 30M) in 597.The quaternary ammonium salt of the hydroxyethyl-cellulose that these polymer also are defined as replacing with the trimethyl ammonium in the CTFA dictionary epoxide reacts;
(3) cationic cellulose derivative, such as cellulose or grafted cellulose derivative and water solublity quaternary ammonium monomer copolymer, particularly at US 4,131, the polymer of narration in 576, such as the special grafted hydroxy alkyl celluloses of salt such as methacryloxyethyl trimethyl ammonium, methacryl aminopropyl trimethyl ammonium, dimethyldiallylammonium of using, as methylol, ethoxy or hydroxypropyl cellulose.
The commodity that are equivalent to this definition more especially National Starch company with the product of trade name Celquat L 200 and Celquat H 100;
(4) be more in particular in US 3,589, the cationic polysaccharide of narration in 578 and 4,031,307 is such as the guar gum that contains the cation trialkyl ammonium.Can use by 2 the guar gum of 3-glycidyl leptodactyline (such as chloride) modification.
Such commodity specifically are that Meyha ll company is with trade name Jaguar C 13S, Jaguar C 15, Jaguar C 17 or Jaguar C 162 etc.;
(5) by piperazinyl and band straight chain or the divalent alkyl of branched chain or the polymer that hydroxy alkylidene is formed, with chain in optional oxygen atom, sulphur atom or the nitrogen-atoms of inserting, perhaps aromatic rings or heterocycle, and the oxidation of these polymer and/or quaternised product.In French Patent (FRP) 2,162, narrated such polymer especially in 025 and 2,280,361;
(6) special water-soluble poly amino amides by acid compound and polyamines condensation prepared, these polyaminoamides can be by epoxyhalopropane (epihalohydrin), di-epoxy compounds, dicarboxylic anhydride, unsaturated dicarboxylic anhydride, two unsaturated derivants, dihalo alcohol, diazetidine, dihalo acyl group diamidogen, saturated dihalide or by two functional activity chemical compounds and dihalo alcohol, diazetidine, dihalo acyl group diamidogen, the dihalo alkyl, epihalohydrin, the oligomer that di-epoxy compounds or two unsaturated derivatives reactions obtain is crosslinked, and the consumption of operable cross-linking agent is that the amido of each polyaminoamide is 0.025～0.35 mole; If these polyaminoamides contain one or more tertiary amines, quaternary ammonium functional group, they can be by alkylation.In French Patent (FRP) 2,252, narrated such polymer in 840 and 2,368,508;
(7) by polyalkylenepolyamines and polybasic carboxylic acid polycondensation, the polyaminoamide derivant that obtains with two functional reagent alkylations then.Can enumerate the polymer such as adipic acid-dialkyl amido hydroxy alkyl two alkylene triamine, alkyl wherein contains 1～4 carbon atom, preferably represents methyl, ethyl and propyl group.In French Patent (FRP) 1,583, narrated such polymer especially in 363.
In these derivants, can enumerate adipic acid-dimethylamino hydroxypropyl diethylenetriamines polymer that Sandoz company sells with the trade name of Cartaretine F, F4 or F8 more especially;
(8) polymer that obtains by polyalkylenepolyamines that contains two primary amine groups and at least one secondary amine and the dicarboxylic acids reaction that is selected from two alkyd and representative examples of saturated aliphatic dicarboxylic acids with 3～8 carbon atoms.The mol ratio of polyalkylenepolyamines and dicarboxylic acids is 0.8: 1～1.4: 1; The polyaminoamide that obtains again with epichlorohydrin reaction, the mol ratio of secondary amine is 0.5: 1～1.8: 1 in epoxychloropropane and the polyaminoamide.At United States Patent (USP) 3,227, narrated such polymer especially in 615 and 2,961,347.
This polymer is special to be given commercialization by Hercules company with the trade name of Hercosett 57 in addition, perhaps under the situation of adipic acid/glycidyl/diethylidene-triamine copolymer, by of the trade name commercialization of Hercules company with PD 170 or Delsett 101 ;
(9) cyclocopolymer of alkyl allyl amine or dialkyl diallyl amine, such as contain useful general formula (V) or (VI) chain link of expression as the homopolymer or the copolymer of the main structure of chain:
In this general formula, k and t equal 0 or 1, k+t and equal 1; Rg represents hydrogen atom or methyl; R
7And R
8Expression has alkyl, the hydroxy alkyl of 1～22 carbon atom independently of one another, and alkyl wherein preferably has 1～5 carbon atom, also represents the rudimentary C of amide groups
1～C
4Alkyl, perhaps R
7And R
8Represent a heterocyclic radical with the nitrogen-atoms that is connected with them, such as piperidyl or morpholinyl; R
7And R
8Preferred expression independently of one another has the alkyl of 1～4 carbon atom; Y
-Be anion, such as bromide ion, chloride ion, acetate, borate, citrate, tartrate anion, bisulfate ion, bisulfite, sulfate radical and phosphate radical.In French Patent (FRP) 2,080,759 and in its certificate of addition 2,190,406, narrated these polymer especially.
In polymer as defined above, can enumerate dimethyl diallyl ammonium chloride homopolymer (and homologue of low weight average molecular weight) that Caglon company sells with trade name Merquat 100 especially and the diallyldimethylammonium chloride sold with trade name Merquat 550 and the copolymer of acrylamide;
(10) contain quaternized two ammonium polymers of the repeating segment that following general formula represents:
In this general formula (VII):
R
10, R
11, R
12And R
13Identical or different, expression has aliphatic, alicyclic or araliphatic group, perhaps lower aliphatic hydroxy alkyl, the perhaps R of 1～20 carbon atom
10, R
11, R
12And R
15Constitute optional nitrogen-atoms second heteroatomic heterocycle, the perhaps R in addition that contain with the nitrogen-atoms that links to each other with them together or respectively
10, R
11, R
12And R
13Expression by itrile group, ester group, acyl group, amide groups or-CO-O-R
14-D or-CO-NH-R
14The C of the straight or branched that-D replaces
1～C
6Alkyl, R here
14Be alkylidene, D is a quaternary ammonium group;
A
1And B
1Expression contains the polymethylene group of 2～20 carbon atoms, they can be straight chain or side chain, saturated or unsaturated, in main chain, can contain, connect or insert one or several aromatic rings or one or several oxygen atom, sulphur atom or sulfoxide group, sulfuryl, disulfide group (disulfure), amino, alkyl amino, hydroxyl, quaternary ammonium group, urea groups, amide groups or ester group
X
-Expression is from mineral acid or organic acid anion;
A
1, R
10And R
12Form piperazine ring with the nitrogen-atoms that links to each other with them, in addition, if A
1The expression straight or branched, saturated or undersaturated alkylidene or hydroxy alkylidene, B
1Can also represent group (CH
2)
n-CO-D-OC-(CH
2)
n-, wherein n is 1～100, and is preferred 1～50, D represents:
A) remainder of the glycol of general formula-O-Z-O-, Z represents to be equivalent to the alkyl of the straight or branched of following general formula here:
-(CH
2-CH
2-O)×-CH
2-CH
2-
-[CH
2-CH(CH
3)-O]y-CH
2-CH(CH
3)-
Here x and y represent 1～4 integer, and representative is determined and unique degree of polymerization, or any number between 1～4, the expression average degree of polymerization;
B) residue of two secondary diamines is such as bridged piperazine derivatives;
C) residue of two primary diamines of general formula-NH-Y-NH-, Y represents the alkyl of straight or branched here, or divalent group-CH
2-CH
2-S-S-CH
2-CH
2-
D) urylene of general formula-NH-CO-NH-.
X
-Preferably as the anion of chlorine or bromine.
The number-average molecular weight of these polymer is generally 1000～100000.
In French Patent (FRP) 2,320,330,2,270,846,2,316,271,2,336,434 and 2,413,907 and United States Patent (USP) 2,273,780,2,375,853,2,388,614,2,454,547,3,206,462,2,261,002,2,271,378,3,875,870,4,001,432,3,929,990,3,966,904,4,005,193,4,025,617,4,025,627,4,025,653,4,026,945 and 4,027,020 has narrated this base polymer especially.
Can use the polymer of the repeating segment formation that is equivalent to following general formula (VIII) more especially:
Wherein, R
10, R
11, R
12And R
13Identical or different, expression has the alkyl or the hydroxy alkyl of about 1～4 carbon atom, and n and p are about 2～20 integers, X
-Be from mineral acid or organic acid anion;
(11) the many quaternary ammonium polymers that constitute by the repeating segment of following general formula (IX):
Wherein p represents about 1～6 integer, and D does not have, and perhaps represents group-(CH
2)
r-CO-wherein r represents to equal 4 or equal 7 numeral, X
-It is anion;
Such polymer can be according at United States Patent (USP) 4,157, the method preparation of narration in 388,4,702,906 and 4,719,282.Especially at patent EP-A-122, narration is arranged in 324.
Wherein can enumerate such as Miranol company with Mirapol A15, Mirapol AD1, Mirapol AZ1 and Mirapol 175 product solds;
(12) quaternary ammonium polymer of vinyl pyrrolidone and vinyl imidazole, such as BASF AG with trade name Luviqua t FC 905, FC 550 and FC 370 product solds;
(13) polyamine of selling with trade name Polyquart H as Henkel company is with reference to " Polyethylene Glycol (15) Adeps Bovis seu Bubali polyamine " (Polyethylenglycol (15) the Tallow Polyamine) in the CTFA dictionary;
(14) by methacryloxy C
1～C
4Alkyl three C
1～C
4The polymer that alkylammonium salt is crosslinked, such as by the quaternised dimethylaminoethyl methacrylate homopolymerization of chloromethanes, the perhaps polymer that obtains by acrylamide and the quaternised dimethylaminoethyl methacrylate copolymerization of chloromethanes, this homopolymerization or copolymerization are had unsaturated ethylene linkage subsequently, and particularly methylene diacrylamine is crosslinked.Can more particularly use the crosslink propylene amide/methacryloxyethyl trimethyl ammonium chloride copolymer (20/80 weight) of described copolymer dispersion of 50 weight % in mineral oil.This dispersion liquid by Allied Colloids company with trade name Salcare SC 92 commercializations.Can also use the homopolymer of the crosslinked methacrylic acyloxy ethyl-trimethyl salmiac that in mineral oil or esters liquid, contains about 50wt% homopolymer form.These dispersion liquids are by the trade name commercialization of Allied Colloids company with Salcare SC 95 and Salcare SC 96.
Operable within the scope of the invention other cationic polymers are polyalkyleneimines, particularly polyethylene imine based, the condensation polymer that contains polymer, polyamines and the epoxychloropropane of vinylpyridine or vinylpyridine chain link, quaternised poly-urylene and chitin derivatives.
In the middle of operable within the scope of the invention all these cationic polymers, preferably use the polymer of (1), (9), (10), (11) and (14) class, more preferably use the polymer of the repeating segment that has following general formula (W) and (U) represent:
Its molecular weight with gel permeation chromatography is in particular 9500～9900;
Especially its molecular weight with gel permeation chromatography is about 1200.
The cationic polymer that is different from cationic polyvinyl base lactams of the present invention that exists in the present composition, its concentration is equivalent to 0.01～10wt% of composition total weight, preferred 0.05～5wt%, more preferably 0.1～3wt%.
Amphiphilic polymers
According to containing the chain link K of random distribution and the polymer of M in the optional comfortable polymer chain of the operable amphiphilic polymers of the present invention, here K represents from containing the monomeric chain link of at least one basic nitrogen atom, and M represents the chain link from the acid monomer that contains one or several carboxyl or sulfo group, and perhaps K and M can represent the group from the zwitterionic monomer of carboxybetaine or sulfobetaines;
K and M can also represent a kind of cationic polymer chain that contains primary amine groups, secondary amine, tertiary amine groups or quaternary ammonium group, wherein at least one in these amidos has carboxyl or the sulfo group that links to each other by means of alkyl, perhaps K and M formation has ethylidene α, the part of β-dicarboxylic acid polymers chain, one of them carboxyl and the polyamines reaction that contains one or several primary amine groups or secondary amine.
Meet preferred as defined above amphiphilic polymers and be selected from following polymer:
(1) origin carries carboxyl, the monomer of the vinyl compound of groups such as acrylic acid, methacrylic acid, maleic acid, α-Lv Daibingxisuan and particularly from the alkaline monomer that contains at least one alkali atom, the polymer that obtains such as the substituted ethylene based compound copolymerization of methacrylic acid and propenoic acid dialkyl aminoalkyl ester, dialkyl aminoalkyl Methacrylamide and acrylamide particularly.At United States Patent (USP) 3,836, narrated such chemical compound in 537.Can also enumerate the copolymer with the sodium acrylate/acrylamido oxypropyl trimethyl ammonium chloride of trade name Polyquart KE 3033 sales by Henkel company.
Vinyl compound can also be the salt of dialkyl diallyl ammonium, such as dimethyl diallyl ammonium chloride.Acrylic acid and after this a kind of monomeric copolymer are called Merquat 280, Merquat 295 and Merquat Plus 3330 by Calgon company.
(2) contain polymer from following chain link:
A) at least a being selected from nitrogen by the monomer of AAM or Methacrylamide;
B) at least a acidic comonomer that contains one or several pendant carboxylic group;
C) at least a alkaline comonomer, such as the esters that has substituent acrylic acid of primary amine groups, secondary amine, tertiary amine groups and quaternary ammonium group and methacrylic acid, and with dimethyl sulfate or dithyl sulfate with the quaternised product of dimethylaminoethyl methacrylate.
Acrylamide that replaces according to the more particularly preferred N-of the present invention or Methacrylamide are that wherein alkyl contains a group of 2～12 carbon atoms, more particularly including N-ethyl acrylamide, N tert butyl acrylamide, uncle's N-octyl acrylamide, N-octyl acrylamide, N-decyl acrylamide, N-dodecyl acrylamide and corresponding Methacrylamide.
Acidic comonomer more particularly is selected from acrylic acid, methacrylic acid .beta.-methylacrylic acid, itaconic acid, maleic acid, fumaric acid and maleic acid or maleic anhydride, perhaps the monoesters with 1～4 carbon atom alkyl of fumaric acid or fumaric acid anhydride.
The amino ethyl ester that preferred alkaline comonomer is a methacrylic acid, butyl amino ethyl ester, N, N '-dimethylamino ethyl ester, N-tert-butyl group amino ethyl ester.
Can use its CTFA (1991 the 4th edition) name especially is the copolymer of octyl acrylamide/acrylate/metering system acid butyl amino ethyl ester copolymer, such as the product of the commodity of NationalStarch company Amphomer by name or Lovocryl 47;
(3) from the crosslinked and partially or completely alkylating polyaminoamide of the polyaminoamide of following general formula:
Wherein, R
19Expression is from the divalent group of the ester of the low-grade alkane alcohol with 1～6 carbon atom of saturated dicarboxylic acid, the aliphatic monocarboxylic acid that has the two keys of vinyl or dicarboxylic acids, these acid or the group that obtains from any described acid and di-primary amine or two secondary amine additions, and Z represents di-primary amine, primary monoamine or two secondary amine groups of polyalkylenepolyamines, preferably has:
A) the following group of 60～100mol%:
Here x=2 and p=2 or 3, perhaps x=3 and p=2
This group is from diethylenetriamines, trien or dipropylenetriamine;
B) the above-mentioned group (XI) of 0～40mo l%, wherein x=2 and p=1, it is from (Asia) second (base) diamidogen or from the group of piperazine:
C) group-NH-(CH of 0～20mol% from hexamethylene diamine
2)
6-NH-, being selected from two functional cross-linking agent such as epoxychloropropane, di-epoxy compounds, dicarboxylic anhydride, two unsaturated derivants by interpolation makes these polyaminoamides crosslinked, the dosage of crosslinking agent of each amido of polyaminoamide is 0.25～0.35 mole of %, can carry out alkylation with the sultones or their reactant salt of acrylic acid, monoxone or alkane.
Saturated carboxylic acid is preferably from having the acid of 6～10 carbon atoms, and such as adipic acid, 2,2,4-trimethyladipic acid and 2,4, has the acid of the two keys of vinyl, such as acrylic acid, methacrylic acid, itaconic acid at 4-trimethyladipic acid, p-phthalic acid.
The alkane sulfonic acid lactone that uses when alkylation is the sultones of propane or butane preferably, and the salt of alkylating reagent is sodium salt or potassium salt preferably;
(4) contain the polymer of the amphion chain link of following general formula:
Wherein, R
20Represent polymerisable unsaturated group, such as acrylic acid foundation group, methacrylic acid foundation group, acrylamide group or methacryl amine groups, y and z represent 1～3 integer, R
21And R
22Expression hydrogen atom, methyl, ethyl or propyl group, R
23And R
24Expression hydrogen atom or alkyl make at R
23And R
24The summation of middle carbon number is no more than 10.
Contain unitary like this polymer and can also contain chain link, such as from the dimethyl of acrylic or methacrylic acid or the chain link of diethyl amido ethyl ester or alkyl acrylate or alkyl methacrylate, acrylamide or Methacrylamide or vinylacetate from non-zwitterionic monomer.
Can enumerate the copolymer of butyl methacrylate/dimethylaminoethyl acrylate methyl base carboxymethylamino ethyl ester as an example, such as the product of Sandoz company commodity Diaformer Z301 by name.
(5) from the chitin derived polymers that meets following general formula (XIII), (XIV), (XV) monomer chain link and these chemical compounds and alkali or the sour salt that forms:
The content of chain link (XIII) is 0～30%, and the content of chain link (XIV) is 5～50%, and the content of chain link (XV) is 30～90%, and condition is in chain link (XV), R
25Be expressed as follows the group of general formula:
Wherein, q represents 0 or 1;
If q=0, R
26, R
27And R
28Identical or different, each represents hydrogen atom, methyl residue, hydroxyl, acetoxyl group or amino, monoalkylamine residue or dialkylamine residue, their optional one or several nitrogen-atoms and/or optional that inserts by one or several amido, hydroxyl, carboxyl, alkylthio group, sulfo group, the replacement of alkylthio group residue, wherein alkyl has amino residue, in the case, radicals R
26, R
27And R
28In at least one is arranged is hydrogen atom;
If perhaps q=1, R
26, R
27And R
28Each represents hydrogen atom,
(6) from the alkylating polymer of chitin N-, such as N-carboxymethyl chitosan or the N-carboxylic butyl chitin of Jan Dekker company with trade name Evalsan sale;
(7) meet the polymer of following general formula (XVI), such as in French Patent (FRP) 1,400, the polymer of narration in 366:
Wherein, R
29Expression hydrogen atom, group CH
3O, CH
3CH
2O, phenyl, R
30Expression hydrogen atom or low alkyl group are such as methyl, ethyl, R
31Expression hydrogen atom or low alkyl group are such as methyl, ethyl, R
32The expression low alkyl group is such as methyl, ethyl or accord with general formula R
33-N (R
31)
2Group, R
33Expression group-CH
2-CH
2-,-CH
2-CH
2-CH
2-,-CH
2-CH (CH
3)-, R
31Have and top identical meaning, and contain higher homologue until these groups of 6 carbon atoms,
The r value makes that molecular weight is 500～6000000, preferred 1000～1000000;
(8)-and D-X-D-X-type amphiphilic polymers, they are selected from:
A) monoxone or sodium chloroacetate and contain at least one as general formula
-D-X-D-X-D- (XVII)
The chemical compound of chain link of expression, the group that is expressed as follows of D here:
X represents symbol E or E ', E or E ' are identical or different, represent a divalent group, it is the alkylidene group that contains on main chain until the straight or branched of 7 carbon atoms, this main chain is not substituted or is replaced by hydroxyl, and can contain oxygen atom, nitrogen-atoms, sulphur atom, 1～3 aromatic rings and/or heterocycle; These oxygen atoms, nitrogen-atoms and sulphur atom can exist with the form of ether, thioether group, sulfoxide, sulfone, sulfonium, alkylamine, alkenyl amine, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, acid imide, alcohol, ester and/or carbamate;
B) as the polymer of general formula-D-X-D-X-(XVIII), at this, D is expressed as follows group:
X represents symbol E or E ', at least be to have only E ', E has and top identical meaning, E ' is a divalent group, it is the alkylidene that has on main chain until the straight or branched of 7 carbon atoms, this main chain is replaced by one or several hydroxyl or does not replace, and contain one or several nitrogen-atoms, the optional alkyl chain replacement of inserting an oxygen atom and must contain one or several carboxyl functional group or one or several hydroxy functional group of this nitrogen-atoms quilt, and by reacting with monoxone or sodium chloroacetate and being alkalized by Radix Betae;
(9) use N, N-dialkyl aminoalkyl amine is such as N, and the N-dimethylamino propylamine carries out half amideization or uses N, and N-dioxane hydramine carries out half esterization and carried out partially modified C
1～C
5The alkyl vinyl ether/maleic anhydride copolymer.These copolymers can also contain other vinyl comonomer, such as caprolactam.
According to the particularly preferred amphiphilic polymers of the present invention polymer that is (1) class.
According to the present invention, the amount of amphiphilic polymers can be 0.01～10wt% of composition total weight, preferred 0.05～5wt%, more preferably 0.1～3wt%.
Compositions of the present invention preferably contains one or more surfactants.These one or more surfactants can at random be selected from anion, both sexes, nonionic, double ion and cationic surfactant separately or with mixed form.
Normally used surfactant is as follows especially when enforcement is of the present invention:
(i) anion surfactant
As the anion surfactant that can be used alone or as a mixture within the scope of the invention, can enumerate the salt (particularly basic salt, particularly sodium salt, ammonium salt, amine salt, amino alkoxide or magnesium salt) of (listing to indefiniteness) following chemical compound especially: alkyl sulfate, alkyl ether sulfate, alkylamidoalkyl ether sulfate, alkyl aryl polyether sulfate, monoglyceride sulfate, alkylsulfonate, alkylphosphonic, alkylamidoalkyl sulfonate, alkylaryl sulfonates ,-alkene sulfonate, paraffin sulfonate, C
6～C
24Alkyl succinate, C
6～C
24Alkyl ether sulfo succinate, C
6～C
24Alkylamidoalkyl sulfosuccinate, C
6～C
24Alkyl sulfoethanoic acid. salt, C
6～C
24Acyl sarcosinates and C
6～C
24Acyl glutamate.Can also use the C of carboxylic acid
6～C
24The alkyl polyglycoside ester; such as citric acid alkyl-glucoside ester, tartaric acid alkyl polyglycoside ester and 2-Sulfosuccinic acid alkyl polyglycoside ester, sulfosuccinamic acid Arrcostab, acyl group isethionic acid ester and N-acyl taurate; the alkyl of the chemical compound that all these are different or acyl group all preferably contain 12～20 carbon atoms, and aryl is preferably represented phenyl or benzyl.In also operable anion surfactant; can also enumerate soap; such as oleate, Semen Ricini alcohol oleate, palmitate, stearate, Oleum Cocois hydrochlorate or hydrogenation Oleum Cocois hydrochlorate, acyl-lactate, acyl group wherein contains 8～20 carbon atoms.Can also use the C of the acid of alditol D alkyl galactoside and salt thereof, polyoxygenated alkylene
6～C
24Alkyl ether carboxylic acid, polyoxygenated alkylene C
6～C
24The C of alkyl aryl ether carboxylic acid, polyoxygenated alkylene
6～C
24Alkylamidoalkyl ether carboxylic acid and salt thereof particularly contain 2～50 oxyalkylenes, the particularly chemical compound of oxygen ethylene and their mixture;
(ii) non-ionic surface active agent
Non-ionic surface active agent itself is known (special in M.R.Porter " surfactant handbook (Handbook of Surfactants), Blackie ﹠amp; Son publishes (Glasgow and London version) 1991,116～178 pages), within the scope of the invention, its character is not crucial.Therefore, they can be selected from (listing to indefiniteness) especially: have alcohols, salmefamol class, polyethoxylated or poly-propenoxylated alkyl phenol such as the aliphatic chain of 8～18 carbon atoms, wherein oxirane or expoxy propane number are in particular 2～50.Can also enumerate the copolymer of oxirane and expoxy propane, the polycondensation product of oxirane and expoxy propane and aliphatic alcohol, the polyethoxylated aliphatic amide that preferably has 2～30 moles of ethylene oxide, on average contain 1～5, the polyglycereol fat family amide that preferably contains 1.5～4 glycerol groups, polyethoxylated fatty amine with 2～30 moles of ethylene oxide, ethoxylation shrink Sorbitol fatty acid ester with 2～30 moles of ethylene oxide, the fatty acid ester of sucrose, cithrol, alkyl poly glucoside, N-alkylated glucamine derivant, the oxide of amine is such as C
10～C
14The oxide of alkylamine or N-acyl amino propyl group morpholine oxide.
(iii) both sexes or zwitterionic surfactant
The kind of both sexes or zwitterionic surfactant is not crucial feature within the scope of the invention, they can be (listing to indefiniteness) secondary aliphatic amine or tertiary amines derived thing especially, aliphatic group wherein is straight chain or the branched chain that contains 8～18 carbon atoms and contain at least one water soluble anion group (such as carboxylate radical, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical), can also enumerate C
8～C
20Alkyl betaine, sulfobetaines, C
8～C
20Alkyl amido C
1～C
6Alkyl betaine or C
8～C
20Alkyl amino C
1～C
6The alkyl sulfobetaines.
In amine derivant, can enumerate the product of selling with trade name Miranol, such as at patent US-2,528,378 and US-2, narration and be sorted in the product of both sexes carboxyl glycine and both sexes carboxyl propanoic acid in 781,354 at CTFA dictionary (nineteen eighty-two the 3rd edition), they have following structure respectively:
R
2-CONHCH
2CH
2-N(R
3)(R
4)(CH
2COO
-)
R wherein
2Be illustrated in the R that exists in the hydrolysis Oleum Cocois
2The alkyl of-COOH acid, heptyl, nonyl or undecyl, R
3Expression-ethoxy and R
4The expression carboxymethyl;
R
2′-CONHCH
2CH
2-N(B)(C)
Wherein:
B represents-CH
2CH
2OX ', C represent-(CH
2)
z-Y ', this moment z=1 or 2,
X ' represents group-CH
2CH
2-COOH or hydrogen atom,
Y ' expression-COOH or group-CH
2-CHOH-SO
3H
R
2' be illustrated in the R that exists in hydrolysis Oleum Cocois or the oleum lini
9The alkyl of-COOH acid, particularly C
7, C
9, C
11Or C
13Alkyl, C
17Alkyl and isomeric form, undersaturated C
17Group.
These chemical compounds are categorized as coco group both sexes two acetic acid disodiums, lauryl both sexes two acetic acid disodiums, octyl group both sexes two acetic acid disodiums, caprylyl (caprylo) both sexes two acetic acid disodiums, coco group both sexes disodium beclomethasone, lauryl both sexes disodium beclomethasone, octyl group both sexes disodium beclomethasone, caprylyl both sexes disodium beclomethasone, lauryl both sexes dipropionic acid, coco group both sexes dipropionic acid in CTFA dictionary (1993, the 5th edition).
Can enumerate the coco group both sexes diacetate that Rhodia Chimie company sells with trade name Miranol C 2M as an example.
(iv) cationic surfactant
In cationic surfactant, can enumerate (listing to indefiniteness) especially: optional by the salt of the Armeen of polyoxygenated alkylene, secondary amine or tertiary amine, quaternary ammonium salt such as the chloride of tetra-allkylammonium, alkylamidoalkyl alkyl trialkyl ammonium, triakyl benzyl ammonium, trialkyl hydroxy alkyl ammonium or alkyl pyridine or bromide, imidazolidine derivatives or amine oxide with cation feature.
The consumption of surfactant in the present composition can be 0.01～40% of a said composition gross weight, preferred 0.5～30%.
The pH value of instant available set compound is generally about 1.5～12.
The pH value of the instant available set compound that is used to decolour according to the present invention is more preferably about 1.5～10, and more more preferably about 1.5～7.
Be used for the pH value of instant available set compound of permanently shaping according to the present invention more preferably about 6～12, and more more preferably about 7～11.
This pH value can be adjusted to required value by means of known acidulant or basifier in the technical field of cutin fiber decolouring or permanently shaping.
In basifier, can enumerate ammonia, alkali carbonate or ammonium carbonate, alkanolamine as an example, such as ethylenediamine, sodium hydroxide or the potassium hydroxide of monoethanolamine, diethanolamine and triethanolamine and derivant, hydroxy alkyl amine and oxyethylation and/or oxypropylation and the chemical compound of following general formula (XIX):
Wherein R is optional by hydroxyl or C
1～C
4The propylidene residue that alkyl replaces, R
38, R
39, R
40And R
41Identical or different, expression hydrogen atom, C
1～C
4Alkyl or C
1～C
4Hydroxy alkyl.
As an example, acidulant is being mineral acid or organic acid traditionally, such as hydrochloric acid, orthophosphoric acid, carboxylic acid, such as tartaric acid, citric acid, lactic acid or sulfonic acid.
The consumption of basifier or acidulant is about 0.01～30wt% of decolouring or permanently shaping composition total weight.
Compositions of the present invention can also contain chelating agen, such as ethylenediaminetetraacetic acid (EDTA).
Additional thickening agent
Compositions of the present invention can also contain other rheology control agent, such as cellulose thickener (hydroxyethyl-cellulose, hydroxypropyl cellulose, carboxymethyl cellulose etc.), guar gum and derivant thereof (hydroxypropyl guar gum), microbe-derived glue xanthene glue, scleroglucan glue), synthetic thickening agent, such as cross-linked homopolymer and the ion-type or the nonionic conjugated polymer of acrylic acid or acrylamido propane sulfonic acid, such as Goodrich company with trade name Pemulen TR1 or TR2, Allied Colloids company is with trade name Salcare SC 500, Rohm ﹠amp; Haas company with trade name Aculyn 22,28,33,44 or 46 and Akzo company with trade name Elfacos T210 and 212 product solds.
These thickening agents of Tian Jiaing can account for 0.01～10wt% of composition total weight in addition.
When the compositions that contains Reducing agent and/or one or more cationic polyvinyl base lactams of the present invention was anhydrous form (powder or mastic), main constituent that said composition contains and the additive of narrating above all were to be solid or water-free substantially liquid form.
When the medium that contains Reducing agent is aqueous medium, this aqueous medium can randomly contain at the acceptable organic solvent of cosmetic field, more specifically is alcohols wherein, such as ethanol, isopropyl alcohol, benzylalcohol or phenylethanol, or polyhydric alcohol or polyol ethers are such as the monomethyl ether of ethylene glycol, single ether and monobutyl ether, propylene glycol and ether thereof, such as propylene glycol monomethyl ether, the alkyl ether of butanediol, dipropylene glycol and diethylene glycol is such as the single ether or the monobutyl ether of diethylene glycol.This moment, the concentration of solvent can be about 0.5～20wt% of said composition gross weight, preferably approximately 2～10wt%.
Known other reagent of prior art at cutin fiber decolouring or permanently shaping that can also contain in addition, effective dose according to decolouring of the present invention or permanently shaping compositions.
Certainly, those skilled in the art will wish to select a kind of or optional multiple above-mentioned additional chemical compound, make and compose with inherent advantageous property for decolouring of the present invention or permanently shaping compositions, simultaneously because the interpolation of being conceived can or can not change these performances substantially.
Be preferably included in the instant available reducing composition of coating on the dry or moistening cutin fiber, allow it act on preferably approximately 1～60 minute according to discoloration method of the present invention, more preferably 10～45 minutes, this fiber of rinsing, optional with the shampoo washing then, and then relaunder and drying.
Be preferably included in the instant available reducing composition of coating on the dry or moistening cutin fiber, allow it act on preferably approximately 1～60 minute according to permanently shaping method of the present invention, more preferably 10～45 minutes, optional this fiber of rinsing, be coated with oxidising composition and then again with its effect 1～20 minute, preferred 1～10 minute, optional with the shampoo washing, and then relaunder and drying.
Can before the coating reducing composition, central or after use the machinery of bestowing stress to cutin fiber, before the rinsing oxidising composition or later on it is taken down.
The following examples explanation the present invention, but do not have restricted feature.
Embodiment 1:
The instant available decolouring Aquo-composition that is prepared as follows (amount is represented with gram):
| Citric acid | 7.4 |
| Two hydration trisodium citrates | 1 |
| Hydroxyethyl-cellulose | 1.5 |
| 2-oxopentanedioic acid | 0.8 |
| Sodium ascorbate | 5.7 |
| The L-cysteine | 2 |
| Polymer of the present invention ** | 0.3MA * |
| Magnesium sulfate | 1 |
| Water arrives in right amount | 100 |
MA
*=active matter
According to polymer of the present invention
*Be vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/lauryl dimethyl methacryl ammonium chloride terpolymer that ISP company provides, be called Polymer ACP-1234.
Above-mentioned decolorizing composition makes and decolours equably with the artificially colored hair of oxidative staining agent.
Embodiment 2:
The permanently shaping compositions that is prepared as follows (amount is represented with gram):
| Thioglycol acid | 9.2 |
| 20% ammonia | 9.3 |
| Ammonium carbonate | 4.5 |
| Cocoyl amido propyl betaine/glyceryl monolaurate (25/5) | 0.4MA * |
| EDTA | 0.4 |
| 60% aqueous solution of general formula W cationic polymer | 1MA * |
| Polymer of the present invention ** | 0.3MA * |
| Water arrives in right amount | 100 |
MA
*=active matter
According to polymer of the present invention
*Be vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/lauryl dimethyl methacryl ammonium chloride terpolymer that ISP company provides, be called Polymer ACP-1234.
Being pre-rolled on the moistening hair of curler the above-mentioned permanently shaping compositions of coating and keeping 15 minutes, use a large amount of water rinses then.The pH value of repaste cloth 8 volumes was 3 oxygenated water solution and kept 5 minutes that rinsing is again then taken off clip and carried out drying this moment.
Embodiment 3:
The instant available decolouring Aquo-composition that is prepared as follows (amount is represented with gram):
| Polymer of the present invention ** | 1MA * |
| Isooctadecanol (the Tego Alkanol 66 of Goldschmidt company) | 12 |
| Benzylalcohol | 10 |
| Hydroxyl methane sulfinic acid sodium | 7 |
| The adjusting pH value arrives | 3 |
| Demineralized water arrives in right amount | 100 |
According to polymer of the present invention
*Be vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/lauryl dimethyl methacryl ammonium chloride terpolymer that ISP company provides, title Polymer ACP-1234.
Aforesaid decolorizing composition is coated on the natural Lycoperdon polymorphum Vitt hair (wherein 90% white hair), uses tone 20 (brown) dyeing of L ' OREAL MOVIDA in advance, the dye bath ratio is that 10 grams are to 1 gram hair.
30 minutes dry then with the post rinse topknot.
Brown gloss disappears, and shows the hair before dyeing again.
Be prepared as follows reducing composition (with the gram expression):
| Thioglycol acid | 9.2 |
| Arginine | 15 |
| 20% ammonia | 9.3 |
| Ammonium carbonate | 4.5 |
| 30% aqueous solution of cocoyl amido propyl betaine/glyceryl monolaurate (25/5) | 1.3 |
| Colloidal sol | 0.8 |
| Polymer of the present invention ** | 1MA * |
| Isooctadecanol (the Tego Alkanol 66 of Goldschmidt company) | 12 |
| Chelating agen | 0.4 |
| Essence | 0.4 |
| Demineralized water arrives in right amount | 100 |
According to polymer of the present invention
*Be vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/lauryl dimethyl methacryl ammonium chloride terpolymer that ISP company provides, be called Polymer ACP-1234.
This reducing composition is coated in advance is being rolled on the moist hair of volume on the curler of 9 millimeters of diameters.
Keep after 10 minutes, with a large amount of water rinses.
Be coated with oxidising composition (8 volume oxygenated waters of pH value=3) then.
Keep after 10 minutes, use a large amount of water rinse topknots again.
Take off clip and carry out drying from hair then.
Topknot has scalded into wave.
Claims (34)
1. be used to handle the cosmetic and/or the skin composition of cutin fiber, said composition contains in the carrier that is suitable for the horn use:
(i) at least a Reducing agent and
(ii) a kind of cationic polyvinyl base lactams, it contains:
-a) the monomer of at least a vinyl lactam type or alkyl vinyl lactams type;
-b) at least a following structure (I) or monomer (II):
Wherein:
X represents oxygen atom or group NR
6,
R
1And R
6Represent hydrogen atom or C independently of one another
1～C
5The alkyl of straight or branched,
R
2Expression C
1～C
4The alkyl of straight or branched,
R
3, R
4And R
5Represent hydrogen atom, C independently of one another
1～C
30Straight or branched alkyl or as the group of general formula (III):
-(Y
2)
r-(CH
2-CH(R
7)-O)
x-R
8 (III)
Y, Y
1And Y
2Represent C independently of one another
2～C
16The alkylidene of straight or branched,
R
7Expression hydrogen atom or C
1～C
4The alkyl of straight or branched, perhaps C
1～C
4The hydroxy alkyl of straight or branched,
R
8Expression hydrogen atom or C
1～C
30The alkyl of straight or branched,
P, q and r represent 0 or 1 integer independently of one another,
M and n represent 0～100 integer independently of one another,
X represents 1～100 integer,
Z-represents the anion of organic acid or mineral acid,
Condition is:
-substituent R
3, R
4, R
5Or R
8In at least one the expression C
9～C
30The alkyl of straight or branched,
If-m or n are not 0, then q equals 1,
If-m or n equal 0, then p or q equal 0.
2. compositions as claimed in claim 1 is characterized in that, this vinyl lactam or alkyl vinyl lactam monomers are the chemical compounds as general formula (IV) structure:
Wherein:
S represents 3～6 numeral,
R
9Expression hydrogen atom or C
1～C
5Alkyl,
R
10Expression hydrogen atom or C
1～C
5Alkyl,
Condition is R
9And R
10In at least one the expression hydrogen atom.
3. compositions as claimed in claim 2 is characterized in that, the monomer of general formula (IV) is a vinyl pyrrolidone.
4. as any one compositions in the claim of front, it is characterized in that, at general formula (I) or (II), R
3, R
4, R
5Represent hydrogen atom or C independently of one another
1～C
30The straight or branched alkyl.
5. as any one compositions among the claim 1-3, it is characterized in that monomer b) be the monomer of general formula (I).
6. compositions as claimed in claim 5 is characterized in that, in general formula (I), m and n equal 0.
7. as any one compositions among the claim 1-3, it is characterized in that the monomeric counter ion counterionsl gegenions Z-of general formula (I) is from halide ion, phosphate anion, methylsulfuric acid radical ion, toluenesulfonic acid radical ion.
8. as any one compositions in the claim 1～3, it is characterized in that these one or more cationic polyvinyl base lactam polymers contain one or more additional cation or non-ionic monomers.
9. compositions as claimed in claim 8 is characterized in that, this cationic polyvinyl base lactams is to contain following monomeric terpolymer:
A) monomer of a kind of general formula (IV);
B) monomer of a kind of general formula (I), p=1 wherein, q=0, R
3And R
4Represent hydrogen atom or C independently of one another
1～C
5Alkyl, and R
5Expression C
9～C
24Alkyl, and
C) monomer of a kind of general formula (II), wherein R
3And R
4Represent hydrogen atom or C independently of one another
1～C
5Alkyl.
10. compositions as claimed in claim 9 is characterized in that, this terpolymer contains 40～95% monomer (a), 0.25～50% monomer (b) and 0.1～55% monomer (c).
11. as any one compositions among the claim 1-3, it is characterized in that this cationic polyvinyl base lactams is selected from: vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/toluenesulfonic acid dodecyl dimethyl methacryl amido propyl ammonium salt terpolymer, vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/toluenesulfonic acid cocoyl dimethylmethacryl amide base propyl group ammonium salt terpolymer, vinyl pyrrolidone/dimethyl aminopropyl Methacrylamide/toluenesulfonic acid or chlorination lauryl dimethyl methacryl amido propyl ammonium salt terpolymer.
12., it is characterized in that the weight molecular weight of this cationic polyvinyl base lactams is 500～20000000 as any one compositions among the claim 1-3.
13., it is characterized in that the consumption of these one or more cationic polyvinyl base lactams is 0.01～30wt% of composition total weight as any one compositions among the claim 1-3.
14. the compositions as claim 13 is characterized in that, the consumption of these one or more cationic polyvinyl base lactams is 0.1～10wt% of composition total weight.
15. the compositions as claim 14 is characterized in that, the consumption of these one or more cationic polyvinyl base lactams is 0.5～2wt% of composition total weight.
16. as any one compositions among the claim 1-3, it is characterized in that, these one or more Reducing agents are selected from sulfur alcohol compound, such as cysteine, thioglycol acid, 2-mercaptopropionic acid, their salt and their ester, cysteamine and salt thereof, sulphite, ascorbic acid, its salt and ester thereof, arabo-ascorbic acid, its salt and ester thereof.
17. the compositions as claim 16 is characterized in that, the concentration of this Reducing agent is 0.1～30wt% of said composition gross weight.
18. the compositions as claim 17 is characterized in that, this concentration is 0.5～20wt% of said composition gross weight.
19., it is characterized in that said composition also contains at least a amphiphilic polymers or is different from the cationic polymer of defined cationic polyvinyl base lactams in the claim 1～3 as any one compositions among the claim 1-3.
20. the compositions as claim 19 is characterized in that, this cationic polymer is by having the polyquaternary amine that following general formula (W) repeating segment constitutes:
21. the compositions as claim 19 is characterized in that, the polyquaternary amine that this cationic polymer is made up of the repeating segment that is equivalent to following general formula (U):
22. the compositions as claim 19 is characterized in that, this amphiphilic polymers is to contain at least a acrylic acid and dimethyldiallylammonium salt as monomeric copolymer.
23. the compositions as claim 19 is characterized in that, these one or more cationic polymers or amphiphilic polymers account for 0.01～10wt% of said composition gross weight.
24., it is characterized in that said composition also contains and is selected from anion, cation, nonionic or amphoteric surfactant as any one compositions among the claim 1-3.
25. the compositions as claim 24 is characterized in that, 0.01～40wt% of this surfactant comprise said composition gross weight.
26. as any one compositions among the claim 1-3, it is characterized in that said composition also contains at least a basifier or acidulant, their content is 0.01～30wt% of said composition gross weight.
27. compositions as claim 26, it is characterized in that, this basifier is selected from ammonia, alkali carbonate, alkanolamine, such as ethylenediamine, sodium hydroxide or the potassium hydroxide of monoethanolamine, diethanolamine and triethanolamine and derivant, hydroxy alkyl amine and oxyethylation and/or oxypropylation and the chemical compound of following general formula (XIX):
Wherein R is optional by hydroxyl or C
1～C
4The propylidene residue that alkyl replaces, R
38, R
39, R
40And R
41Identical or different, expression hydrogen atom, C
1～C
4Alkyl or C
1-C
4Hydroxy alkyl.
28. the compositions as claim 26 is characterized in that, this acidulant is selected from mineral acid or organic acid, and such as hydrochloric acid, orthophosphoric acid, carboxylic acid is as tartaric acid, citric acid, lactic acid or sulfonic acid.
29. as any one defined preparation of compositions method in the claim 1～28, it is characterized in that, carve in use, instant anhydrous composition and at least a Aquo-composition that contains at least a Reducing agent that mix, this anhydrous composition or Aquo-composition at least a contain at least a as defined cationic polyvinyl base lactams in any one in the claim 1～12.
30. as any one compositions in the claim 1～3, it is characterized in that said composition is an anhydrous composition, be used for human cutin fiber's decolouring or distortion.
31. the compositions as claim 30 is characterized in that, this anhydrous composition is the form of fine powder.
32. human cutin fiber's the decolouring or the method for permanently shaping, this method comprises, a kind of instant available compositions of coating on dry or moistening fiber, said composition contains at least a Reducing agent and at least a as any one defined cationic polyvinyl base lactams in claim 1～12 in the medium that is suitable for decolouring, allowing said composition keep worked 1～60 minute, rinsing fiber randomly, wash with shampoo, again rinsing and drying, under the situation of permanently shaping, after being coated with described compositions, choose wantonly after rinsing, be coated with a kind of oxidising composition, kept again 1～20 minute, optional then with shampoo washing or rinsing and drying again.
33. the device with 2 boxes that is used for human cutin fiber decolouring or permanently shaping is " external member " in other words, it is characterized in that, at least a powder or Aquo-composition are housed in first box, second box-packed Aquo-composition, in two boxes at least one comprises at least a Reducing agent, and in two boxes at least one contains at least a as any one defined cationic polyvinyl base lactams in the claim 1～12.
34. as the application as thickening agent and/or gelating agent in cosmetic that contains at least a Reducing agent and/or skin composition of any one defined cationic polyvinyl base lactams in the claim 1～12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0101105A FR2820035B1 (en) | 2001-01-26 | 2001-01-26 | REDUCING COMPOSITION FOR THE TREATMENT OF KERATINIC MATERIAL COMPRISING A CATIONIC POLY (VINYLLACTAM) |
| FR01/01105 | 2001-01-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1460016A CN1460016A (en) | 2003-12-03 |
| CN1254227C true CN1254227C (en) | 2006-05-03 |
Family
ID=8859298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02800867 Expired - Fee Related CN1254227C (en) | 2001-01-26 | 2002-01-22 | Reducing composition for treating keratinous materials comprising cationic poly (vinyllactam) |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1357891A1 (en) |
| CN (1) | CN1254227C (en) |
| FR (1) | FR2820035B1 (en) |
| WO (1) | WO2002058661A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1019434A3 (en) | 2010-07-23 | 2012-07-03 | Auriga Internat | STABILIZATION OF SULFORAPHANE. |
| WO2012027369A2 (en) * | 2010-08-23 | 2012-03-01 | Diversapack Of California, Llc | System and method for straightening or shaping hair |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4956430A (en) * | 1989-05-01 | 1990-09-11 | Gaf Chemicals Corporation | Process for preparing substantially pure high molecular weight vinyl lactam-quaternized acrylamide copolymers |
| US6207778B1 (en) * | 1999-05-07 | 2001-03-27 | Isp Investments Inc. | Conditioning/styling terpolymers |
-
2001
- 2001-01-26 FR FR0101105A patent/FR2820035B1/en not_active Expired - Fee Related
-
2002
- 2002-01-22 WO PCT/FR2002/000254 patent/WO2002058661A1/en not_active Application Discontinuation
- 2002-01-22 EP EP02700363A patent/EP1357891A1/en not_active Withdrawn
- 2002-01-22 CN CN 02800867 patent/CN1254227C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1460016A (en) | 2003-12-03 |
| FR2820035B1 (en) | 2003-05-02 |
| FR2820035A1 (en) | 2002-08-02 |
| WO2002058661A1 (en) | 2002-08-01 |
| EP1357891A1 (en) | 2003-11-05 |
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